# Electronic Supplementary Material (ESI) for Chemical Communications.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# 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_Mercaptopurine_Hemihydrate
_database_code_depnum_ccdc_archive 'CCDC 1447142'
_audit_update_record             
;
2016-01-13 deposited with the CCDC.
2016-03-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        'Mercaptopurine Hemihydrate'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C5 H4 N4 S), (H2 O)'
_chemical_formula_sum            'C10 H10 N8 O S2'
_chemical_formula_weight         322.38

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P2(1)/n

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

_cell_length_a                   9.3608(13)
_cell_length_b                   11.0691(2)
_cell_length_c                   13.0914(9)
_cell_angle_alpha                90.00
_cell_angle_beta                 110.300(10)
_cell_angle_gamma                90.00
_cell_volume                     1272.2(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    85(2)
_cell_measurement_reflns_used    17168
_cell_measurement_theta_min      5.40
_cell_measurement_theta_max      68.30

_exptl_crystal_description       needle
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.683
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             664
_exptl_absorpt_coefficient_mu    3.941
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.783
_exptl_absorpt_correction_T_max  0.858
_exptl_absorpt_process_details   
;
    Higashi, T. (1995). Program for Absorption Correction.
    Rigaku Corporation, Tokyo, Japan.
;

_exptl_special_details           
; 
 3857 images x 1 sec / 8 sec @ 42.00 mm; 1.0 deg omega sc ans; 40kV/30mA 
;

_diffrn_ambient_temperature      85(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'micro-focus rotating anode'
_diffrn_radiation_monochromator  confocal
_diffrn_measurement_device_type  'Rigaku Saturn944+ CCD'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean 29.257
_diffrn_reflns_number            33466
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_sigmaI/netI    0.0221
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         5.08
_diffrn_reflns_theta_max         68.21
_reflns_number_total             2311
_reflns_number_gt                2039
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r12'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r12'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0766P)²+0.4981P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2311
_refine_ls_number_parameters     208
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0420
_refine_ls_R_factor_gt           0.0391
_refine_ls_wR_factor_ref         0.1154
_refine_ls_wR_factor_gt          0.1132
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_restrained_S_all      1.093
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O 0.21699(17) 0.15605(15) 0.48290(12) 0.0236(4) Uani 1 1 d . . .
H1A H 0.266(3) 0.102(3) 0.448(2) 0.035 Uiso 1 1 d . . .
H1B H 0.195(3) 0.101(3) 0.533(2) 0.035 Uiso 1 1 d . . .
S1 S 0.13544(5) -0.05360(4) 0.64869(3) 0.01363(19) Uani 1 1 d . . .
N1 N 0.34594(18) 0.09612(16) 0.77922(12) 0.0135(4) Uani 1 1 d . . .
H1 H 0.272(3) 0.163(2) 0.7449(18) 0.016 Uiso 1 1 d . . .
N2 N 0.58731(18) 0.05117(15) 0.91046(12) 0.0126(4) Uani 1 1 d . . .
N3 N 0.61993(17) -0.16656(15) 0.93621(12) 0.0126(4) Uani 1 1 d . . .
H3 H 0.722(3) -0.170(2) 0.9886(17) 0.015 Uiso 1 1 d . . .
N4 N 0.39550(18) -0.23080(15) 0.81991(12) 0.0143(4) Uani 1 1 d . . .
C1 C 0.2981(2) -0.02246(19) 0.75009(15) 0.0130(4) Uani 1 1 d . . .
C2 C 0.4828(2) 0.12785(19) 0.85314(14) 0.0142(4) Uani 1 1 d . . .
H2A H 0.5044 0.2098 0.8641 0.017 Uiso 1 1 calc R . .
C3 C 0.5415(2) -0.06543(19) 0.88890(14) 0.0126(4) Uani 1 1 d . . .
C4 C 0.5274(2) -0.26257(19) 0.89285(15) 0.0145(4) Uani 1 1 d . . .
H4 H 0.5545 -0.3423 0.9127 0.017 Uiso 1 1 calc R . .
C5 C 0.4034(2) -0.10704(18) 0.81583(14) 0.0124(4) Uani 1 1 d . . .
S2 S 0.37300(5) -0.03714(5) 0.35295(3) 0.01455(19) Uani 1 1 d . . .
N5 N 0.16876(18) -0.18094(16) 0.21072(13) 0.0146(4) Uani 1 1 d . . .
H5 H 0.245(3) -0.246(2) 0.2404(18) 0.018 Uiso 1 1 d . . .
N6 N -0.07594(17) -0.13451(16) 0.08511(12) 0.0140(4) Uani 1 1 d . . .
N7 N -0.11843(18) 0.08237(16) 0.07645(13) 0.0134(4) Uani 1 1 d . . .
H7 H -0.206(3) 0.085(2) 0.026(2) 0.016 Uiso 1 1 d . . .
N8 N 0.10296(18) 0.14506(16) 0.19726(13) 0.0148(4) Uani 1 1 d . . .
C6 C 0.2114(2) -0.06413(19) 0.24862(15) 0.0127(4) Uani 1 1 d . . .
C7 C 0.0331(2) -0.21158(19) 0.13539(15) 0.0154(4) Uani 1 1 d . . .
H7A H 0.0156 -0.2930 0.1178 0.019 Uiso 1 1 calc R . .
C8 C -0.0351(2) -0.01904(19) 0.11482(14) 0.0132(4) Uani 1 1 d . . .
C9 C -0.0304(2) 0.1781(2) 0.12772(15) 0.0154(4) Uani 1 1 d . . .
H9 H -0.0614 0.2582 0.1148 0.019 Uiso 1 1 calc R . .
C10 C 0.1023(2) 0.02138(19) 0.19074(15) 0.0142(4) Uani 1 1 d . . .


