# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2014

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#                                CCDC 
# 
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# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
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#  fide research purposes only. It may contain copyright material
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data_mo_20111205D_0m

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C4 H4 Br Cu O4 P S'
_chemical_formula_sum            'C4 H4 Br Cu O4 P S'
_chemical_formula_weight         322.55

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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_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+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   15.899(4)
_cell_length_b                   7.627(2)
_cell_length_c                   7.3440(19)
_cell_angle_alpha                90
_cell_angle_beta                 100.075(4)
_cell_angle_gamma                90
_cell_volume                     876.7(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    3841
_cell_measurement_theta_min      2.602
_cell_measurement_theta_max      28.287

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.444
_exptl_crystal_F_000             620
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.120
_exptl_absorpt_coefficient_mu    7.437
_shelx_estimated_absorpt_T_min   0.258
_shelx_estimated_absorpt_T_max   0.469
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.182
_exptl_absorpt_correction_T_max  0.411
_exptl_absorpt_process_details   'SADABS(Bruker, 2000)'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX II'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5973
_diffrn_reflns_av_unetI/netI     0.0649
_diffrn_reflns_av_R_equivalents  0.0706
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_theta_min         1.301
_diffrn_reflns_theta_max         25.995
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measured_fraction_theta_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_point_group_measured_fraction_full 0.985
_reflns_number_total             1696
_reflns_number_gt                1529
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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       'SMART (Bruker, 2000)'
_computing_cell_refinement       SMART
_computing_data_reduction        'SAINT (Bruker, 2000)'
_computing_structure_solution    'SHELXTL (Bruker, 2000)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    SHELXTL
_computing_publication_material  SHELXTL

_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)+(0.0917P)²+7.9831P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1696
_refine_ls_number_parameters     109
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0632
_refine_ls_R_factor_gt           0.0591
_refine_ls_wR_factor_ref         0.1572
_refine_ls_wR_factor_gt          0.1549
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_restrained_S_all      1.001
_refine_ls_shift/su_max          0.001
_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
Cu1 Cu 0.02159(5) 0.30976(8) 0.45225(9) 0.0089(3) Uani 1 1 d . . . . .
Br1 Br 0.44842(6) -0.12351(16) 0.18980(16) 0.0548(4) Uani 1 1 d . . . . .
P1 P 0.09954(10) -0.04482(17) 0.3857(2) 0.0079(4) Uani 1 1 d . . . . .
S1 S 0.25990(11) -0.1702(2) 0.2384(3) 0.0219(4) Uani 1 1 d . . . . .
O1 O 0.0855(3) 0.0997(5) 0.5224(6) 0.0105(8) Uani 1 1 d . . . . .
O2 O 0.0806(3) -0.2267(5) 0.4570(6) 0.0102(8) Uani 1 1 d . . . . .
O3 O 0.0473(3) -0.0091(5) 0.1931(5) 0.0106(8) Uani 1 1 d . . . . .
O1W O 0.1255(3) 0.4209(5) 0.3863(6) 0.0130(9) Uani 1 1 d . . . . .
H1WA H 0.1333 0.5257 0.4249 0.016 Uiso 1 1 d R U . . .
H1WB H 0.1094 0.4189 0.2697 0.016 Uiso 1 1 d R U . . .
C1 C 0.2103(4) -0.0311(7) 0.3713(9) 0.0121(12) Uani 1 1 d . . . . .
C2 C 0.2648(5) 0.0956(9) 0.4498(11) 0.0256(16) Uani 1 1 d . . . . .
H1A H 0.2490 0.1829 0.5256 0.031 Uiso 1 1 calc R U . . .
C3 C 0.3481(5) 0.0825(11) 0.4057(13) 0.0323(18) Uani 1 1 d . . . . .
H3 H 0.3930 0.1583 0.4492 0.039 Uiso 1 1 calc R U . . .
C4 C 0.3535(5) -0.0544(10) 0.2924(11) 0.0264(16) 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
Cu1 0.0132(5) 0.0035(4) 0.0098(4) 0.0010(2) 0.0011(3) 0.0007(2)
Br1 0.0226(5) 0.0783(8) 0.0691(8) -0.0210(6) 0.0240(5) -0.0026(4)
P1 0.0115(8) 0.0025(7) 0.0093(7) 0.0001(5) 0.0003(6) 0.0000(5)
S1 0.0160(9) 0.0244(9) 0.0261(9) -0.0110(7) 0.0058(7) -0.0002(6)
O1 0.016(2) 0.0058(19) 0.0090(19) -0.0023(15) 0.0016(17) -0.0011(15)
O2 0.012(2) 0.0066(19) 0.0120(19) 0.0008(16) 0.0026(17) -0.0017(15)
O3 0.016(2) 0.0056(19) 0.0089(19) -0.0007(15) -0.0015(17) -0.0018(15)
O1W 0.019(2) 0.010(2) 0.011(2) 0.0006(16) 0.0029(17) 0.0004(16)
C1 0.012(3) 0.010(3) 0.015(3) 0.000(2) 0.002(2) 0.001(2)
C2 0.027(4) 0.014(3) 0.037(4) -0.010(3) 0.007(3) -0.002(3)
C3 0.014(4) 0.032(4) 0.050(5) -0.011(4) 0.003(3) -0.012(3)
C4 0.017(4) 0.029(4) 0.034(4) 0.001(3) 0.007(3) 0.000(3)

