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

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  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.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_mf3-4c-final

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'Bi Ge S4, C2 H8 N'
_chemical_formula_sum            'C2 H8 Bi Ge N S4'
_chemical_formula_weight         455.90

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ge Ge 0.1547 1.8001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Bi Bi -4.1077 10.2566 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_space_group_IT_number           4
_space_group_name_H-M_alt        'P 21'
_space_group_name_Hall           'P 2yb'

_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'

_cell_length_a                   6.7290(7)
_cell_length_b                   6.9404(5)
_cell_length_c                   10.6748(11)
_cell_angle_alpha                90
_cell_angle_beta                 105.789(6)
_cell_angle_gamma                90
_cell_volume                     479.72(8)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1520
_cell_measurement_theta_min      3.1459
_cell_measurement_theta_max      27.4642

_exptl_crystal_description       plane
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    3.156
_exptl_crystal_F_000             412
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.05
_exptl_absorpt_coefficient_mu    22.244
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.1529
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Mercury70 (2x2 bin mode)'
_diffrn_measurement_method       CCD_Profile_fitting
_diffrn_detector_area_resol_mean 14.6306
_diffrn_reflns_number            3025
_diffrn_reflns_av_unetI/netI     0.1091
_diffrn_reflns_av_R_equivalents  0.0640
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         3.146
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.966
_reflns_number_total             1656
_reflns_number_gt                1485
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.836
_reflns_Friedel_fraction_max     0.999
_reflns_Friedel_fraction_full    0.966

_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       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_cell_refinement       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_data_reduction        'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     'w=1/[σ²(Fo²)] 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     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.349(18)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1656
_refine_ls_number_parameters     85
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0465
_refine_ls_R_factor_gt           0.0447
_refine_ls_wR_factor_ref         0.0844
_refine_ls_wR_factor_gt          0.0839
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_restrained_S_all      0.999
_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
Bi1 Bi 0.76772(10) 0.71306(10) 0.45529(7) 0.0199(3) Uani 1 1 d . . . . .
Ge1 Ge 0.7832(3) 0.3112(3) 0.6553(2) 0.0135(5) Uani 1 1 d . . . . .
S1 S 0.9766(9) 0.5718(9) 0.6968(6) 0.0237(14) Uani 1 1 d . . . . .
S2 S 0.9878(8) 0.0559(9) 0.6695(6) 0.0205(14) Uani 1 1 d . . . . .
S3 S 0.5726(8) 0.2668(8) 0.7769(6) 0.0222(17) Uani 1 1 d . . . . .
S4 S 0.3986(8) 0.8687(9) 0.5513(6) 0.0196(13) Uani 1 1 d . . . . .
N1 N 0.680(3) 0.808(3) 0.861(2) 0.039(6) Uani 1 1 d . . . . .
H1A H 0.7067 0.7110 0.8022 0.047 Uiso 1 1 calc R U . . .
H1B H 0.6694 0.9311 0.8172 0.047 Uiso 1 1 calc R U . . .
C1 C 0.478(3) 0.764(4) 0.885(2) 0.039(7) Uani 1 1 d . . . . .
H1C H 0.4011 0.6786 0.8191 0.058 Uiso 1 1 calc R U . . .
H1D H 0.4017 0.8818 0.8834 0.058 Uiso 1 1 calc R U . . .
H1E H 0.4999 0.7046 0.9691 0.058 Uiso 1 1 calc R U . . .
C2 C 0.855(4) 0.814(5) 0.975(3) 0.061(9) Uani 1 1 d . . . . .
H2A H 0.9695 0.7490 0.9568 0.091 Uiso 1 1 calc R U . . .
H2B H 0.8194 0.7522 1.0463 0.091 Uiso 1 1 calc R U . . .
H2C H 0.8911 0.9461 0.9970 0.091 Uiso 1 1 calc R U . . .