_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
O1 H1A 0.96(3) . ?
O1 H1B 0.97(3) . ?
S1 C1 1.6722(19) . ?
N1 C2 1.357(3) . ?
N1 C1 1.397(3) . ?
N1 H1 1.00(3) . ?
N2 C2 1.316(3) . ?
N2 C3 1.358(3) . ?
N3 C4 1.364(3) . ?
N3 C3 1.364(3) . ?
N3 H3 0.96(2) . ?
N4 C4 1.320(3) . ?
N4 C5 1.374(3) . ?
C1 C5 1.414(3) . ?
C2 H2A 0.9300 . ?
C3 C5 1.393(3) . ?
C4 H4 0.9300 . ?
S2 C6 1.6761(19) . ?
N5 C7 1.353(3) . ?
N5 C6 1.393(3) . ?
N5 H5 0.99(3) . ?
N6 C7 1.318(3) . ?
N6 C8 1.352(3) . ?
N7 C8 1.360(3) . ?
N7 C9 1.368(3) . ?
N7 H7 0.86(3) . ?
N8 C9 1.316(3) . ?
N8 C10 1.372(3) . ?
C6 C10 1.406(3) . ?
C7 H7A 0.9300 . ?
C8 C10 1.398(3) . ?
C9 H9 0.9300 . ?

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
H1A O1 H1B 100(3) . . ?
C2 N1 C1 124.90(17) . . ?
C2 N1 H1 117.4(14) . . ?
C1 N1 H1 117.6(14) . . ?
C2 N2 C3 112.07(17) . . ?
C4 N3 C3 106.63(15) . . ?
C4 N3 H3 126.7(16) . . ?
C3 N3 H3 126.7(16) . . ?
C4 N4 C5 104.16(16) . . ?
N1 C1 C5 111.48(16) . . ?
N1 C1 S1 121.87(15) . . ?
C5 C1 S1 126.66(16) . . ?
N2 C2 N1 124.82(19) . . ?
N2 C2 H2A 117.6 . . ?
N1 C2 H2A 117.6 . . ?
N2 C3 N3 127.14(16) . . ?
N2 C3 C5 127.43(18) . . ?
N3 C3 C5 105.41(17) . . ?
N4 C4 N3 113.15(18) . . ?
N4 C4 H4 123.4 . . ?
N3 C4 H4 123.4 . . ?
N4 C5 C3 110.63(17) . . ?
N4 C5 C1 130.41(17) . . ?
C3 C5 C1 118.94(19) . . ?
C7 N5 C6 124.95(17) . . ?
C7 N5 H5 118.0(14) . . ?
C6 N5 H5 117.1(14) . . ?
C7 N6 C8 112.07(17) . . ?
C8 N7 C9 106.73(16) . . ?
C8 N7 H7 125.7(18) . . ?
C9 N7 H7 127.4(18) . . ?
C9 N8 C10 104.59(16) . . ?
N5 C6 C10 111.60(17) . . ?
N5 C6 S2 121.46(15) . . ?
C10 C6 S2 126.93(16) . . ?
N6 C7 N5 124.8(2) . . ?
N6 C7 H7A 117.6 . . ?
N5 C7 H7A 117.6 . . ?
N6 C8 N7 127.28(17) . . ?
N6 C8 C10 127.25(18) . . ?
N7 C8 C10 105.47(18) . . ?
N8 C9 N7 112.91(19) . . ?
N8 C9 H9 123.5 . . ?
N7 C9 H9 123.5 . . ?
N8 C10 C8 110.30(17) . . ?
N8 C10 C6 130.66(18) . . ?
C8 C10 C6 119.01(19) . . ?

