#\#CIF_1.1

data_global

_audit_creation_date              'March 25, 2003'
_audit_creation_method            'from SHELXL-97 with Word-Perfect Macro PRPKAPPA'
_audit_update_record              
;   March 25, 2003  Assembled, pass-1
    April 01, 2003  Add text
    April 15, 2003  Minor changes
    April 21, 2003  VRF responses at the start of 
                    the _data_I section of this CIF
;
_publ_contact_author_name         'Dr Christopher Glidewell'
_publ_contact_author_address      
;
School of Chemistry
University of St Andrews
St Andrews
Fife KY16 9ST
Scotland
;
_publ_contact_author_phone        '01334-463839'
_publ_contact_author_fax          '01334-483808'
_publ_contact_author_email        med@iucr.org
_publ_requested_journal           'Acta Crystallographica C'
_publ_requested_category          FO
_publ_requested_coeditor_name     ?
_publ_contact_letter              
;
April 22, 2003

Please consider this CIF submission for publication in Acta 
Crystallographica Section C.  All authors have seen and 
approved this submission.

The CIF has passed the Chester CHECKCIF routines and gives a 
satisfactory PRINTCIF file.  VRF responses are at the start of
the _data_I section of the CIF.

Christopher Glidewell
;
_journal_date_recd_electronic     ?
_journal_date_to_coeditor         ?
_journal_date_from_coeditor       ?
_journal_date_accepted            ?
_journal_date_printers_first      ?
_journal_date_printers_final      ?
_journal_date_proofs_out          ?
_journal_date_proofs_in           ?
_journal_coeditor_name            ?
_journal_coeditor_code            ?
_journal_coeditor_notes           
; ?
;
_journal_techeditor_code          ?
_journal_techeditor_notes         
; ?
;
_journal_coden_ASTM               ?
_journal_name_full                ?
_journal_year                     ?
_journal_volume                   ?
_journal_issue                    ?
_journal_page_first               ?
_journal_page_last                ?
_journal_suppl_publ_number        ?
_journal_suppl_publ_pages         ?
_publ_section_title               
;
Example CIF - Not for publication
;

loop_
_publ_author_name
_publ_author_footnote
_publ_author_address
'Bowes, Katharine F.' ? 
;    
School of Chemistry
University of St Andrews
St Andrews
Fife KY16 9ST
Scotland
;
'Ferguson, George' 
;    
Permanent address: Department of Chemistry
University of Guelph
Guelph
Ontario
Canada N1G 2W1
; 
;    
School of Chemistry
University of St Andrews
St Andrews
Fife KY16 9ST
Scotland
;
'Lough, Alan J.' ? 
;    
Lash Miller Chemical Laboratories
University of Toronto
Toronto
Ontario
Canada M5S 3H6
;
'Glidewell, Christopher' . 
;    
School of Chemistry
University of St Andrews
St Andrews
Fife KY16 9ST
Scotland
;

_publ_section_abstract            
;
The title compound is a methanol-solvated salt 
[(C₁₆H₃₆N₄)H₂]²⁺.C₄H₄O₅²⁻.2CH₃OH,
in which the ionic components are linked into chains by two pairs of 
N---H...O hydrogen bonds [H...O = 1.78--2.21Å, N...O = 
2.702(14)--3.094(8)Å and N---H...O = 160--179°]. The methanol molecules 
are pendent from the chain, and are  linked to it by O---H...O hydrogen bonds 
[H...O = 1.86 and 1.89Å, O...O = 2.691(9) and 2.708(16)Å, and O---H...O =
168 and 165°].
;
_publ_section_comment             
;
In the salt-type adducts formed between 
meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane 
(tet-a, C₁₆H₃₆N₄) and phenols or carboxylic acids, the 
cations of type [{(C₁₆H₃₆N₄)H₂}²⁺] generally lie across 
centres of inversion (Gregson et al., 2000; Lough et al., 2000; 
Burchell et al., 2000; Bowes, Ferguson, Lough & Glidewell, 2003;
Bowes, Ferguson, Lough, Zakaria & Glidewell, 2003). An exception occurs 
in the salt formed with 5-hydroxyisophthalic acid, where the cation lies 
in a general position in space group P2₁2₁2₁ (Burchell et al., 2000).  
In all of these examples, the cation adopts the trans-III configuration 
(Barefield et al., 1986), and even in the 5-hydroxyisophthalate salt, 
the cation is very nearly centrosymmetric.

We have now investigated an example where a non-centrosymmetric cation 
environment is specifically imposed by the presence of an enantiopure chiral 
acid component, chosen in this case to be (S)-malic acid 
[(S)-2-hydroxy-butane-1,4-dioic acid, C₄H₆O₅]. The 1:1 salt form 
by tet-a and (S)-malic acid crystallises from methanol solution as a 
methanol solvate, (I), in the space group P1 so that none of the components
has any internal crystallographic symmetry. The presence of the chiral anion 
precludes any further symmetry

The fully-ordered cation adopts the usual trans-III configuration (Fig. 1)
with four methyl groups in equatorial sites and two in axial sites, and with 
paired intracation N---H...N hydrogen bonds generating an R₂²(10) 
motif (Bernstein et al., 1995). There is almost perfect staggering about 
all of the C---C and C---N bonds in the cation, and the values of the 
torsion angles are clearly indicative of the near-centrosymmetric 
conformation of the cation (Table 1); there are four axial N---H bonds 
available for intermolecular hydrogen-bond formation, two on each face 
of the disk-like cation. 