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
Bi1 0.0172(4) 0.0218(5) 0.0210(5) 0.0025(5) 0.0058(3) 0.0005(5)
Ge1 0.0146(12) 0.0133(12) 0.0138(14) -0.0005(10) 0.0059(10) -0.0010(9)
S1 0.027(3) 0.021(3) 0.017(3) 0.003(3) -0.004(3) -0.009(3)
S2 0.021(3) 0.019(3) 0.026(4) 0.004(3) 0.013(3) 0.001(2)
S3 0.021(3) 0.033(5) 0.014(3) 0.000(3) 0.009(3) 0.000(2)
S4 0.020(3) 0.026(4) 0.010(3) -0.001(3) 0.000(2) 0.012(3)
N1 0.050(14) 0.043(14) 0.030(15) -0.015(11) 0.019(12) -0.007(11)
C1 0.058(17) 0.04(2) 0.022(16) 0.006(12) 0.012(13) -0.010(12)
C2 0.060(19) 0.10(3) 0.014(17) 0.011(17) -0.009(14) 0.013(18)

_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
Bi1 S2 2.619(5) 2_756 ?
Bi1 S4 2.632(6) 2_646 ?
Bi1 S1 2.759(6) . ?
Bi1 S3 2.905(6) 2_656 ?
Bi1 S4 3.126(5) . ?
Bi1 S2 3.353(6) 1_565 ?
Bi1 S1 3.649(7) 2_756 ?
Ge1 S3 2.188(5) . ?
Ge1 S1 2.201(6) . ?
Ge1 S2 2.224(6) . ?
Ge1 S4 2.248(7) 2_646 ?
S2 Bi1 2.619(5) 2_746 ?
S3 Bi1 2.905(6) 2_646 ?
S4 Ge1 2.248(7) 2_656 ?
S4 Bi1 2.632(6) 2_656 ?
N1 C2 1.44(3) . ?
N1 C1 1.48(2) . ?
N1 H1A 0.9700 . ?
N1 H1B 0.9700 . ?
C1 H1C 0.9600 . ?
C1 H1D 0.9600 . ?
C1 H1E 0.9600 . ?
C2 H2A 0.9600 . ?
C2 H2B 0.9600 . ?
C2 H2C 0.9600 . ?

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
S2 Bi1 S4 85.96(18) 2_756 2_646 ?
S2 Bi1 S1 95.54(19) 2_756 . ?
S4 Bi1 S1 78.88(18) 2_646 . ?
S2 Bi1 S3 94.47(18) 2_756 2_656 ?
S4 Bi1 S3 82.12(17) 2_646 2_656 ?
S1 Bi1 S3 157.79(15) . 2_656 ?
S2 Bi1 S4 167.30(17) 2_756 . ?
S4 Bi1 S4 87.28(9) 2_646 . ?
S1 Bi1 S4 93.69(16) . . ?
S3 Bi1 S4 73.93(15) 2_656 . ?
S2 Bi1 S2 114.85(11) 2_756 1_565 ?
S4 Bi1 S2 140.23(16) 2_646 1_565 ?
S1 Bi1 S2 66.23(17) . 1_565 ?
S3 Bi1 S2 126.17(15) 2_656 1_565 ?
S4 Bi1 S2 76.95(14) . 1_565 ?
S2 Bi1 S1 67.69(16) 2_756 2_756 ?
S4 Bi1 S1 148.89(16) 2_646 2_756 ?
S1 Bi1 S1 118.45(11) . 2_756 ?
S3 Bi1 S1 83.71(14) 2_656 2_756 ?
S4 Bi1 S1 115.04(15) . 2_756 ?
S2 Bi1 S1 69.20(13) 1_565 2_756 ?
S3 Ge1 S1 116.1(2) . . ?
S3 Ge1 S2 109.7(2) . . ?
S1 Ge1 S2 108.6(2) . . ?
S3 Ge1 S4 109.9(2) . 2_646 ?
S1 Ge1 S4 100.7(2) . 2_646 ?
S2 Ge1 S4 111.7(2) . 2_646 ?
Ge1 S1 Bi1 88.9(2) . . ?
Ge1 S2 Bi1 95.6(2) . 2_746 ?
Ge1 S3 Bi1 89.97(19) . 2_646 ?
Ge1 S4 Bi1 91.2(2) 2_656 2_656 ?
Ge1 S4 Bi1 83.43(17) 2_656 . ?
Bi1 S4 Bi1 132.4(2) 2_656 . ?
C2 N1 C1 116(2) . . ?
C2 N1 H1A 108.3 . . ?
C1 N1 H1A 108.3 . . ?
C2 N1 H1B 108.3 . . ?
C1 N1 H1B 108.3 . . ?
H1A N1 H1B 107.4 . . ?
N1 C1 H1C 109.5 . . ?
N1 C1 H1D 109.5 . . ?
H1C C1 H1D 109.5 . . ?
N1 C1 H1E 109.5 . . ?
H1C C1 H1E 109.5 . . ?
H1D C1 H1E 109.5 . . ?
N1 C2 H2A 109.5 . . ?
N1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
N1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?