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 C5 6.4(2) . . . . ?
C2 N1 C1 S1 -173.28(14) . . . . ?
C3 N2 C2 N1 -1.2(2) . . . . ?
C1 N1 C2 N2 -2.5(3) . . . . ?
C2 N2 C3 N3 -177.95(16) . . . . ?
C2 N2 C3 C5 0.4(3) . . . . ?
C4 N3 C3 N2 177.40(17) . . . . ?
C4 N3 C3 C5 -1.27(18) . . . . ?
C5 N4 C4 N3 0.1(2) . . . . ?
C3 N3 C4 N4 0.8(2) . . . . ?
C4 N4 C5 C3 -0.90(19) . . . . ?
C4 N4 C5 C1 177.74(18) . . . . ?
N2 C3 C5 N4 -177.29(16) . . . . ?
N3 C3 C5 N4 1.38(19) . . . . ?
N2 C3 C5 C1 3.9(3) . . . . ?
N3 C3 C5 C1 -177.44(15) . . . . ?
N1 C1 C5 N4 174.76(17) . . . . ?
S1 C1 C5 N4 -5.6(3) . . . . ?
N1 C1 C5 C3 -6.7(2) . . . . ?
S1 C1 C5 C3 172.98(14) . . . . ?
C7 N5 C6 C10 -6.3(2) . . . . ?
C7 N5 C6 S2 172.37(14) . . . . ?
C8 N6 C7 N5 2.0(2) . . . . ?
C6 N5 C7 N6 2.0(3) . . . . ?
C7 N6 C8 N7 177.96(17) . . . . ?
C7 N6 C8 C10 -1.4(3) . . . . ?
C9 N7 C8 N6 -178.58(17) . . . . ?
C9 N7 C8 C10 0.87(19) . . . . ?
C10 N8 C9 N7 0.3(2) . . . . ?
C8 N7 C9 N8 -0.8(2) . . . . ?
C9 N8 C10 C8 0.3(2) . . . . ?
C9 N8 C10 C6 -177.50(19) . . . . ?
N6 C8 C10 N8 178.72(16) . . . . ?
N7 C8 C10 N8 -0.7(2) . . . . ?
N6 C8 C10 C6 -3.2(3) . . . . ?
N7 C8 C10 C6 177.34(15) . . . . ?
N5 C6 C10 N8 -175.92(18) . . . . ?
S2 C6 C10 N8 5.6(3) . . . . ?
N5 C6 C10 C8 6.5(2) . . . . ?
S2 C6 C10 C8 -172.07(14) . . . . ?

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
O1 H1A S2 0.96(3) 2.41(3) 3.3652(16) 176(2) .
O1 H1B S1 0.97(3) 2.48(3) 3.4392(16) 175(2) .
N1 H1 N4 1.00(3) 1.91(3) 2.903(2) 170(2) 2_556
N3 H3 N6 0.96(2) 1.92(2) 2.860(2) 166(2) 1_656
N5 H5 N8 0.99(3) 1.83(3) 2.818(2) 175(2) 2_545
N7 H7 N2 0.86(3) 2.03(3) 2.877(2) 168(2) 1_454

_diffrn_measured_fraction_theta_max 0.994
_diffrn_reflns_theta_full        68.21
_diffrn_measured_fraction_theta_full 0.994
_refine_diff_density_max         0.587
_refine_diff_density_min         -0.344
_refine_diff_density_rms         0.088
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Methanol and Water'
