Strong antiferromagnetic coupling of the cobalt(ii)‒semiquinone radical in a dinuclear complex with 2,2′-bipyrimidine ligands
Wang, Jin-Hua; Dai, Jing-Wei; Li, Zhao-Yang; Yamashita, Masahiro; New Journal of Chemistry 44 (2020) 8471–8476; doi:10.1039/D0NJ00767F

data_7059544
_publ_section_title
;
 Strong antiferromagnetic coupling of the cobalt(ii)--semiquinone radical
 in a dinuclear complex with 2,2&#x2032;-bipyrimidine ligands
;
_journal_issue                   20
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              8471
_journal_page_last               8476
_journal_paper_doi               10.1039/D0NJ00767F
_journal_volume                  44
_journal_year                    2020
_chemical_formula_moiety         'C64 H86 Co2 N4 O8, 4(C14 H22 O2)'
_chemical_formula_sum            'C120 H174 Co2 N4 O16'
_chemical_formula_weight         2046.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-04-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-04-23 deposited with the CCDC.	2020-04-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 120.352(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   19.1994(4)
_cell_length_b                   24.9081(5)
_cell_length_c                   14.3120(3)
_cell_measurement_reflns_used    9371
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.7410
_cell_measurement_theta_min      3.2440
_cell_volume                     5906.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_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_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0161
_diffrn_reflns_av_unetI/netI     0.0227
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14352
_diffrn_reflns_point_group_measured_fraction_full 0.809
_diffrn_reflns_point_group_measured_fraction_max 0.809
_diffrn_reflns_theta_full        68.984
_diffrn_reflns_theta_max         68.984
_diffrn_reflns_theta_min         3.203
_exptl_absorpt_coefficient_mu    2.684
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72661
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.151
_exptl_crystal_description       block
_exptl_crystal_F_000             2208
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.566
_refine_diff_density_min         -0.458
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.531(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     861
_refine_ls_number_reflns         8908
_refine_ls_number_restraints     1046
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0603
_refine_ls_R_factor_gt           0.0577
_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^)+(0.0638P)^2^+10.0055P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1493
_refine_ls_wR_factor_ref         0.1512
_reflns_Friedel_coverage         0.585
_reflns_Friedel_fraction_full    0.613
_reflns_Friedel_fraction_max     0.613
_reflns_number_gt                8333
_reflns_number_total             8908
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0nj00767f2.cif
_cod_data_source_block           c2
_cod_depositor_comments
;Adding full bibliography for 7059544--7059545.cif.

 Adding full bibliography for 7059544--7059545.cif.
;
_cod_database_code               7059544
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.689
_shelx_estimated_absorpt_t_min   0.453
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.469(8)
 0.531(8)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3. Restrained distances
 C20-O4
 1.3 with sigma of 0.02
 O6B-C33 \\sim O6-C29
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O6 \\sim O6B: within 1.7A with sigma of 0.0001 and sigma for terminal atoms of
0.0002
O1 \\sim O2 \\sim O3 \\sim O4 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5
\\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11A \\sim C12A \\sim C13A
\\sim C14A \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26A \\sim C27A \\sim C28A
\\sim O1A \\sim O2A \\sim O3A \\sim O4A \\sim C1A \\sim C2A \\sim C3A \\sim C4A
\\sim C5A \\sim C6A \\sim C7A \\sim C8A \\sim C9A \\sim C10A \\sim C11B \\sim
C12B \\sim C13B \\sim C14B \\sim C15A \\sim C16A \\sim C17A \\sim C18A \\sim
C19A \\sim C20A \\sim C21A \\sim C22A \\sim C23A \\sim C24A \\sim C25A \\sim
C26B \\sim C27B \\sim C28B \\sim O5 \\sim C29 \\sim C30 \\sim C31 \\sim C32
\\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim O6
\\sim C40A \\sim C41A \\sim C42A \\sim O6B \\sim C40B \\sim C41B \\sim C42B
\\sim O7 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim O8 \\sim C54A \\sim C55A \\sim
C56A \\sim O8B \\sim C54B \\sim C55B \\sim C56B: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.02
Uanis(O6B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O2A) \\sim Ueq, Uanis(C1A) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(O1A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C11B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C40B)=Sof(H40D)=Sof(H40E)=Sof(H40F)=Sof(C41B)=Sof(H41D)=Sof(H41E)=
