Aromatic dicarboxylate incorporated new di- and tetranuclear cobalt(II) complexes: Synthetic and structural aspects, and evaluation of properties and catalytic activity
Majumder, Avishek; Dutta, Nityananda; Haldar, Shobhraj; Das, Arpan; Carrella, Luca; Bera, Manindranath; Inorganica Chimica Acta 510 (2020) 119752–; doi:10.1016/j.ica.2020.119752

data_1564406
_publ_section_title
;
 Aromatic dicarboxylate incorporated new di- and tetranuclear cobalt(II)
 complexes: Synthetic and structural aspects, and evaluation of properties
 and catalytic activity
;
_journal_name_full               'Inorganica Chimica Acta'
_journal_page_first              119752
_journal_paper_doi               10.1016/j.ica.2020.119752
_journal_volume                  510
_journal_year                    2020
_chemical_formula_moiety         'C70 H62 Co4 N8 O14, 4.5(C H4 O), 5.5(H2 O)'
_chemical_formula_sum            'C74.5 H91 Co4 N8 O24'
_chemical_formula_weight         1718.27
_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   mixed
_cell_angle_alpha                73.494(4)
_cell_angle_beta                 85.949(3)
_cell_angle_gamma                74.975(4)
_cell_formula_units_Z            2
_cell_length_a                   14.1314(6)
_cell_length_b                   17.5517(8)
_cell_length_c                   18.0791(7)
_cell_measurement_reflns_used    8450
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.0290
_cell_measurement_theta_min      1.9450
_cell_volume                     4152.4(3)
_computing_molecular_graphics    'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0230
_diffrn_reflns_av_unetI/netI     0.0430
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            21440
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.896
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.862
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.374
_exptl_crystal_description       block
_exptl_crystal_F_000             1788
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.715
_refine_diff_density_min         -0.806
_refine_diff_density_rms         0.108
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1153
_refine_ls_number_reflns         14493
_refine_ls_number_restraints     227
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.1014
_refine_ls_R_factor_gt           0.0839
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1507P)^2^+10.9924P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2410
_refine_ls_wR_factor_ref         0.2601
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                11220
_reflns_number_total             14493
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            Co4-terephthalate.cif
_cod_data_source_block           Co4-terephthalate
_cod_original_formula_sum        'C74.50 H91 Co4 N8 O24'
_cod_database_code               1564406
_shelx_estimated_absorpt_t_max   0.874
_shelx_estimated_absorpt_t_min   0.741
_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, All C(H,H,H,H,H,H) groups, All O(H) groups, All O(H,H)
  groups
2. Restrained distances
 C73A-O22
 1.37 with sigma of 0.02
 C47-C48 \\sim C47A-C48A
 with sigma of 0.02
 C42-C41 \\sim C42A-C41A
 with sigma of 0.02
 C48-O7 \\sim C48A-O7A
 with sigma of 0.02
 C48-O8 \\sim C48A-O8A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O8A \\sim O8: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
C48A \\sim C48: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
O7A \\sim O7: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
C47A \\sim C47: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
C46A \\sim C46: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
C45A \\sim C45: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
C44A \\sim C44: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
C43A \\sim C43: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
C42A \\sim C42: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
C41A \\sim C41: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
Co4A \\sim Co4: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
Co2A \\sim Co2: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
Uanis(C71) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C41A) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42A) \\sim Ueq, Uanis(C42)
\\sim Ueq, Uanis(C43A) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq,
Uanis(C44A) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C45A) \\sim Ueq, Uanis(C47)
\\sim Ueq, Uanis(C46A) \\sim Ueq, Uanis(C47A) \\sim Ueq, Uanis(C48) \\sim Ueq,
Uanis(C48A) \\sim Ueq, Uanis(O8A) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(O7)
\\sim Ueq, Uanis(O7A) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(O26A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C73A) \\sim Ueq, Uanis(O22) \\sim Ueq, Uanis(O21A) \\sim Ueq, Uanis(O21)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(Co2A)=1-FVAR(1)
 Sof(Co2)=FVAR(1)
 Sof(Co4A)=1-FVAR(2)
 Sof(Co4)=FVAR(2)
 Fixed Sof: O7(0.5) O8(0.5) C41(0.5) H41A(0.5) H41B(0.5) C42(0.5) C47(0.5)
 C46(0.5) H46(0.5) C45(0.5) H45(0.5) C44(0.5) H44(0.5) C43(0.5) H43(0.5)
 C48(0.5) C75(0.6) H75A(0.6) H75B(0.6) H75C(0.6) H24(0.6) H24C(0.4) O26A(0.5)
 H26A(0.5) H26B(0.5) O15(0.75) H15A(0.75) O15A(0.25) H15B(0.25) H71A(0.75)
 H71B(0.75) H71C(0.75) H71D(0.25) H71E(0.25) H71F(0.25) O21(0.5) H21A(0.5)
 H21B(0.5) O21A(0.5) H21C(0.5) H21D(0.5) O22(0.5) H22A(0.5) C73A(0.5) H73A(0.5)
 H73B(0.5) H73C(0.5) O8A(0.5) C48A(0.5) O7A(0.5) C42A(0.5) C47A(0.5) C46A(0.5)
 H46A(0.5) C45A(0.5) H45A(0.5) C44A(0.5) H44A(0.5) C43A(0.5) H43A(0.5)
 C41A(0.5) H41C(0.5) H41D(0.5) C75A(0.4) H75D(0.4) H75E(0.4) H75F(0.4)
5.a Riding coordinates:
 O24(H24), O24(H24C), C71(H71A,H71B,H71C), C71(H71D,H71E,H71F)
5.b Free rotating group:
 O26A(H26A,H26B), O25(H25A,H25B), O17(H17A,H17B), O18(H18C,H18D), O20(H20A,
 H20B), O21(H21A,H21B), O21A(H21C,H21D)
5.c Ternary CH refined with riding coordinates:
 C1(H1), C32(H32)
5.d Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C10(H10A,H10B), C18(H18A,H18B),
 C24(H24A,H24B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C41(H41A,H41B),
  C49(H49A,H49B), C55(H55A,H55B), C41A(H41C,H41D)
5.e Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C12(H12), C13(H13), C14(H14), C15(H15),
 C20(H20), C21(H21), C22(H22), C23(H23), C26(H26), C27(H27), C28(H28), C29(H29),
  C37(H37), C38(H38), C39(H39), C40(H40), C46(H46), C45(H45), C44(H44),
 C43(H43), C51(H51), C52(H52), C53(H53), C54(H54), C57(H57), C58(H58), C59(H59),
  C60(H60), C65(H65), C66(H66), C68(H68), C69(H69), C46A(H46A), C45A(H45A),
 C44A(H44A), C43A(H43A)
5.f Fitted hexagon refined as free rotating group:
 C42(C47,C46,C45,C44,C43), C42A(C47A,C46A,C45A,C44A,C43A)
5.g Idealised Me refined as rotating group:
 C75(H75A,H75B,H75C), C74(H74A,H74B,H74C), C72(H72A,H72B,H72C), C73A(H73A,H73B,
 H73C), C75A(H75D,H75E,H75F)
5.h Idealised tetrahedral OH refined as rotating group:
 O23(H23A), O15(H15A), O15A(H15B), O16(H16), O22(H22A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              42030
_shelx_hkl_checksum              65751
_shelx_fab_checksum              78222
_olex2_submission_special_instructions 'No special instructions were received'