Synthesis, structures, redox properties, and theoretical calculations of thiohalide capped octahedral hexanuclear technetium(iii) clusters.
Yoshimura, Takashi; Nagata, Kojiro; Matsuda, Ayumi; Omote, Toshiki; Kino, Yasushi; Takayama, Tsutomu; Sekine, Tsutomu; Shinohara, Atsushi; Dalton transactions (Cambridge, England : 2003) 48 (2019) 14085–14095; doi:10.1039/c9dt02909e

data_7701601
_publ_section_title
;
 Synthesis, structures, redox properties, and theoretical calculations of
 thiohalide capped octahedral hexanuclear technetium(iii) clusters.
;
_journal_issue                   37
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14085
_journal_page_last               14095
_journal_paper_doi               10.1039/c9dt02909e
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         '2(Cl3.5 S3.5 Tc3), 3(C24 H20 P), C2 H3 N'
_chemical_formula_sum            'C74 H63 Cl7 N P3 S7 Tc6'
_chemical_formula_weight         2125.19
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_audit_creation_date             2019-05-13
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-07-15 deposited with the CCDC.	2019-09-06 downloaded from the CCDC.
;
_cell_angle_alpha                77.2560(10)
_cell_angle_beta                 78.5140(10)
_cell_angle_gamma                77.6280(10)
_cell_formula_units_Z            2
_cell_length_a                   12.4941(2)
_cell_length_b                   13.6855(3)
_cell_length_c                   24.1157(5)
_cell_measurement_reflns_used    28339
_cell_measurement_temperature    170
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      3.1
_cell_volume                     3878.28(13)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      170
_diffrn_detector_area_resol_mean 10
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  RAPID
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0330
_diffrn_reflns_av_unetI/netI     0.0431
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            38854
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.464
_diffrn_reflns_theta_min         3.057
_exptl_absorpt_coefficient_mu    1.574
_exptl_absorpt_correction_T_max  0.855
_exptl_absorpt_correction_T_min  0.697
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'ABSCOR (Rigaku, 1995)'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.820
_exptl_crystal_description       block
_exptl_crystal_F_000             2096
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.921
_refine_diff_density_min         -0.855
_refine_diff_density_rms         0.142
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.204
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     892
_refine_ls_number_reflns         17602
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.204
_refine_ls_R_factor_all          0.0425
_refine_ls_R_factor_gt           0.0289
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+6.5471P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0544
_refine_ls_wR_factor_ref         0.0741
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14538
_reflns_number_total             17602
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt02909e2.cif
_cod_data_source_block           PPh4[Tc6S7Cl7]
_cod_database_code               7701601
_shelx_shelxl_version_number     2018/3
_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. Shared sites
{Cl24, S24}
{Cl23, S23}
{Cl22, S22}
{Cl21, S21}
{Cl11, S11}
{Cl12, S12}
{Cl13, S13}
{Cl14, S14}
3. Uiso/Uaniso restraints and constraints
Uanis(Cl24) = Uanis(S24)
Uanis(Cl23) = Uanis(S23)
Uanis(Cl22) = Uanis(S22)
Uanis(Cl21) = Uanis(S21)
Uanis(Cl11) = Uanis(S11)
Uanis(Cl12) = Uanis(S12)
Uanis(Cl13) = Uanis(S13)
Uanis(Cl14) = Uanis(S14)
4. Others
 1*[Sof(Cl24)+Sof(S24)]+1*[Sof(Cl23)+Sof(S23)]+1*[Sof(Cl22)+Sof(S22)]+1*
 [Sof(Cl21)+Sof(S21)]=0.5 with esd of 0.0001
 1*[Sof(Cl11)+Sof(S11)]+1*[Sof(Cl12)+Sof(S12)]+1*[Sof(Cl13)+Sof(S13)]+1*
 [Sof(Cl14)+Sof(S14)]=0.5 with esd of 0.0001
 Sof(S24)=1-FVAR(1)
 Sof(Cl24)=FVAR(1)
 Sof(S23)=1-FVAR(2)
 Sof(Cl23)=FVAR(2)
 Sof(S22)=1-FVAR(3)
 Sof(Cl22)=FVAR(3)
 Sof(S21)=1-FVAR(4)
 Sof(Cl21)=FVAR(4)
 Sof(S11)=1-FVAR(5)
 Sof(Cl11)=FVAR(5)
 Sof(S12)=1-FVAR(6)
 Sof(Cl12)=FVAR(6)
 Sof(S13)=1-FVAR(7)
 Sof(Cl13)=FVAR(7)
 Sof(S14)=1-FVAR(8)
 Sof(Cl14)=FVAR(8)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21),
  C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29),
 C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39),
  C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47),
 C48(H48), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57),
  C58(H58), C59(H59), C60(H60), C62(H62), C63(H63), C64(H64), C65(H65),
 C66(H66), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72)
5.b Idealised Me refined as rotating group:
 C73(H73A,H73B,H73C)
;
_olex2_submission_special_instructions 'No special instructions were received'