Metal–organic polyhedron from a flexible tetrakis(thiobenzyl-carboxylate)-tetrathiafulvalene
Cheret, Yohan; Avarvari, Narcis; Zigon, Nicolas; CrystEngComm 26 (2024) 2072–2077; doi:10.1039/D3CE01251D

data_7248226
_publ_section_title
;
 Metal--organic polyhedron from a flexible
 tetrakis(thiobenzyl-carboxylate)-tetrathiafulvalene
;
_journal_issue                   15
_journal_name_full               CrystEngComm
_journal_page_first              2072
_journal_page_last               2077
_journal_paper_doi               10.1039/D3CE01251D
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety
'C152 H96 Cu8 O40 S32, 0.25(C6 H14 N2 O2), 0.66(C3 N O)'
_chemical_formula_sum            'C155.9 H101.1 Cu8 N1.3 O41.3 S32'
_chemical_formula_weight         4187.51
_chemical_name_systematic
'[tetrakis(\m~2~-4,4',4'',4'''-(([2,2'-bi(1,3-dithiolylidene)]-4,4',5,5'-tetrayltetrakis(sulfanediyl))tetrakis(methylene))tetrabenzoate-O,O')-bis(water)-di-copper(ii)]4, dimethylformamide solvate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_Hall           '-P 2yb'
_space_group_name_H-M_alt        'P 1 21/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-01-19
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2024-01-24 deposited with the CCDC.	2024-02-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.324(15)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   19.081(3)
_cell_length_b                   31.525(6)
_cell_length_c                   20.060(2)
_cell_measurement_reflns_used    3080
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      60.0850
_cell_measurement_theta_min      3.1880
_cell_volume                     11692(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 42.102a (release 15-09-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_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_environment      N~2~
_diffrn_ambient_temperature      180.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1990
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -69.00  -9.00   1.00  100.00    --    0.00 -57.00 150.00   60
  2  \w    -31.00  25.00   1.00  100.00    --    0.00  77.00-120.00   56
  3  \w     99.00 147.00   1.00  400.00    --   80.52  61.00  60.00   48
  4  \w      9.00  42.00   1.00  400.00    --   80.52 -45.00  90.00   33
  5  \w      7.00  33.00   1.00  400.00    --   80.52 -30.00-180.00   26
  6  \w      6.00  35.00   1.00  400.00    --   80.52 -30.00 -30.00   29
  7  \w      9.00  34.00   1.00  400.00    --   80.52 -30.00  60.00   25
  8  \w    114.00 145.00   1.00  400.00    --   80.52  77.00  90.00   31
  9  \w      6.00  32.00   1.00  400.00    --   80.52 -30.00 150.00   26
 10  \w     10.00  68.00   1.00  400.00    --   80.52 -61.00-120.00   58
 11  \w     11.00  43.00   1.00  400.00    --   80.52 -45.00 120.00   32
 12  \w     43.00  70.00   1.00  400.00    --   80.52 -61.00 -60.00   27
 13  \w     10.00  37.00   1.00  400.00    --   80.52 -45.00-180.00   27
 14  \w     18.00  62.00   1.00  400.00    --   80.52 -61.00 -90.00   44
 15  \w      7.00  29.00   1.00  400.00    --   80.52 -30.00 -60.00   22
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0615464000
_diffrn_orient_matrix_UB_12      0.0152584000
_diffrn_orient_matrix_UB_13      -0.0313806000
_diffrn_orient_matrix_UB_21      0.0479905000
_diffrn_orient_matrix_UB_22      -0.0367693000
_diffrn_orient_matrix_UB_23      0.0359257000
_diffrn_orient_matrix_UB_31      -0.0290833000
_diffrn_orient_matrix_UB_32      -0.0283633000
_diffrn_orient_matrix_UB_33      -0.0632841000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0962
_diffrn_reflns_av_unetI/netI     0.1165
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            11535
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        33.411
_diffrn_reflns_theta_max         33.411
_diffrn_reflns_theta_min         2.771
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.929
_exptl_absorpt_correction_T_max  0.812
_exptl_absorpt_correction_T_min  0.229
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.189
_exptl_crystal_description       needle
_exptl_crystal_F_000             4240
_exptl_crystal_recrystallization_method 'solvothermal in DMF'
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.865
_refine_diff_density_min         -0.515
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.430
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     586
_refine_ls_number_reflns         4566
_refine_ls_number_restraints     287
_refine_ls_restrained_S_all      1.395
_refine_ls_R_factor_all          0.1717
_refine_ls_R_factor_gt           0.1460
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3817
_refine_ls_wR_factor_ref         0.4082
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3178
_reflns_number_total             4566
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ce01251d2.cif
_cod_data_source_block           cy082_dmf_cuaco-131023
_cod_depositor_comments
'Adding full bibliography for 7248225--7248227.cif.'