_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
Cu1 O1 1.919(4) . ?
Cu1 O3 1.960(4) 2 ?
Cu1 O2 1.965(4) 3_556 ?
Cu1 O1W 1.991(4) . ?
Cu1 O3 2.314(4) 4_566 ?
Br1 C4 1.877(7) . ?
P1 O2 1.531(4) . ?
P1 O3 1.534(4) . ?
P1 O1 1.534(4) . ?
P1 C1 1.786(6) . ?
S1 C4 1.716(8) . ?
S1 C1 1.723(6) . ?
O2 Cu1 1.965(4) 3_556 ?
O3 Cu1 1.960(4) 2_545 ?
O3 Cu1 2.314(4) 4_565 ?
O1W H1WA 0.8500 . ?
O1W H1WB 0.8500 . ?
C1 C2 1.357(9) . ?
C2 C3 1.422(11) . ?
C2 H1A 0.9300 . ?
C3 C4 1.347(11) . ?
C3 H3 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
O1 Cu1 O3 162.63(17) . 2 ?
O1 Cu1 O2 94.04(17) . 3_556 ?
O3 Cu1 O2 89.74(17) 2 3_556 ?
O1 Cu1 O1W 89.86(18) . . ?
O3 Cu1 O1W 88.62(18) 2 . ?
O2 Cu1 O1W 171.94(17) 3_556 . ?
O1 Cu1 O3 109.17(16) . 4_566 ?
O3 Cu1 O3 87.75(16) 2 4_566 ?
O2 Cu1 O3 89.93(16) 3_556 4_566 ?
O1W Cu1 O3 82.12(16) . 4_566 ?
O2 P1 O3 111.7(2) . . ?
O2 P1 O1 111.5(2) . . ?
O3 P1 O1 111.0(2) . . ?
O2 P1 C1 109.2(3) . . ?
O3 P1 C1 108.4(3) . . ?
O1 P1 C1 104.7(3) . . ?
C4 S1 C1 91.0(3) . . ?
P1 O1 Cu1 123.7(3) . . ?
P1 O2 Cu1 129.2(3) . 3_556 ?
P1 O3 Cu1 122.5(2) . 2_545 ?
P1 O3 Cu1 144.7(2) . 4_565 ?
Cu1 O3 Cu1 92.25(16) 2_545 4_565 ?
Cu1 O1W H1WA 113.5 . . ?
Cu1 O1W H1WB 97.0 . . ?
H1WA O1W H1WB 110.8 . . ?
C2 C1 S1 111.0(5) . . ?
C2 C1 P1 125.4(5) . . ?
S1 C1 P1 123.5(4) . . ?
C1 C2 C3 113.9(6) . . ?
C1 C2 H1A 123.1 . . ?
C3 C2 H1A 123.1 . . ?
C4 C3 C2 110.9(7) . . ?
C4 C3 H3 124.5 . . ?
C2 C3 H3 124.5 . . ?
C3 C4 S1 113.3(6) . . ?
C3 C4 Br1 127.4(6) . . ?
S1 C4 Br1 119.3(4) . . ?

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
O2 P1 O1 Cu1 -132.0(3) . . . . ?
O3 P1 O1 Cu1 -6.7(4) . . . . ?
C1 P1 O1 Cu1 110.1(3) . . . . ?
O3 P1 O2 Cu1 -73.1(4) . . . 3_556 ?
O1 P1 O2 Cu1 51.8(4) . . . 3_556 ?
C1 P1 O2 Cu1 167.1(3) . . . 3_556 ?
O2 P1 O3 Cu1 -8.1(4) . . . 2_545 ?
O1 P1 O3 Cu1 -133.3(3) . . . 2_545 ?
C1 P1 O3 Cu1 112.2(3) . . . 2_545 ?
O2 P1 O3 Cu1 -177.5(4) . . . 4_565 ?
O1 P1 O3 Cu1 57.3(5) . . . 4_565 ?
C1 P1 O3 Cu1 -57.2(5) . . . 4_565 ?
C4 S1 C1 C2 0.2(6) . . . . ?
C4 S1 C1 P1 175.5(4) . . . . ?
O2 P1 C1 C2 -126.5(6) . . . . ?
O3 P1 C1 C2 111.6(6) . . . . ?
O1 P1 C1 C2 -7.0(7) . . . . ?
O2 P1 C1 S1 58.8(5) . . . . ?
O3 P1 C1 S1 -63.0(4) . . . . ?
O1 P1 C1 S1 178.4(4) . . . . ?
S1 C1 C2 C3 -0.5(9) . . . . ?
P1 C1 C2 C3 -175.7(6) . . . . ?
C1 C2 C3 C4 0.6(11) . . . . ?
C2 C3 C4 S1 -0.5(10) . . . . ?
C2 C3 C4 Br1 178.2(6) . . . . ?
C1 S1 C4 C3 0.2(7) . . . . ?
C1 S1 C4 Br1 -178.6(5) . . . . ?

