# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_Purine_100K
_database_code_depnum_ccdc_archive 'CCDC 1528479'
_audit_update_record             
;
2017-01-19 deposited with the CCDC.
2017-03-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/6
_chemical_name_systematic        Purine
_chemical_name_common            9H-purine
_chemical_melting_point          487
_chemical_formula_moiety         C5H4N4
_chemical_formula_sum            'C5 H4 N4'
_chemical_formula_weight         120.12

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_H-M_alt        'P n a 21'
_space_group_name_Hall           'P 2c -2n'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z+1/2'
'-x+1/2, y+1/2, z+1/2'
'x+1/2, -y+1/2, z'

_cell_length_a                   15.534(5)
_cell_length_b                   9.382(3)
_cell_length_c                   3.6126(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     526.5(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    1126
_cell_measurement_theta_min      2.536
_cell_measurement_theta_max      29.033

_exptl_crystal_description       needle
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.514
_exptl_crystal_F_000             248
_exptl_transmission_factor_min   0.992
_exptl_transmission_factor_max   0.996
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_exptl_absorpt_coefficient_mu    0.105
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS V2012/1 (Bruker AXS Inc.)'
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5373
_diffrn_reflns_av_unetI/netI     0.0473
_diffrn_reflns_av_R_equivalents  0.0511
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -4
_diffrn_reflns_limit_l_max       4
_diffrn_reflns_theta_min         2.536
_diffrn_reflns_theta_max         29.033
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.841
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.841
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.803
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             1126
_reflns_number_gt                935
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.658
_reflns_Friedel_fraction_max     0.751
_reflns_Friedel_fraction_full    0.995

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker APEX2 (Bruker, 2011)'
_computing_cell_refinement       'SAINT V8.30C (Bruker AXS Inc., 2013)'
_computing_data_reduction        'SAINT V8.30C (Bruker AXS Inc., 2013)'
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXL-2014/6 (Sheldrick, 2014)'
_computing_molecular_graphics    'CrystalMaker (Palmer, 2010)'
_computing_publication_material  'Bruker SHELXTL (Bruker, 2011)'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0397P)²+0.1039P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 337 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   2.9(10)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1126
_refine_ls_number_parameters     82
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0595
_refine_ls_R_factor_gt           0.0406
_refine_ls_wR_factor_ref         0.0871
_refine_ls_wR_factor_gt          0.0810
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_restrained_S_all      1.036
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
N1 N 0.08628(14) 0.4058(2) 0.0155(7) 0.0174(6) Uani 1 1 d . . . . .
N2 N 0.23767(13) 0.3798(2) 0.1733(7) 0.0178(6) Uani 1 1 d . . . . .
N3 N 0.00031(14) 0.1955(2) 0.1400(7) 0.0198(6) Uani 1 1 d . . . . .
N4 N 0.23045(13) 0.1543(2) 0.3812(7) 0.0170(5) Uani 1 1 d . . . . .
H3 H 0.2473 0.0722 0.4741 0.020 Uiso 1 1 calc R U . . .
C1 C 0.01280(16) 0.3312(3) 0.0240(9) 0.0195(7) Uani 1 1 d . . . . .
H1 H -0.0369 0.3798 -0.0624 0.023 Uiso 1 1 calc R U . . .
C2 C 0.15363(15) 0.3316(3) 0.1460(9) 0.0140(6) Uani 1 1 d . . . . .
C3 C 0.27997(17) 0.2701(3) 0.3158(8) 0.0179(6) Uani 1 1 d . . . . .
H2 H 0.3399 0.2726 0.3674 0.021 Uiso 1 1 calc R U . . .
C4 C 0.06889(16) 0.1234(3) 0.2657(8) 0.0174(7) Uani 1 1 d . . . . .
H4 H 0.0632 0.0278 0.3484 0.021 Uiso 1 1 calc R U . . .
C5 C 0.14813(17) 0.1908(3) 0.2730(8) 0.0142(6) Uani 1 1 d . . . . .