_cod_original_formula_sum        'C155.90 H101.10 Cu8 N1.30 O41.30 S32'
_cod_database_code               7248226
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C152 H96 Cu8 O40 S32'
_shelx_estimated_absorpt_t_max   0.828
_shelx_estimated_absorpt_t_min   0.366
_diffrn_oxdiff_digest_frames
;
018597a471a5eda839fadd18bfe423f91d00566791d
;
_diffrn_oxdiff_digest_hkl
;
01af7c84ed74cdb470a7db8cbd540f7c405f49
;
_reflns_odcompleteness_completeness 97.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     44.45
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1A-C3A = N1B-C3B
 1.33 with sigma of 0.02
 N1A-C2A = N1A-C1A = N1B-C2B = N1B-C1B
 1.44 with sigma of 0.02
 C3A-O1A = C3B-O1B
 1.22 with sigma of 0.02
 C30-C30_$1
 1.2 with sigma of 0.02
 C11_$1-C11
 1.25 with sigma of 0.02
 C1A-C3A = C2A-C3A = C2A-C1A = C2B-C3B = C1B-C3B = C1B-C2B
 2.45 with sigma of 0.04
 N1A-O1A = N1B-O1B
 2.25 with sigma of 0.04
 O5-C57 \\sim O6-C57 \\sim O4-C19 \\sim O3-C19 \\sim O1-C1 \\sim O2-C1 \\sim
O11-C76 \\sim O12-C76 \\sim O10-
 C20 \\sim O9-C20 \\sim O18-C68 \\sim O17-C68 \\sim O19-C39 \\sim O20-C39 \\sim
O16-C38 \\sim O15-C38
 with sigma of 0.02
3. Restrained planarity
 S14, C49, S11, C58, S15, S10
 with sigma of 0.1
 O1B, C3B, C1B, C2B, N1B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C58)
\\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C59) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.025
Uanis(C30) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(S6)
\\sim Ueq, Uanis(S7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.025
Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(S3) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(S2) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms
of 0.1
5. Rigid body (RIGU) restrains
 C30, C28, C29, S6, S7
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C9, C10, S3, C11, S2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Fixed Sof: C1A(0.25) H1AA(0.25) H1AB(0.25) H1AC(0.25) N1A(0.25) C2A(0.25)
 H2AA(0.25) H2AB(0.25) H2AC(0.25) C3A(0.25) H3A(0.25) O1A(0.25) C2B(0.33)
 C3B(0.33) N1B(0.33) O1B(0.33) C1B(0.33)
7.a Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C8(H8A,H8B), C50(H50A,H50B), C46(H46A,H46B), C27(H27A,H27B),
 C69(H69A,H69B), C61(H61A,H61B), C12(H12A,H12B)
7.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C26(H26), C22(H22), C23(H23), C72(H72), C71(H71), C75(H75),
 C74(H74), C4(H4), C3(H3), C7(H7), C6(H6), C36(H36), C37(H37), C33(H33),
 C34(H34), C42(H42), C41(H41), C45(H45), C44(H44), C17(H17), C18(H18), C14(H14),
  C15(H15), C55(H55), C56(H56), C52(H52), C53(H53), C64(H64), C66(H66),
 C67(H67), C63(H63), C3A(H3A)
7.c Fitted hexagon refined as free rotating group:
 C24(C25,C26,C21,C22,C23), C73(C72,C71,C70,C75,C74), C35(C36,C37,C32,C33,C34),
 C43(C42,C41,C40,C45,C44), C16(C17,C18,C13,C14,C15), C55(C56,C51,C52,C53,C54),
 C64(C65,C66,C67,C62,C63)
7.d Idealised Me refined with riding coordinates:
 C1A(H1AA,H1AB,H1AC), C2A(H2AA,H2AB,H2AC)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_ins_header
;
TITL CY082_DMF_CuAcO-131023 in P2(1)/m 
REM P2(1)/m (#11 in standard setting)
CELL 1.54184  19.080747  31.525297  20.060428  90.0000 104.3237  90.0000
ZERR    3.00   0.003253   0.006107   0.002468   0.0000   0.0150   0.0000
LATT  1
SYMM -x, y+1/2,-z 
SFAC C H O S Cu
UNIT 456.00 288.00 120.00 96.00 24.00
REM  CrysAlisPro recorded range (K): Min=180.0; max=180.0; aver:180.0
TEMP -93
SIZE 0.05 0.06 0.32
TREF
HKLF 4
END
;
_olex2_exptl_crystal_mounting_method 'paraffin oil'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.451
_oxdiff_exptl_absorpt_empirical_full_min 0.681