The anion  by contrast, exhibits orientational disorder, which was modelled 
using two sets of atomic sites with refined occupancies of 0.702(8) and 
0.298(8), respectively (Fig. 2). This disorder is such that the atom sites 
O22 and O32 are very close to one another, as are the sites O23 and 
O33; accordingly, the inter-ion hydrogen bonding is very similar for the 
two orientations, and hence only the major orientation will be considered 
further. The anion disorder observed in (I) is rather similar to that 
observed for the racemic tartrate anions C₄H₅O₆⁻ in the salt 
with the monocation derived from 1,2-bis(4-pyridyl)ethene (Farrell et al., 
2002a). Within the anion there is an O---H...O hydrogen bond, forming 
an S(6) motif, and this undoubtedly plays a role in the controlling the 
anion conformation. (Fig. 1 and Table 2).

The ionic components within the asymmetric unit are linked by paired 
N---H...O hydrogen bonds; N4 and N8 act as hydrogen-bond donors, 
via the axial H4 and H8A, respectively to carboxylate atoms O22 and 
O21, so generating an R₂²(10) motif (Fig. 1), of precisely the same 
type as observed in the tetrahydrate salt formed between the tet-a cation 
and the terephthalate anion (Lough et al., 2000).  The two independent 
methanol molecules are linked to the anion via O---H...O hydrogen 
bonds, both having carboxylate O as the acceptor.

Despite the large number of hydrogen bonds within the asymmetric 
unit, the supramolecular structure depends upon just one further pair 
of N---H...O hydrogen bonds. Atoms N1 and N11 in the cation at 
(x, y, z) act as hydrogen-bond donors, via H1B and H11, respectively 
to carboxylate O23 and O24 in the anion at (-1+x, -1+y, z), so 
generating by translation a chain of rings (Fig. 3) running parallel to 
the [110] direction. The methanol molecules are simply pendent 
from this chain and play no further role in the supramolecular 
aggregation. The only significant direction-specific interaction 
between adjacent chains is provided by a C---H...O hydrogen bond; C2 
in the cation at (x, y, z), which is adjacent to the cationic N1, acts as 
hydrogen bond donor, via H2B, to carboxylate O21 in the anion 
at (-1+x, y, z), and propagation of this interaction thus links the 
[110] chains generated by the hard (Desiraju & Steiner, 1999) 
hydrogen bonds into (001) sheets.

As with other amine salts of (S)-malic acid (Farrell et al., 2002b), the 
supramolecular structure of (I) closely mimics a centrosymmetric 
arrangement, even though exact centrosymmetry is ruled out by the 
chiral anion.
;
_publ_section_exptl_prep          
;
Equimolar quantities of tet-a (Hay et al., 1975) and (S)-malic acid 
(purchased from Aldrich) were separately dissolved in methanol. The 
solutions were mixed, and the mixture was set aside to crystallise, 
providing analytically pure (I). Analysis found: C 54.7, H 11.0, N 11.7%; 
C₂₂H₅₀N₄O₇ requires: C 54.7, H 10.4, N 11.6%. Crystals of (I) 
suitable for single-crystal X-ray diffraction were selected directly 
from the sample as prepared.
;
_publ_section_exptl_refinement    
;
Crystals of (I) are triclinic; space group P1 was chosen as the acid component 
used was enantiopure (S)-malic acid. The anion is disordered over a major 
and a minor orientation with refined occupancies 0.702(8) and 0.298(8). 
Standard DFIX restraints were used for the dimensions of the disordered anion.  
The atoms of the minor anion were refined with an overall Uiso value; all
other non-H atoms were refined anisotropically. H atoms were visible in
difference maps and were subsequently treated as riding atoms with distances 
C---H = 0.98 (CH₃), 0.99 (CH₂) or 1.00Å (CH), N---H = 0.92Å and 
O---H = 0.84Å. The cation was positioned so that is lies with its centre at 
(0.5, 0.5, 0.5) and the anion is then centred approximately at (1.0, 1.0, 0.5).
In the absence of any significant anomalous scattering, the Flack (1983) 
parameter was indeterminate (Flack & Bernardinelli, 2000). Hence, the Friedel 
equivalents were merged prior to the final refinements, and the absolute 
structure was set by reference to the known chirality of the enantiopure acid 
employed.
;
_publ_section_references          
;
Barefield, E. K., Bianchi, A., Billo, E. J., Connolly, P. J., Paoletti, P., 
Summers, J. S. & Van Derveer, D. G. (1986).  Inorg. Chem. 25, 4197-4202.

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). 
Angew. Chem. Int. Ed. Engl. 34, 1555-1573.

Bowes, K. F., Ferguson, G., Lough, A. J. & Glidewell, C., (2003).
Acta Cryst. C59, o147-o149.

Bowes, K. F., Ferguson, G., Lough, A. J., Zakaria, C. M. & Glidewell, C. 
(2003).  Acta Cryst. B59, 87-99.

Burchell, C. J., Ferguson, G., Lough, A. J. & Glidewell, C. (2000).  
Acta Cryst. B56, 1054-1062.

Desiraju, G. R. & Steiner, T. (1999).  The Weak Hydrogen Bond, pp. 86-89.  
Oxford University Press.

Farrell, D. M. M., Ferguson, G., Lough, A. J. & Glidewell, C. (2002a).  
Acta Cryst. B58, 272-288.

Farrell, D. M. M., Ferguson, G., Lough, A. J. & Glidewell, C. (2002b).  
Acta Cryst. B58, 530-544.

Ferguson, G. (1999).  PRPKAPPA.  University of Guelph, Canada.

Flack, H. D. (1983).  Acta Cryst. A39, 876-881.

Flack, H. D. & Bernardinelli, G. (2000).  J. Appl. Cryst. 33, 1143-1148.

Gregson, R. M., Glidewell, C., Ferguson, G. & Lough, A. J. (2000). 
 Acta Cryst. B56, 39-57.

Hay, R. W., Lawrance, G. A. & Curtis, N. F. (1975). 
J. Chem. Soc. Perkin Trans. 1, pp. 591-593.

Lough, A. J., Gregson, R. M.,  Ferguson, G. &  Glidewell, C. (2000).  
Acta Cryst. B56, 85-93.