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 0.0204(12) 0.0155(10) 0.0164(13) 0.0011(10) 0.0006(12) 0.0033(9)
N2 0.0176(11) 0.0148(10) 0.0210(15) 0.0015(10) 0.0013(11) -0.0007(9)
N3 0.0185(12) 0.0181(10) 0.0227(15) -0.0019(12) -0.0009(11) 0.0006(10)
N4 0.0192(12) 0.0124(9) 0.0193(13) 0.0045(10) -0.0008(11) 0.0032(9)
C1 0.0187(14) 0.0184(13) 0.0213(17) -0.0001(13) -0.0010(13) 0.0054(11)
C2 0.0176(14) 0.0135(12) 0.0109(13) -0.0022(12) 0.0025(13) 0.0000(10)
C3 0.0159(13) 0.0184(12) 0.0193(17) 0.0004(13) 0.0012(14) -0.0002(10)
C4 0.0211(15) 0.0137(11) 0.0174(17) 0.0004(12) 0.0026(13) -0.0003(10)
C5 0.0182(13) 0.0128(11) 0.0117(15) 0.0001(12) 0.0015(12) 0.0025(10)

_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

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 C1 1.340(3) . ?
N1 C2 1.342(3) . ?
N2 C3 1.325(3) . ?
N2 C2 1.386(3) . ?
N3 C4 1.342(3) . ?
N3 C1 1.355(3) . ?
N4 C3 1.352(3) . ?
N4 C5 1.381(3) . ?
N4 H3 0.8800 . ?
C1 H1 0.9500 . ?
C2 C5 1.402(4) . ?
C3 H2 0.9500 . ?
C4 C5 1.385(3) . ?
C4 H4 0.9500 . ?

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
C1 N1 C2 112.7(2) . . ?
C3 N2 C2 104.0(2) . . ?
C4 N3 C1 117.7(2) . . ?
C3 N4 C5 106.2(2) . . ?
C3 N4 H3 126.9 . . ?
C5 N4 H3 126.9 . . ?
N1 C1 N3 128.3(2) . . ?
N1 C1 H1 115.8 . . ?
N3 C1 H1 115.8 . . ?
N1 C2 N2 126.3(2) . . ?
N1 C2 C5 123.8(2) . . ?
N2 C2 C5 110.0(2) . . ?
N2 C3 N4 114.2(2) . . ?
N2 C3 H2 122.9 . . ?
N4 C3 H2 122.9 . . ?
N3 C4 C5 118.9(2) . . ?
N3 C4 H4 120.5 . . ?
C5 C4 H4 120.5 . . ?
N4 C5 C4 135.8(2) . . ?
N4 C5 C2 105.6(2) . . ?
C4 C5 C2 118.6(2) . . ?

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
C2 N1 C1 N3 -0.9(4) . . . . ?
C4 N3 C1 N1 0.3(5) . . . . ?
C1 N1 C2 N2 -179.8(3) . . . . ?
C1 N1 C2 C5 0.8(4) . . . . ?
C3 N2 C2 N1 -180.0(3) . . . . ?
C3 N2 C2 C5 -0.5(3) . . . . ?
C2 N2 C3 N4 0.4(3) . . . . ?
C5 N4 C3 N2 -0.1(3) . . . . ?
C1 N3 C4 C5 0.4(4) . . . . ?
C3 N4 C5 C4 180.0(3) . . . . ?
C3 N4 C5 C2 -0.2(3) . . . . ?
N3 C4 C5 N4 179.4(3) . . . . ?
N3 C4 C5 C2 -0.4(4) . . . . ?
N1 C2 C5 N4 179.9(3) . . . . ?
N2 C2 C5 N4 0.5(3) . . . . ?
N1 C2 C5 C4 -0.2(4) . . . . ?
N2 C2 C5 C4 -179.7(3) . . . . ?

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
C4 H4 N3 0.95 2.54 3.455(4) 160.8 2
C3 H2 N3 0.95 2.64 3.498(4) 150.1 4
C1 H1 N1 0.95 2.64 3.440(4) 142.4 2_564
N4 H3 N2 0.88 1.96 2.827(3) 169.4 3_545
C4 H4 N3 0.95 2.54 3.455(4) 160.8 2
C3 H2 N3 0.95 2.64 3.498(4) 150.1 4
C1 H1 N1 0.95 2.64 3.440(4) 142.4 2_564
N4 H3 N2 0.88 1.96 2.827(3) 169.4 3_545
N4 H3 N2 0.88 1.96 2.827(3) 169.4 3_545
C1 H1 N1 0.95 2.64 3.440(4) 142.4 2_564
C3 H2 N3 0.95 2.64 3.498(4) 150.1 4
C4 H4 N3 0.95 2.54 3.455(4) 160.8 2
N4 H3 N2 0.88 1.96 2.827(3) 169.4 3_545
C1 H1 N1 0.95 2.64 3.440(4) 142.4 2_564
C3 H2 N3 0.95 2.64 3.498(4) 150.1 4
C4 H4 N3 0.95 2.54 3.455(4) 160.8 2