_refine_diff_density_max         1.077
_refine_diff_density_min         -1.750
_refine_diff_density_rms         0.268

_shelxl_version_number           2013-4

_shelx_res_file                  
;
TITL GY in P2(1)/c
CELL 0.71073  15.8988   7.6265   7.3440  90.000 100.075  90.000
ZERR    4.00   0.0041   0.0020   0.0019   0.000   0.004   0.000
LATT 1
SYMM -X, 0.5+Y, 0.5-Z
SFAC C  H  O  P  S  Cu Br
UNIT 16 16 16 4 4 4 4
OMIT     0   1   4
OMIT    -6   0   4
OMIT    -5   3   4
OMIT    -4   5   4
OMIT     7   1   4
OMIT   0.00  52.00
L.S. 5
ACTA
BOND $H
FMAP 2
PLAN 5
CONF
HTAB
SIZE 0.25 0.20 0.12
TEMP 23.000
WGHT    0.091700    7.983100
FVAR       0.12841
CU1   6    0.021587    0.309757    0.452250    11.00000    0.01318    0.00348 =
         0.00979    0.00103    0.00107    0.00066
BR1   7    0.448421   -0.123509    0.189798    11.00000    0.02260    0.07828 =
         0.06914   -0.02099    0.02397   -0.00262
P1    4    0.099539   -0.044817    0.385677    11.00000    0.01147    0.00254 =
         0.00926    0.00011    0.00033   -0.00002
S1    5    0.259898   -0.170167    0.238433    11.00000    0.01601    0.02442 =
         0.02609   -0.01096    0.00579   -0.00020
O1    3    0.085545    0.099748    0.522425    11.00000    0.01649    0.00585 =
         0.00900   -0.00230    0.00160   -0.00112
O2    3    0.080560   -0.226693    0.457048    11.00000    0.01209    0.00657 =
         0.01200    0.00077    0.00262   -0.00166
O3    3    0.047342   -0.009092    0.193146    11.00000    0.01600    0.00561 =
         0.00892   -0.00070   -0.00152   -0.00181
O1W   3    0.125489    0.420927    0.386274    11.00000    0.01868    0.00959 =
         0.01081    0.00063    0.00289    0.00039
AFIX   3
H1WA  2    0.133319    0.525719    0.424942    11.00000   -1.20000
H1WB  2    0.109410    0.418862    0.269654    11.00000   -1.20000
AFIX   0
C1    1    0.210307   -0.031097    0.371294    11.00000    0.01211    0.00954 =
         0.01462    0.00048    0.00237    0.00092
C2    1    0.264786    0.095560    0.449818    11.00000    0.02656    0.01364 =
         0.03717   -0.01002    0.00734   -0.00195
AFIX  43
H1A   2    0.249044    0.182923    0.525584    11.00000   -1.20000
AFIX   0
C3    1    0.348139    0.082505    0.405677    11.00000    0.01402    0.03210 =
         0.04993   -0.01067    0.00307   -0.01195
AFIX  43
H3    2    0.392969    0.158334    0.449199    11.00000   -1.20000
AFIX   0
C4    1    0.353481   -0.054402    0.292379    11.00000    0.01658    0.02941 =
         0.03426    0.00094    0.00742    0.00025
HKLF 4

REM  GY in P2(1)/c
REM R1 =  0.0591 for    1529 Fo > 4sig(Fo)  and  0.0632 for all    1696 data
REM    109 parameters refined using      0 restraints

END

WGHT      0.0971      3.8186

REM Instructions for potential hydrogen bonds
EQIV $1 x, -y+1/2, z+1/2
HTAB O1W S1_$1
EQIV $2 x, y+1, z
HTAB O1W O2_$2
EQIV $3 x, -y+1/2, z-1/2
HTAB O1W O1_$3

REM Highest difference peak  1.077,  deepest hole -1.750,  1-sigma level  0.268
Q1    1  -0.0200  0.3167  0.3412  11.00000  0.05    1.08
Q2    1  -0.0030  0.3141  0.5758  11.00000  0.05    1.06
Q3    1   0.2723 -0.1673  0.0857  11.00000  0.05    0.91
Q4    1   0.0505  0.3128  0.3457  11.00000  0.05    0.90
Q5    1   0.2133  0.6313  0.4578  11.00000  0.05    0.88
;
_shelx_res_checksum              67195
_database_code_depnum_ccdc_archive 'CCDC 998012'
