Electronic Structure of Ni2E2 Complexes (E = S, Se, Te) and a Global Analysis of M2E2 Compounds: A Case for Quantized E2(n-) Oxidation Levels with n = 2, 3, or 4.
Yao, Shu A.; Martin-Diaconescu, Vlad; Infante, Ivan; Lancaster, Kyle M.; Götz, Andreas W; DeBeer, Serena; Berry, John F.; Journal of the American Chemical Society 137 (2015) 4993–5011; doi:10.1021/ja511607j

data_4123557
_publ_section_title
;
 Electronic Structure of Ni2E2 Complexes (E = S, Se, Te) and a Global
 Analysis of M2E2 Compounds: A Case for Quantized E2(n-) Oxidation Levels
 with n = 2, 3, or 4.
;
_journal_issue                   15
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4993
_journal_page_last               5011
_journal_paper_doi               10.1021/ja511607j
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C51 H87 Ni3 S4, B F4'
_chemical_formula_sum            'C51 H87 B F4 Ni3 S4'
_chemical_formula_weight         1091.38
_space_group_crystal_system      hexagonal
_space_group_IT_number           170
_space_group_name_Hall           'P 65'
_space_group_name_H-M_alt        'P 65'
_symmetry_space_group_name_Hall  'P 65'
_symmetry_space_group_name_H-M   'P 65'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-11-11
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   13.5182(4)
_cell_length_b                   13.5182(4)
_cell_length_c                   50.6155(16)
_cell_measurement_temperature    100.0
_cell_volume                     8010.4(4)
_computing_cell_refinement       'SAINT Ver. 7.24A (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 Ver. 2.1-4 (Bruker-AXS, 2009)'
_computing_data_reduction        'SAINT Ver. 7.24A'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXTL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_unetI/netI     0.1557
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       60
_diffrn_reflns_limit_l_min       -60
_diffrn_reflns_number            73165
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.117
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    1.250
_exptl_absorpt_correction_T_max  0.7881
_exptl_absorpt_correction_T_min  0.6347
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
'SADABS was used for absorption correction (Bruker-AXS, 2007)'
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.357
_exptl_crystal_description       block
_exptl_crystal_F_000             3492
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.071
_refine_diff_density_min         -0.488
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 2604 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.807
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     639
_refine_ls_number_reflns         73165
_refine_ls_number_restraints     262
_refine_ls_restrained_S_all      0.810
_refine_ls_R_factor_all          0.1022
_refine_ls_R_factor_gt           0.0756
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1130P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1734
_refine_ls_wR_factor_ref         0.1899
_reflns_Friedel_coverage         0.976
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                8104
_reflns_number_total             9396
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja511607j_si_001.cif
_cod_data_source_block           berry176
_cod_depositor_comments
'Adding full bibliography for 4123556--4123563.cif.'
_cod_original_cell_volume        8010.4(5)
_cod_database_code               4123557
_shelxl_version_number           2014/5
_shelx_estimated_absorpt_t_max   0.788
_shelx_estimated_absorpt_t_min   0.635
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 B1-F1 \\sim B1-F2 \\sim B1-F3 \\sim B1-F4 \\sim B1A-F1A \\sim B1A-F2A \\sim
B1A-F3A \\sim B1A-F4A
 with sigma of 0.001
 F1-F3 \\sim F1-F4 \\sim F2-F3 \\sim F2-F4 \\sim F3-F4 \\sim F1A-F2A
 with sigma of 0.005
 F1-F2 \\sim F1A-F3A \\sim F1A-F4A \\sim F2A-F3A \\sim F2A-F4A \\sim F3A-F4A
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
F3A \\sim F1A \\sim B1A \\sim F2A \\sim F4A \\sim B1 \\sim F1 \\sim F2 \\sim F3
\\sim F4: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
C19 \\sim C20 \\sim C21: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C43 \\sim C44 \\sim C45: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C13 \\sim C14 \\sim C15 \\sim C11 \\sim C12: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C13, C14, C15, C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(B1A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19), C22(H22), C25(H25), C28(H28), C31(H31), C34(H34),
 C37(H37), C40(H40), C43(H43), C46(H46), C49(H49)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C12(H12)
6.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C),
 C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,
 H38C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,
 H44B,H44C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C),
 C50(H50A,H50B,H50C), C51(H51A,H51B,H51C)
;