_refine_diff_density_max         0.168
_refine_diff_density_min         -0.208
_refine_diff_density_rms         0.051

_shelxl_version_number           2014/6

_shelx_res_file                  
;
TITL mo_matrix_0ma in Pna2(1)
CELL 0.71073 15.5440 9.3824 3.6126 90.000 90.000 90.000
ZERR 4.00 0.0052 0.0032 0.0012 0.000 0.000 0.000
LATT -1
SYMM -x, -y, z+1/2
SYMM -x+1/2, y+1/2, z+1/2
SYMM x+1/2, -y+1/2, z
SFAC C  H  N
UNIT 20  16  16
L.S. 50
ACTA
BOND $H
FMAP 2
PLAN -1
HTAB C4 N3_$4
HTAB C3 N3_$3
HTAB C1 N1_$2
HTAB N4 N2_$1
HTAB C4 N3_$4
HTAB C3 N3_$3
HTAB C1 N1_$2
HTAB N4 N2_$1
HTAB
CONF
EQIV $1 -x+1/2, y-1/2, z+1/2
HTAB N4 N2_$1
EQIV $2 -x, -y+1, z-1/2
HTAB C1 N1_$2
EQIV $3 x+1/2, -y+1/2, z
HTAB C3 N3_$3
EQIV $4 -x, -y, z+1/2
HTAB C4 N3_$4
HTAB N4 N2_$1
HTAB C1 N1_$2
HTAB C3 N3_$3
HTAB C4 N3_$4
TEMP -178.000
WGHT    0.039700    0.103900
FVAR       0.31091
N1    3    0.086284    0.405796    0.015457    11.00000    0.02044    0.01549 =
         0.01636    0.00113    0.00062    0.00330
N2    3    0.237672    0.379755    0.173299    11.00000    0.01760    0.01482 =
         0.02102    0.00155    0.00128   -0.00073
N3    3    0.000305    0.195487    0.139978    11.00000    0.01855    0.01813 =
         0.02269   -0.00189   -0.00085    0.00055
N4    3    0.230455    0.154313    0.381209    11.00000    0.01918    0.01244 =
         0.01926    0.00450   -0.00079    0.00324
AFIX  43
H3    2    0.247302    0.072223    0.474102    11.00000   -1.20000
AFIX   0
C1    1    0.012801    0.331246    0.023983    11.00000    0.01866    0.01843 =
         0.02132   -0.00006   -0.00099    0.00537
AFIX  43
H1    2   -0.036929    0.379806   -0.062392    11.00000   -1.20000
AFIX   0
C2    1    0.153625    0.331642    0.145965    11.00000    0.01764    0.01351 =
         0.01087   -0.00222    0.00252    0.00000
C3    1    0.279973    0.270092    0.315771    11.00000    0.01588    0.01843 =
         0.01926    0.00038    0.00116   -0.00024
AFIX  43
H2    2    0.339879    0.272597    0.367444    11.00000   -1.20000
AFIX   0
C4    1    0.068891    0.123430    0.265730    11.00000    0.02113    0.01368 =
         0.01740    0.00044    0.00256   -0.00034
AFIX  43
H4    2    0.063177    0.027782    0.348431    11.00000   -1.20000
AFIX   0
C5    1    0.148131    0.190760    0.272989    11.00000    0.01817    0.01280 =
         0.01172    0.00011    0.00154    0.00249
HKLF 4 1 1 0 0 0 1 0 0 0 1

REM  mo_matrix_0ma in Pna2(1)
REM R1 =  0.0406 for     935 Fo > 4sig(Fo)  and  0.0595 for all    1126 data
REM     82 parameters refined using      1 restraints

END

WGHT      0.0384      0.1186

REM Instructions for potential hydrogen bonds
HTAB N4 N2_$1
HTAB C1 N1_$2
HTAB C3 N3_$3
HTAB C4 N3_$4

REM Highest difference peak  0.168,  deepest hole -0.208,  1-sigma level  0.051
Q1    1   0.2298  0.4785 -0.0989  11.00000  0.05    0.17
;
_shelx_res_checksum              30608

_exptl_crystal_recrystallization_method Sublimation