Nonius (1997). KappaCCD Server Software. Windows 3.11 Version. Nonius BV,
Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M.
Sweet, pp. 307-326. New York: Academic Press.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, 
Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.
;
_publ_section_figure_captions     
;
Fig. 1. The independent components of (I), showing the atom-labelling 
scheme. Displacement ellipsoids are drawn at the 30% probability level 
and, for the sake of clarity, only the major component of the anion is 
shown.

Fig. 2. The major  (full lines) and minor (broken lines) components of the 
anion: for the sake of clarity, the H atoms have been omitted.

Fig. 3. Part of the crystal structure of (I), showing formation of a chain 
along [110]. For the sake of clarity, H atoms bonded to C atoms have been 
omitted, and only the major orientation of the anion is shown. Atoms 
marked with an asterisk (*) or a hash (#) are at the symmetry positions 
(-1+x, -1+y, z) and (1+x, 1+y, z) respectively.
;
_publ_section_table_legends       
;
Table 1.  Selected geometric parameters (Å, °) for compound (I)

Table 2.  Hydrogen bond parameters (Å, °) for compound (I)
;
_publ_section_acknowledgements    
;
X-ray data were collected at the University of Toronto using a Nonius 
KappaCCD diffractometer purchased with funds from from NSERC Canada.
;

data_I

_vrf_PLAT_111_I                   
;
PROBLEM: _A ADDSYM Detects (Pseudo) Centre of Symmetry ...        100 Perc Fit
RESPONSE:  The acid used was enantiopure (S)-malic acid and the 
ADDSYM result is an artefact of the anion disorder.  ADDSYM reaches 
its conclusion having excluded all the atoms of the disordered 
anion, i.e. of the very component which is chiral. See Comment text.  
;
_vrf_PLAT_113_I                   
;
PROBLEM: _A ADDSYM Suggests Possible Pseudo/New Spacegroup       P-1          
RESPONSE: .See above
;
_chemical_name_systematic         
;
meso-5,5,7,12,12,14-Hexamethyl-4,11-diaza-1,8-diazoniacyclotetradecane 
(S)-malate(2-) methanol disolvate
;
_chemical_name_common             ?
_chemical_melting_point           ?
_chemical_formula_iupac           'C16 H38 N4 2+, C4 H4 O5 2-, 2C H4 O'
_chemical_formula_moiety          'C16 H38 N4 2+, C4 H4 O5 2-, 2C H4 O'
_chemical_formula_sum             'C22 H50 N4 O7'
_chemical_formula_weight          482.660
_chemical_compound_source         'synthesised by authors, see text'
_chemical_absolute_configuration  rm

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.003  0.000  'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.000  0.000  'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.006  0.000  'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'O' 'O' 0.011  0.000  'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting            triclinic
_symmetry_space_group_name_H-M    'P 1'
_symmetry_space_group_name_Hall   'P 1'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'

_cell_length_a                    8.656 (9)
_cell_length_b                    9.328 (9)
_cell_length_c                    10.104(12)
_cell_angle_alpha                 113.379(5)
_cell_angle_beta                  108.908(4)
_cell_angle_gamma                 100.345(4)
_cell_volume                      662.310(12)
_cell_formula_units_Z             1
_cell_measurement_temperature     150(1)
_cell_measurement_reflns_used     8456
_cell_measurement_theta_min       3.540 
_cell_measurement_theta_max       27.610
_exptl_crystal_description        plate
_exptl_crystal_colour             colourless
_exptl_crystal_size_max           0.300 
_exptl_crystal_size_mid           0.280 
_exptl_crystal_size_min           0.100 
_exptl_crystal_density_meas       ?
_exptl_crystal_density_diffrn     1.210 
_exptl_crystal_density_method     'not measured'
_exptl_crystal_F_000              266
_exptl_absorpt_coefficient_mu     0.089 
_exptl_absorpt_correction_type    Multi-scan
_exptl_absorpt_process_details    '(DENZO-SMN; Otwinowski & Minor, 1997)'
_exptl_absorpt_correction_T_min   0.950 
_exptl_absorpt_correction_T_max   0.988 
_exptl_special_details            
;
?
;
_diffrn_ambient_temperature       150(1)
_diffrn_radiation_wavelength      0.711 
_diffrn_radiation_type            MoK\a
_diffrn_radiation_source          'fine-focus sealed X-ray tube'
_diffrn_radiation_monochromator   graphite
_diffrn_measurement_device_type   'Nonius KappaCCD'
_diffrn_measurement_method        'φ scans, and ω scans with κ offsets'
_diffrn_standards_decay_%         0
_diffrn_reflns_number             8456
_diffrn_reflns_av_R_equivalents   0.064 
_diffrn_reflns_av_sigmaI/netI     0.085 
_diffrn_reflns_limit_h_min        -11
_diffrn_reflns_limit_h_max        11
_diffrn_reflns_limit_k_min        -12
_diffrn_reflns_limit_k_max        12
_diffrn_reflns_limit_l_min        -12
_diffrn_reflns_limit_l_max        13
_diffrn_reflns_theta_min          3.540 
_diffrn_reflns_theta_max          27.610
_diffrn_reflns_theta_full         27.610
_diffrn_measured_fraction_theta_max 0.985 
_diffrn_measured_fraction_theta_full 0.985 
_reflns_number_total              3022
_reflns_number_gt                 1802
_reflns_threshold_expression      I>2σ(I)
_computing_data_collection        'KappaCCD Server Software (Nonius, 1997)'
_computing_cell_refinement        'DENZO-SMN (Otwinowski & Minor, 1997)'
_computing_data_reduction         'DENZO-SMN'
_computing_structure_solution     'SHELXS97 (Sheldrick, 1997)'
_computing_structure_refinement   'SHELXL97 (Sheldrick, 1997)'
_computing_molecular_graphics     'PLATON (Spek, 2003)'
_computing_publication_material   'SHELXL97 and PRPKAPPA (Ferguson, 1999)'
_refine_ls_structure_factor_coef  Fsqd
_refine_ls_matrix_type            full
_refine_ls_weighting_scheme       calc
_refine_ls_weighting_details      'w = 1/[σ²(Fo²)+(0.1019P)²+0.0709P] where P = (Fo²+2Fc²)/3'
_atom_sites_solution_primary      direct
_atom_sites_solution_secondary    difmap
_atom_sites_solution_hydrogens    geom
_refine_ls_hydrogen_treatment     constr
_refine_ls_extinction_method      SHELXL97
_refine_ls_extinction_coef        0.080 (2)
_refine_ls_extinction_expression  'Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^'
_refine_ls_number_reflns          3022
_refine_ls_number_parameters      333
_refine_ls_number_restraints      23
_refine_ls_R_factor_all           0.117 
_refine_ls_R_factor_gt            0.064 
_refine_ls_wR_factor_ref          0.201 
_refine_ls_wR_factor_gt           0.168 
_refine_ls_goodness_of_fit_ref    1.033 
_refine_ls_restrained_S_all       1.032 
_refine_ls_shift/su_max           0.001 
_refine_ls_shift/su_mean          0.000 
_refine_diff_density_max          0.360 
_refine_diff_density_min          -0.319