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
N1 H1A S1 0.97 2.57 3.41(2) 145.3 .
N1 H1B S3 0.97 2.43 3.34(2) 156.2 1_565
C1 H1C S1 0.96 2.90 3.68(2) 139.3 1_455
C1 H1E S3 0.96 2.92 3.71(2) 141.3 2_657

_refine_diff_density_max         1.653
_refine_diff_density_min         -2.275
_refine_diff_density_rms         0.296

_shelxl_version_number           2013-4

_shelx_res_file                  
;
TITL FML in P2(1)
CELL 0.71073   6.7290   6.9404  10.6748  90.000 105.789  90.000
ZERR    2.00   0.0007   0.0005   0.0011   0.000   0.006   0.000
LATT -1
SYMM -X, 0.5+Y, -Z
SFAC C H N S GE BI
UNIT 4 16 2 8 2 2
omit 0 -1 1
L.S. 41
BOND $H
shel 999 0.84
FMAP 2
PLAN 5
eqiv $1 x, y+1, z
eqiv $2 2-x, 1/2+y, 1-z
bind bi1 s1_$2
bind bi1 s2_$1
htab n1 s1
htab n1 s3_$1
EQIV $3 x-1, y, z
HTAB C1 S1_$3
EQIV $4 -x+1, y+1/2, -z+2
HTAB C1 S3_$4
twin
acta
WGHT    0.000000
BASF   0.34872
FVAR       0.46286
BI1   6    0.767718    0.713059    0.455291    11.00000    0.01716    0.02179 =
         0.02104    0.00245    0.00585    0.00045
GE1   5    0.783166    0.311235    0.655348    11.00000    0.01459    0.01328 =
         0.01383   -0.00045    0.00590   -0.00097
S1    4    0.976566    0.571766    0.696833    11.00000    0.02702    0.02077 =
         0.01739    0.00342   -0.00406   -0.00947
S2    4    0.987822    0.055934    0.669456    11.00000    0.02066    0.01852 =
         0.02595    0.00358    0.01257    0.00115
S3    4    0.572582    0.266785    0.776886    11.00000    0.02112    0.03350 =
         0.01428   -0.00040    0.00878   -0.00037
S4    4    0.398627    0.868652    0.551325    11.00000    0.01973    0.02643 =
         0.01015   -0.00108   -0.00010    0.01206
N1    3    0.679825    0.807720    0.861167    11.00000    0.04952    0.04251 =
         0.02988   -0.01490    0.01858   -0.00737
AFIX  23
H1A   2    0.706730    0.711013    0.802242    11.00000   -1.20000
H1B   2    0.669351    0.931142    0.817212    11.00000   -1.20000
AFIX   0
C1    1    0.477873    0.764368    0.885295    11.00000    0.05843    0.03703 =
         0.02169    0.00553    0.01244   -0.00950
AFIX 137
H1C   2    0.401109    0.678618    0.819107    11.00000   -1.50000
H1D   2    0.401724    0.881810    0.883354    11.00000   -1.50000
H1E   2    0.499899    0.704578    0.969061    11.00000   -1.50000
AFIX   0
C2    1    0.854568    0.814318    0.974822    11.00000    0.06014    0.09739 =
         0.01359    0.01075   -0.00913    0.01302
AFIX 137
H2A   2    0.969501    0.748989    0.956809    11.00000   -1.50000
H2B   2    0.819407    0.752244    1.046276    11.00000   -1.50000
H2C   2    0.891103    0.946113    0.997027    11.00000   -1.50000

AFIX   0
HKLF 4

REM  FML in P2(1)
REM R1 =  0.0447 for    1485 Fo > 4sig(Fo)  and  0.0465 for all    1656 data
REM     85 parameters refined using      1 restraints

END

WGHT      0.0135      0.0000

REM Highest difference peak  1.653,  deepest hole -2.275,  1-sigma level  0.296
Q1    1   0.6060  0.5763  0.3659  11.00000  0.05    1.55
Q2    1   0.8115  0.7140  0.5715  11.00000  0.05    1.46
Q3    1   0.7413  0.8449  0.5126  11.00000  0.05    1.38
Q4    1   0.6165  0.8241  0.3766  11.00000  0.05    1.35
Q5    1   0.9132  0.8435  0.5329  11.00000  0.05    1.33
;
_shelx_res_checksum              24247

_database_code_depnum_ccdc_archive 'CCDC 981627'
