A redox active rod coordination polymer from tetrakis(4-carboxylic acid biphenyl)tetrathiafulvalene.
Zigon, Nicolas; Solano, Federica; Auban-Senzier, Pascale; Grolleau, Stéphane; Devic, Thomas; Zolotarev, Pavel N.; Proserpio, Davide M.; Barszcz, Bolesław; Olejniczak, Iwona; Avarvari, Narcis; Dalton transactions (Cambridge, England : 2003) 53 (2024) 4805–4813; doi:10.1039/d3dt04280d

data_7715087
_publ_section_title
;
 A redox active rod coordination polymer from tetrakis(4-carboxylic acid
 biphenyl)tetrathiafulvalene.
;
_journal_issue                   10
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4805
_journal_page_last               4813
_journal_paper_doi               10.1039/d3dt04280d
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         '0.5(C116 H64 O16 S8 Zn4), 2(C4 H9 N O)'
_chemical_formula_sum            'C66 H50 N2 O10 S4 Zn2'
_chemical_formula_weight         1290.06
_chemical_name_systematic        'TTF(PhPhCOO)4 Zn2 DMAc'
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-C 2y'
_space_group_name_H-M_alt        'C 1 2/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-21
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2023-10-10 deposited with the CCDC.	2024-02-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.076(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.8818(3)
_cell_length_b                   34.912(2)
_cell_length_c                   18.5705(12)
_cell_measurement_reflns_used    2193
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      71.5240
_cell_measurement_theta_min      5.0780
_cell_volume                     3784.3(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1990
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.955
_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   -113.00 -25.00   1.00   20.00    --  -41.11 -38.00-120.00   88
  2  \w    -27.00  66.00   1.00   20.00    --   41.11 -77.00  30.00   93
  3  \w     32.00  71.00   1.00   70.00    --  103.45 -61.00 -30.00   39
  4  \w     31.00 105.00   1.00   70.00    --  103.45 -77.00 -90.00   74
  5  \w     82.00 158.00   1.00   70.00    --  103.45  77.00 120.00   76
  6  \w     30.00 111.00   1.00   70.00    --  103.45-125.00 -90.00   81
  7  \w     33.00  71.00   1.00   70.00    --  103.45 -61.00 150.00   38
  8  \w     59.00 149.00   1.00   70.00    --  103.45  15.00  90.00   90
  9  \w     40.00  86.00   1.00   70.00    --  103.45 -77.00  90.00   46
;
_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      -0.0793291000
_diffrn_orient_matrix_UB_12      -0.0196809000
_diffrn_orient_matrix_UB_13      0.0668910000
_diffrn_orient_matrix_UB_21      0.0270601000
_diffrn_orient_matrix_UB_22      0.0381367000
_diffrn_orient_matrix_UB_23      0.0419473000
_diffrn_orient_matrix_UB_31      -0.2500401000
_diffrn_orient_matrix_UB_32      0.0104102000
_diffrn_orient_matrix_UB_33      -0.0274429000
_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  0.0365
_diffrn_reflns_av_unetI/netI     0.0536
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            7072
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.847
_diffrn_reflns_theta_min         2.531
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.210
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.917
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.45a (Rigaku Oxford Diffraction, 2019)
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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.132
_exptl_crystal_description       prism
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.084
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.058
_refine_diff_density_max         0.406
_refine_diff_density_min         -0.553
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     292
_refine_ls_number_reflns         3615
_refine_ls_number_restraints     106
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0748
_refine_ls_R_factor_gt           0.0548
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0895P)^2^+0.7089P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1455
_refine_ls_wR_factor_ref         0.1595
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2574
_reflns_number_total             3615
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt04280d2.cif
_cod_data_source_block           exp_1480
_cod_depositor_comments
'Adding full bibliography for 7715087--7715088.cif.'
_cod_database_code               7715087
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C56H32S4O8Zn1N1O3
_chemical_oxdiff_usercomment     'purple plate'
_diffrn_oxdiff_digest_frames
;
013e0bf6671986d61549b91e30e0e1bcd500653cc3d
;
_diffrn_oxdiff_digest_hkl
;
01376fa8478da3c77d242dc25617beb19cab71
;
_reflns_odcompleteness_completeness 98.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 N22A-C20A = N22A-C23A
 1.44 with sigma of 0.02
 N22A-C25A
 1.36 with sigma of 0.02
 C20A-C23A
 2.48 with sigma of 0.04
 C23A-C25A
 2.41 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C9A \\sim C10A \\sim C12A \\sim C13A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C9B \\sim C10B \\sim C12B \\sim C13B: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C22A \\sim C25A \\sim C23A \\sim N22A \\sim O21A \\sim C20A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C22A) \\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(C23A) \\sim Ueq,
Uanis(N22A) \\sim Ueq, Uanis(O21A) \\sim Ueq, Uanis(C20A) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(N22B) = Uanis(C25B) = Uanis(C22B) = Uanis(C23B) = Uanis(O21B) =
Uanis(C20B)
Uanis(N22A) = Uanis(C25A) = Uanis(C22A) = Uanis(C23A) = Uanis(O21A) =
Uanis(C20A)
4. Same fragment restrains
{C25A, N22A, C22A, C23A, O21A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C25B, N22B, C22B, C23B, O21B, C20B}
5. Others
 Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=1-
 FVAR(1)
 Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=FVAR(1)
 Sof(C9B)=Sof(H9B)=Sof(C10B)=Sof(H10B)=Sof(C12B)=Sof(H12B)=Sof(C13B)=Sof(H13B)=
 1-FVAR(2)
 Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13A)=
 FVAR(2)
 Fixed Sof: C22A(0.25) H22A(0.25) H22B(0.25) H22C(0.25) C25A(0.25) C23A(0.25)
 H23A(0.25) H23B(0.25) H23C(0.25) N22A(0.25) O21A(0.25) C20A(0.25) H20A(0.25)
 H20B(0.25) H20C(0.25) C25B(0.25) N22B(0.25) C22B(0.25) H22D(0.25) H22E(0.25)
 H22F(0.25) C23B(0.25) H23D(0.25) H23E(0.25) H23F(0.25) O21B(0.25) C20B(0.25)
 H20D(0.25) H20E(0.25) H20F(0.25)
6.a Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C6A(H6A), C7A(H7A), C9A(H9A), C10A(H10A), C12A(H12A),
 C13A(H13A), C3B(H3B), C4B(H4B), C6B(H6B), C7B(H7B), C9B(H9B), C10B(H10B),
 C12B(H12B), C13B(H13B)
6.b Idealised Me refined with everything fixed:
 C23A(H23A,H23B,H23C)
6.c Idealised Me refined as rotating group:
 C22A(H22A,H22B,H22C), C20A(H20A,H20B,H20C), C22B(H22D,H22E,H22F), C23B(H23D,
 H23E,H23F), C20B(H20D,H20E,H20F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_ins_header
;
TITL exp_1480 in C2/m 
REM C2/m (#12 in standard setting)
CELL 1.54184   5.881754  34.912023  18.570473  90.0000  97.0760  90.0000
ZERR    3.00   0.000321   0.002222   0.001219   0.0000   0.0056   0.0000
LATT  7
SYMM -x, y,-z 
SFAC C H N O S Zn
UNIT 168.00 96.00 3.00 33.00 12.00 3.00
TREF
HKLF 4
END
;
_olex2_exptl_crystal_mounting_method 'paraffin oil + loop'
_olex2_submission_original_sample_id exp_1480
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.191
_oxdiff_exptl_absorpt_empirical_full_min 0.841