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
N1 N 0.349 (7) 0.589 (7) 0.615 (6) 0.035 (12) Uani 1 1 d . . .
C2 C 0.265 (9) 0.646 (9) 0.504 (8) 0.042 (17) Uani 1 1 d . . .
C3 C 0.203 (9) 0.512 (10) 0.328 (9) 0.045 (18) Uani 1 1 d . . .
N4 N 0.351 (7) 0.485 (7) 0.294 (6) 0.035 (13) Uani 1 1 d . . .
C5 C 0.304 (9) 0.358 (8) 0.126 (8) 0.043 (17) Uani 1 1 d . . .
C51 C 0.203 (11) 0.411 (11) 0.006 (8) 0.052 (2) Uani 1 1 d . . .
C52 C 0.184 (9) 0.188 (9) 0.088 (9) 0.051 (2) Uani 1 1 d . . .
C6 C 0.470 (9) 0.347 (8) 0.111 (7) 0.041 (17) Uani 1 1 d . . .
C7 C 0.585 (9) 0.287 (9) 0.211 (8) 0.039 (16) Uani 1 1 d . . .
C71 C 0.735 (11) 0.266 (11) 0.169 (10) 0.054 (2) Uani 1 1 d . . .
N8 N 0.649 (8) 0.411 (7) 0.386 (6) 0.041 (14) Uani 1 1 d . . .
C9 C 0.736 (9) 0.355 (9) 0.502 (8) 0.043 (18) Uani 1 1 d . . .
C10 C 0.800 (8) 0.485 (9) 0.670 (8) 0.040 (16) Uani 1 1 d . . .
N11 N 0.654 (7) 0.516 (8) 0.707 (6) 0.040 (14) Uani 1 1 d . . .
C12 C 0.704 (8) 0.640 (9) 0.875 (8) 0.041 (17) Uani 1 1 d . . .
C121 C 0.794 (10) 0.585 (12) 0.994 (9) 0.057 (2) Uani 1 1 d . . .
C122 C 0.820 (10) 0.810 (10) 0.919 (10) 0.057 (2) Uani 1 1 d . . .
C13 C 0.534 (9) 0.652 (9) 0.891 (8) 0.043 (18) Uani 1 1 d . . .
C14 C 0.420 (9) 0.712 (9) 0.790 (8) 0.040 (16) Uani 1 1 d . . .
C141 C 0.268 (10) 0.736 (11) 0.832 (10) 0.055 (2) Uani 1 1 d . . .
O21 O 0.876 (18) 0.698 (15) 0.453 (14) 0.055 (3) Uani 0.702 (8) 1 d PD A -1
O22 O 0.649 (12) 0.767 (2) 0.352 (2) 0.060 (3) Uani 0.702 (8) 1 d PD A -1
O23 O 1.123 (15) 1.285 (13) 0.531 (17) 0.053 (2) Uani 0.702 (8) 1 d PD A -1
O24 O 1.351 (8) 1.232 (8) 0.651 (9) 0.042 (17) Uani 0.702 (8) 1 d PD A -1
O25 O 0.847 (7) 0.992 (7) 0.325 (7) 0.054 (16) Uani 0.702 (8) 1 d P A -1
C21 C 0.808 (11) 0.790 (11) 0.411 (12) 0.042 (3) Uani 0.702 (8) 1 d PD A -1
C22 C 0.935 (13) 0.930 (15) 0.416 (15) 0.067 (17) Uani 0.702 (8) 1 d PD A -1
C23 C 1.066 (14) 1.056 (15) 0.580 (15) 0.067 (17) Uani 0.702 (8) 1 d PD A -1
C24 C 1.190 (8) 1.204 (11) 0.592 (12) 0.045 (3) Uani 0.702 (8) 1 d PD A -1
O41 O 0.471 (9) 0.944 (8) 0.253 (8) 0.076 (19) Uani 1 1 d . B -1
C42 C 0.330 (13) 0.900 (12) 0.278 (10) 0.069 (2) Uani 1 1 d . B -1
O51 O 1.529 (9) 1.057 (8) 0.749 (8) 0.076 (18) Uani 1 1 d . . .
C53 C 1.670 (12) 1.091 (10) 0.719 (10) 0.063 (2) Uani 1 1 d . . .
C31 C 0.829 (3) 0.820 (3) 0.461 (3) 0.074 (3) Uiso 0.298 (8) 1 d PD A -2
C32 C 0.956 (2) 0.995 (3) 0.538 (2) 0.074 (3) Uiso 0.298 (8) 1 d PD A -2
C33 C 1.062 (3) 1.010 (2) 0.450 (2) 0.074 (3) Uiso 0.298 (8) 1 d PD A -2
C34 C 1.179 (2) 1.186 (2) 0.519 (2) 0.074 (3) Uiso 0.298 (8) 1 d PD A -2
O31 O 0.891 (6) 0.719 (5) 0.490 (5) 0.074 (3) Uiso 0.298 (8) 1 d PD A -2
O32 O 0.671 (4) 0.782 (6) 0.372 (6) 0.074 (3) Uiso 0.298 (8) 1 d PD A -2
O33 O 1.127 (5) 1.305 (4) 0.531 (4) 0.074 (3) Uiso 0.298 (8) 1 d PD A -2
O34 O 1.337 (2) 1.203 (2) 0.561 (2) 0.074 (3) Uiso 0.298 (8) 1 d PD A -2
O35 O 1.100 (2) 1.028 (2) 0.679 (2) 0.074 (3) Uiso 0.298 (8) 1 d PD A -2
H1A H 0.439  0.562  0.596  0.042  Uiso 1 1 calc R . .
H1B H 0.269  0.493  0.593  0.042  Uiso 1 1 calc R . .
H2A H 0.348  0.751  0.529  0.050  Uiso 1 1 calc R . .
H2B H 0.163  0.669  0.520  0.050  Uiso 1 1 calc R . .
H3A H 0.125  0.406  0.306  0.054  Uiso 1 1 calc R . .
H3B H 0.136  0.549  0.256  0.054  Uiso 1 1 calc R . .
H4 H 0.423  0.585  0.317  0.042  Uiso 1 1 calc R . .
H51A H 0.086  0.400  0.002  0.078  Uiso 1 1 calc R . .
H51B H 0.192  0.339  -0.101 0.078  Uiso 1 1 calc R . .
H51C H 0.267  0.527  0.042  0.078  Uiso 1 1 calc R . .
H52A H 0.232  0.168  0.179  0.076  Uiso 1 1 calc R . .
H52B H 0.179  0.098  -0.008 0.076  Uiso 1 1 calc R . .
H52C H 0.067  0.190  0.070  0.076  Uiso 1 1 calc R . .
H6A H 0.542  0.459  0.139  0.049  Uiso 1 1 calc R . .
H6B H 0.438  0.271  -0.003 0.049  Uiso 1 1 calc R . .
H7 H 0.512  0.176  0.189  0.047  Uiso 1 1 calc R . .
H71A H 0.804  0.373  0.186  0.082  Uiso 1 1 calc R . .
H71B H 0.688  0.181  0.056  0.082  Uiso 1 1 calc R . .
H71C H 0.808  0.230  0.236  0.082  Uiso 1 1 calc R . .
H8A H 0.728  0.509  0.409  0.049  Uiso 1 1 calc R . .
H8B H 0.556  0.435  0.402  0.049  Uiso 1 1 calc R . .
H9A H 0.652  0.252  0.481  0.052  Uiso 1 1 calc R . .
H9B H 0.836  0.327  0.484  0.052  Uiso 1 1 calc R . .
H10A H 0.869  0.450  0.743  0.048  Uiso 1 1 calc R . .
H10B H 0.878  0.590  0.689  0.048  Uiso 1 1 calc R . .
H11 H 0.579  0.417  0.683  0.047  Uiso 1 1 calc R . .
H12A H 0.902  0.574  0.988  0.086  Uiso 1 1 calc R . .
H12B H 0.716  0.477  0.967  0.086  Uiso 1 1 calc R . .
H12C H 0.821  0.668  1.103  0.086  Uiso 1 1 calc R . .
H12D H 0.933  0.805  0.921  0.086  Uiso 1 1 calc R . .
H12E H 0.837  0.893  1.025  0.086  Uiso 1 1 calc R . .
H12F H 0.763  0.841  0.839  0.086  Uiso 1 1 calc R . .
H13A H 0.462  0.540  0.863  0.051  Uiso 1 1 calc R . .
H13B H 0.566  0.728  1.005  0.051  Uiso 1 1 calc R . .
H14 H 0.493  0.822  0.811  0.048  Uiso 1 1 calc R . .
H14A H 0.204  0.784  0.773  0.082  Uiso 1 1 calc R . .
H14B H 0.313  0.811  0.947  0.082  Uiso 1 1 calc R . .
H14C H 0.189  0.627  0.802  0.082  Uiso 1 1 calc R . .
H25 H 0.902  1.095  0.367  0.081  Uiso 0.702 (8) 1 calc PR A -1
H22 H 1.003  0.876  0.361  0.080  Uiso 0.702 (8) 1 calc PR A -1
H23A H 1.136  1.001  0.627  0.080  Uiso 0.702 (8) 1 calc PR A -1
H23B H 1.004  1.099  0.645  0.080  Uiso 0.702 (8) 1 calc PR A -1
H41 H 0.541  0.900  0.283  0.114  Uiso 1 1 calc R B -1
H42D H 0.366  0.944  0.394  0.103  Uiso 1 1 calc R B -1
H42E H 0.277  0.778  0.223  0.103  Uiso 1 1 calc R B -1
H42F H 0.244  0.946  0.237  0.103  Uiso 1 1 calc R B -1
H51 H 1.467  1.111  0.727  0.114  Uiso 1 1 calc R . .
H53A H 1.664  1.169  0.677  0.095  Uiso 1 1 calc R . .
H53B H 1.670  0.987  0.639  0.095  Uiso 1 1 calc R . .
H53C H 1.778  1.141  0.818  0.095  Uiso 1 1 calc R . .
H32 H 0.899  1.081  0.560  0.089  Uiso 0.298 (8) 1 calc PR A -2
H33A H 1.134  0.939  0.453  0.089  Uiso 0.298 (8) 1 calc PR A -2
H33B H 0.982  0.968  0.336  0.089  Uiso 0.298 (8) 1 calc PR A -2
H35 H 1.081  0.947  0.696  0.111  Uiso 0.298 (8) 1 calc PRD A -2


loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
N1 0.026 (3) 0.034 (3) 0.038 (3) 0.014 (2) 0.012 (2) 0.012 (2)
C2 0.033 (4) 0.044 (4) 0.052 (4) 0.026 (4) 0.018 (3) 0.016 (3)
C3 0.035 (4) 0.049 (4) 0.045 (4) 0.022 (4) 0.012 (3) 0.014 (3)
N4 0.027 (3) 0.031 (3) 0.043 (3) 0.017 (3) 0.014 (3) 0.006 (2)
C5 0.046 (4) 0.036 (4) 0.047 (4) 0.019 (3) 0.023 (4) 0.016 (3)
C51 0.067 (5) 0.057 (5) 0.036 (4) 0.023 (4) 0.024 (4) 0.027 (4)
C52 0.042 (4) 0.029 (3) 0.063 (5) 0.014 (3) 0.019 (4) -0.001(3)
C6 0.037 (4) 0.034 (4) 0.037 (4) 0.011 (3) 0.012 (3) 0.006 (3)
C7 0.038 (4) 0.035 (3) 0.042 (4) 0.018 (3) 0.017 (3) 0.008 (3)
C71 0.060 (5) 0.065 (5) 0.058 (5) 0.037 (5) 0.032 (5) 0.038 (5)
N8 0.041 (3) 0.041 (3) 0.045 (3) 0.028 (3) 0.017 (3) 0.013 (3)
C9 0.044 (4) 0.050 (4) 0.046 (4) 0.031 (4) 0.018 (3) 0.024 (3)
C10 0.026 (4) 0.049 (4) 0.047 (4) 0.029 (4) 0.013 (3) 0.013 (3)
N11 0.033 (3) 0.041 (3) 0.041 (3) 0.022 (3) 0.012 (3) 0.010 (2)
C12 0.027 (3) 0.043 (4) 0.038 (4) 0.019 (3) 0.002 (3) 0.006 (3)
C121 0.042 (4) 0.074 (5) 0.056 (5) 0.039 (4) 0.009 (4) 0.027 (4)
C122 0.044 (5) 0.055 (5) 0.062 (5) 0.025 (4) 0.016 (4) 0.014 (4)
C13 0.048 (5) 0.050 (4) 0.042 (4) 0.032 (4) 0.020 (4) 0.021 (3)
C14 0.039 (4) 0.042 (4) 0.044 (4) 0.022 (3) 0.018 (3) 0.020 (3)
C141 0.048 (5) 0.073 (6) 0.047 (5) 0.029 (4) 0.022 (4) 0.026 (4)
O21 0.039 (4) 0.047 (5) 0.075 (7) 0.039 (5) 0.017 (5) 0.003 (4)
O22 0.040 (5) 0.039 (5) 0.087 (8) 0.029 (6) 0.018 (5) 0.007 (4)
O23 0.030 (4) 0.035 (4) 0.082 (5) 0.034 (4) 0.010 (3) 0.000 (3)
O24 0.039 (4) 0.029 (3) 0.050 (4) 0.015 (3) 0.019 (3) 0.006 (3)
O25 0.044 (3) 0.045 (3) 0.058 (3) 0.029 (3) 0.005 (2) 0.006 (2)
C21 0.050 (7) 0.025 (5) 0.046 (6) 0.018 (5) 0.025 (5) -0.002(4)
C22 0.047 (3) 0.065 (3) 0.064 (3) 0.045 (3) -0.003(2) -0.013(2)
C23 0.047 (3) 0.065 (3) 0.064 (3) 0.045 (3) -0.003(2) -0.013(2)
C24 0.027 (5) 0.041 (5) 0.045 (6) 0.016 (5) 0.002 (4) 0.002 (4)
O41 0.071 (5) 0.068 (4) 0.075 (4) 0.041 (4) 0.015 (3) 0.017 (3)
C42 0.068 (6) 0.061 (5) 0.059 (5) 0.024 (5) 0.017 (5) 0.017 (5)
O51 0.086 (5) 0.071 (4) 0.083 (4) 0.048 (4) 0.039 (4) 0.025 (4)
C53 0.083 (7) 0.053 (5) 0.069 (6) 0.043 (5) 0.034 (5) 0.027 (5)


loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
N1 C2 1.466 (7) . no
N1 C14 1.502 (8) . no
N1 H1A 0.920  . no
N1 H1B 0.920  . no
C2 C3 1.550 (9) . no
C2 H2A 0.990  . no
C2 H2B 0.990  . no
C3 N4 1.465 (8) . no
C3 H3A 0.990  . no
C3 H3B 0.990  . no
N4 C5 1.499 (8) . no
N4 H4 0.920  . no
C5 C6 1.509 (9) . no
C5 C52 1.549 (9) . no
C5 C51 1.554 (9) . no
C51 H51A 0.980  . no
C51 H51B 0.980  . no
C51 H51C 0.980  . no
C52 H52A 0.980  . no
C52 H52B 0.980  . no
C52 H52C 0.980  . no
C6 C7 1.525 (9) . no
C6 H6A 0.990  . no
C6 H6B 0.990  . no
C7 N8 1.509 (9) . no
C7 C71 1.515 (10) . no
C7 H7 1.000  . no
C71 H71A 0.980  . no
C71 H71B 0.980  . no
C71 H71C 0.980  . no
N8 C9 1.507 (7) . no
N8 H8A 0.920  . no
N8 H8B 0.920  . no
C9 C10 1.480 (9) . no
C9 H9A 0.990  . no
C9 H9B 0.990  . no
C10 N11 1.474 (8) . no
C10 H10A 0.990  . no
C10 H10B 0.990  . no
N11 C12 1.484 (8) . no
N11 H11 0.920  . no
C12 C122 1.515 (10) . no
C12 C121 1.531 (8) . no
C12 C13 1.549 (9) . no
C121 H12A 0.980  . no
C121 H12B 0.980  . no
C121 H12C 0.980  . no
C122 H12D 0.980  . no
C122 H12E 0.980  . no
C122 H12F 0.980  . no
C13 C14 1.529 (9) . no
C13 H13A 0.990  . no
C13 H13B 0.990  . no
C14 C141 1.533 (10) . no
C14 H14 1.000  . no
C141 H14A 0.980  . no
C141 H14B 0.980  . no
C141 H14C 0.980  . no
O21 C21 1.250 (5) . no
O22 C21 1.250 (5) . no
O23 C24 1.254 (5) . no
O24 C24 1.250 (5) . no
O25 C22 1.377 (11) . no
O25 H25 0.840  . no
C21 C22 1.518 (7) . no
C22 C23 1.474 (7) . no
C22 H22 1.000  . no
C23 C24 1.524 (8) . no
C23 H23A 0.990  . no
C23 H23B 0.990  . no
O41 C42 1.352 (10) . no
O41 H41 0.840  . no
C42 H42D 0.980  . no
C42 H42E 0.980  . no
C42 H42F 0.980  . no
O51 C53 1.367 (9) . no
O51 H51 0.840  . no
C53 H53A 0.980  . no
C53 H53B 0.980  . no
C53 H53C 0.980  . no
C31 O31 1.250 (5) . no
C31 O32 1.251 (5) . no
C31 C32 1.504 (5) . no
C32 O35 1.432 (10) . no
C32 C33 1.498 (5) . no
C32 H32 1.000  . no
C33 C34 1.498 (5) . no
C33 H33A 0.990  . no
C33 H33B 0.990  . no
C34 O33 1.249 (5) . no
C34 O34 1.249 (5) . no
O35 H35 0.840  . no


loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C2 N1 C14 115.200(5) . . no
C2 N1 H1A 108.500 . . no
C14 N1 H1A 108.500 . . no
C2 N1 H1B 108.500 . . no
C14 N1 H1B 108.500 . . no
H1A N1 H1B 107.500 . . no
N1 C2 C3 111.200(5) . . no
N1 C2 H2A 109.400 . . no
C3 C2 H2A 109.400 . . no
N1 C2 H2B 109.400 . . no
C3 C2 H2B 109.400 . . no
H2A C2 H2B 108.000 . . no
N4 C3 C2 111.600(5) . . no
N4 C3 H3A 109.300 . . no
C2 C3 H3A 109.300 . . no
N4 C3 H3B 109.300 . . no
C2 C3 H3B 109.300 . . no
H3A C3 H3B 108.000 . . no
C3 N4 C5 115.400(5) . . no
C3 N4 H4 108.400 . . no
C5 N4 H4 108.400 . . no
N4 C5 C6 108.600(5) . . no
N4 C5 C52 108.700(5) . . no
C6 C5 C52 111.600(5) . . no
N4 C5 C51 109.900(5) . . no
C6 C5 C51 109.200(5) . . no
C52 C5 C51 108.800(6) . . no
C5 C51 H51A 109.500 . . no
C5 C51 H51B 109.500 . . no
H51A C51 H51B 109.500 . . no
C5 C51 H51C 109.500 . . no
H51A C51 H51C 109.500 . . no
H51B C51 H51C 109.500 . . no
C5 C52 H52A 109.500 . . no
C5 C52 H52B 109.500 . . no
H52A C52 H52B 109.500 . . no
C5 C52 H52C 109.500 . . no
H52A C52 H52C 109.500 . . no
H52B C52 H52C 109.500 . . no
C5 C6 C7 118.000(6) . . no
C5 C6 H6A 107.800 . . no
C7 C6 H6A 107.800 . . no
C5 C6 H6B 107.800 . . no
C7 C6 H6B 107.800 . . no
H6A C6 H6B 107.100 . . no
N8 C7 C71 111.500(6) . . no
N8 C7 C6 108.000(5) . . no
C71 C7 C6 110.900(5) . . no
N8 C7 H7 108.800 . . no
C71 C7 H7 108.800 . . no
C6 C7 H7 108.800 . . no
C7 C71 H71A 109.500 . . no
C7 C71 H71B 109.500 . . no
H71A C71 H71B 109.500 . . no
C7 C71 H71C 109.500 . . no
H71A C71 H71C 109.500 . . no
H71B C71 H71C 109.500 . . no
C9 N8 C7 114.800(5) . . no
C9 N8 H8A 108.600 . . no
C7 N8 H8A 108.600 . . no
C9 N8 H8B 108.600 . . no
C7 N8 H8B 108.600 . . no
H8A N8 H8B 107.500 . . no
C10 C9 N8 111.500(5) . . no
C10 C9 H9A 109.300 . . no
N8 C9 H9A 109.300 . . no
C10 C9 H9B 109.300 . . no
N8 C9 H9B 109.300 . . no
H9A C9 H9B 108.000 . . no
N11 C10 C9 111.100(5) . . no
N11 C10 H10A 109.400 . . no
C9 C10 H10A 109.400 . . no
N11 C10 H10B 109.400 . . no
C9 C10 H10B 109.400 . . no
H10A C10 H10B 108.000 . . no
C10 N11 C12 115.500(5) . . no
C10 N11 H11 108.400 . . no
C12 N11 H11 108.400 . . no
N11 C12 C122 110.700(6) . . no
N11 C12 C121 112.200(6) . . no
C122 C12 C121 110.200(6) . . no
N11 C12 C13 107.800(5) . . no
C122 C12 C13 109.800(6) . . no
C121 C12 C13 106.000(5) . . no
C12 C121 H12A 109.500 . . no
C12 C121 H12B 109.500 . . no
H12A C121 H12B 109.500 . . no
C12 C121 H12C 109.500 . . no
H12A C121 H12C 109.500 . . no
H12B C121 H12C 109.500 . . no
C12 C122 H12D 109.500 . . no
C12 C122 H12E 109.500 . . no
H12D C122 H12E 109.500 . . no
C12 C122 H12F 109.500 . . no
H12D C122 H12F 109.500 . . no
H12E C122 H12F 109.500 . . no
C14 C13 C12 117.500(5) . . no
C14 C13 H13A 107.900 . . no
C12 C13 H13A 107.900 . . no
C14 C13 H13B 107.900 . . no
C12 C13 H13B 107.900 . . no
H13A C13 H13B 107.200 . . no
N1 C14 C13 109.600(5) . . no
N1 C14 C141 109.500(6) . . no
C13 C14 C141 111.500(5) . . no
N1 C14 H14 108.700 . . no
C13 C14 H14 108.700 . . no
C141 C14 H14 108.700 . . no
C14 C141 H14A 109.500 . . no
C14 C141 H14B 109.500 . . no
H14A C141 H14B 109.500 . . no
C14 C141 H14C 109.500 . . no
H14A C141 H14C 109.500 . . no
H14B C141 H14C 109.500 . . no
O21 C21 O22 126.800(11) . . no
O21 C21 C22 114.100(10) . . no
O22 C21 C22 118.700(10) . . no
O25 C22 C23 115.100(7) . . no
O25 C22 C21 110.800(8) . . no
C23 C22 C21 113.200(7) . . no
O25 C22 H22 105.600 . . no
C23 C22 H22 105.600 . . no
C21 C22 H22 105.600 . . no
C22 C23 C24 115.100(7) . . no
C22 C23 H23A 108.500 . . no
C24 C23 H23A 108.500 . . no
C22 C23 H23B 108.500 . . no
C24 C23 H23B 108.500 . . no
H23A C23 H23B 107.500 . . no
O24 C24 O23 123.200(9) . . no
O24 C24 C23 119.400(8) . . no
O23 C24 C23 117.200(8) . . no
C53 O51 H51 109.500 . . no
O51 C53 H53A 109.500 . . no
O51 C53 H53B 109.500 . . no
H53A C53 H53B 109.500 . . no
O51 C53 H53C 109.500 . . no
H53A C53 H53C 109.500 . . no
H53B C53 H53C 109.500 . . no
O31 C31 O32 123(4) . . no
O31 C31 C32 116(3) . . no
O32 C31 C32 121(3) . . no
O35 C32 C33 95.100(15) . . no
O35 C32 C31 110(2) . . no
C33 C32 C31 112.700(5) . . no
O35 C32 H32 112.800 . . no
C33 C32 H32 112.800 . . no
C31 C32 H32 112.800 . . no
C34 C33 C32 113.100(5) . . no
C34 C33 H33A 109.000 . . no
C32 C33 H33A 109.000 . . no
C34 C33 H33B 109.000 . . no
C32 C33 H33B 109.000 . . no
H33A C33 H33B 107.800 . . no
O33 C34 O34 122(3) . . no
O33 C34 C33 124(3) . . no
O34 C34 C33 113.200(19) . . no
C32 O35 H35 109.500 . . no


loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N1 C2 C3 N4 -65.000(9) . . . . y
C2 C3 N4 C5 179.900(7) . . . . y
C3 N4 C5 C6 179.200(7) . . . . y
N4 C5 C6 C7 63.600(9) . . . . y
C5 C6 C7 N8 -63.600(9) . . . . y
C6 C7 N8 C9 168.900(7) . . . . y
C7 N8 C9 C10 178.400(7) . . . . y
O22 C21 C22 C23 119.700(14) . . . . y
C21 C22 C23 C24 -176.700(10) . . . . y
N8 C9 C10 N11 65.800(9) . . . . y
C9 C10 N11 C12 177.400(7) . . . . y
C10 N11 C12 C13 -178.500(7) . . . . y
N11 C12 C13 C14 -62.200(9) . . . . y
C12 C13 C14 N1 64.900(9) . . . . y
C13 C14 N1 C2 -169.100(7) . . . . y
C14 N1 C2 C3 177.700(7) . . . . y
O25 C22 C23 C24 -47.800(15) . . . . y
C22 C23 C24 O23 55.500(16) . . . . y


loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
N1 H1A N11 0.920  2.050  2.799 (8) 138 . y
N8 H8B N4 0.920  2.000  2.758 (8) 138 . y
O25 H25 O23 0.840  1.980  2.721 (12) 146 . y
O35 H35 O31 0.840  2.140  2.600 (5) 114 . n
N4 H4 O22 0.920  2.170  3.046 (15) 160 . y
N4 H4 O32 0.920  2.290  3.170 (4) 159 . n
N8 H8A O21 0.920  1.780  2.702 (14) 179 . y
N8 H8A O31 0.920  1.870  2.780 (5) 171 . n
O41 H41 O22 0.840  1.890  2.708 (16) 165 . y
O51 H51 O24 0.840  1.860  2.691 (9) 168 . y
O51 H51 O34 0.840  2.250  3.005 (18) 150 . n
N1 H1B O23 0.920  1.850  2.760 (11) 172 1_445 y
N1 H1B O33 0.920  1.680  2.600 (4) 173 1_445 n
N11 H11 O24 0.920  2.210  3.094 (8) 161 1_445 y
N11 H11 O34 0.920  2.180  3.060 (2) 158 1_445 n
C2 H2B O21 0.990  2.450  3.390 (2) 159 1_455 n