 Sof(H41F)=Sof(C42B)=Sof(H42D)=Sof(H42E)=Sof(H42F)=1-FVAR(1)
 Sof(C40A)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C41A)=Sof(H41A)=Sof(H41B)=
 Sof(H41C)=Sof(C42A)=Sof(H42A)=Sof(H42B)=Sof(H42C)=FVAR(1)
 Sof(C54B)=Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C55B)=Sof(H55D)=Sof(H55E)=
 Sof(H55F)=Sof(C56B)=Sof(H56D)=Sof(H56E)=Sof(H56F)=1-FVAR(2)
 Sof(C54A)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55A)=Sof(H55A)=Sof(H55B)=
 Sof(H55C)=Sof(C56A)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(2)
 Sof(H43)=Sof(O8B)=Sof(H8BA)=1-FVAR(3)
 Sof(H47)=Sof(O8)=Sof(H8)=FVAR(3)
 Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(O4A)=Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(H3A)=
 Sof(C4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(C7A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=
 Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=Sof(C11B)=Sof(C12B)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13B)=
 Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14B)=Sof(H14D)=Sof(H14E)=Sof(H14F)=
 Sof(C15A)=Sof(C16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(C19A)=Sof(H19A)=
 Sof(C20A)=Sof(C21A)=Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C23A)=
 Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=
 Sof(C25A)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27B)=Sof(H27D)=
 Sof(H27E)=Sof(H27F)=Sof(C28B)=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(4)
 Sof(O1)=Sof(O2)=Sof(O3)=Sof(O4)=Sof(C1)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=
 Sof(C5)=Sof(H5)=Sof(C6)=Sof(C7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=
 Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11A)=
 Sof(C12A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13A)=Sof(H13A)=Sof(H13B)=
 Sof(H13C)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(C16)=Sof(C17)=
 Sof(H17)=Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(C21)=Sof(C22)=Sof(H22A)=
 Sof(H22B)=Sof(H22C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C24)=Sof(H24A)=
 Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27A)=
 Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28A)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(4)
 Sof(H29)=Sof(O6B)=Sof(H6B)=1-FVAR(5)
 Sof(H33)=Sof(O6)=Sof(H6)=FVAR(5)
 Fixed X: C1(0.2872) C2(0.36648) C3(0.37307) C4(0.31059) C5(0.236769)
 C6(0.2227) C7(0.434969) C8(0.51698) C9(0.416039) C10(0.44177) C11A(0.326281)
 C12A(0.38209) C13A(0.368871) C14A(0.25113) C21(0.20229) C22(0.240549)
 C23(0.240669) C24(0.112221) C25(0.31511) C26A(0.402029) C27A(0.316449)
 C28A(0.275569) C7A(0.43298) C8A(0.51283) C9A(0.416679) C10A(0.45162)
 C11B(0.33418) C12B(0.39958) C13B(0.36163) C14B(0.258321) C21A(0.20859)
 C22A(0.2534) C23A(0.247519) C24A(0.118811) C25A(0.30307) C26B(0.369981)
 C27B(0.240669) C28B(0.33225) C35(-0.062171) C36(-0.01173) C37(-0.11098) C38(-
 0.00382) C39(-0.336009) C40A(-0.36561) C41A(-0.378389) C42A(-0.35654) C40B(-
 0.356119) C41B(-0.3845) C42B(-0.379959) C49(0.05964) C50(0.00117) C51(0.01713)
 C52(0.111731) C53(0.339549) C54A(0.38171) C55A(0.36713) C56A(0.37026)
 C54B(0.36272) C55B(0.381391) C56B(0.353971)
 Fixed Y: C1(0.8829) C2(0.87115) C3(0.82485) C4(0.788469) C5(0.79878)
 C6(0.84546) C7(0.91089) C8(0.88932) C9(0.96315) C10(0.92058) C11A(0.740109)
 C12A(0.70309) C13A(0.761161) C14A(0.707809) C21(0.95416) C22(0.90144)
 C23(0.971049) C24(0.946219) C25(1.135509) C26A(1.118761) C27A(1.17636)
 C28A(1.161231) C7A(0.96996) C8A(0.98786) C9A(0.911921) C10A(0.96504)
 C11B(1.14005) C12B(1.17504) C13B(1.129861) C14B(1.17637) C21A(0.92696)
 C22A(0.9779) C23A(0.908509) C24A(0.935809) C25A(0.739519) C26B(0.732309)
 C27B(0.694449) C28B(0.734009) C35(0.769469) C36(0.71707) C37(0.759549)
 C38(0.817841) C39(0.818181) C40A(0.79906) C41A(0.776079) C42A(0.8742)
 C40B(0.86143) C41B(0.77076) C42B(0.85057) C49(1.111871) C50(1.06699)
 C51(1.162841) C52(1.12205) C53(1.06988) C54A(1.113851) C55A(1.01335)
 C56A(1.076139) C54B(1.09376) C55B(1.09476) C56B(1.0122)
 Fixed Z: C1(0.5501) C2(0.56559) C3(0.51997) C4(0.457589) C5(0.44176)
 C6(0.484479) C7(0.631061) C8(0.653851) C9(0.566469) C10(0.74029) C11A(0.40232)
 C12A(0.49323) C13A(0.33968) C14A(0.3226) C21(0.17718) C22(0.234519)
 C23(0.11048) C24(0.09873) C25(0.35929) C26A(0.39423) C27A(0.44078)
 C28A(0.24618) C7A(0.63381) C8A(0.642241) C9A(0.58966) C10A(0.74988)
 C11B(0.41062) C12B(0.496019) C13B(0.322121) C14B(0.33998) C21A(0.18737)
 C22A(0.24966) C23A(0.12252) C24A(0.110701) C25A(0.35777) C26B(0.473129)
 C27B(0.33791) C28B(0.277369) C35(0.123811) C36(0.17799) C37(0.004519)
 C38(0.14497) C39(0.08046) C40A(-0.047911) C41A(0.11903) C42A(0.07982) C40B(-
 0.023272) C41B(0.01895) C42B(0.125541) C49(0.87089) C50(0.8526) C51(0.82077)
 C52(0.994539) C53(0.92307) C54A(0.89029) C55A(0.902659) C56A(1.03597)
 C54B(1.03376) C55B(0.86795) C56B(0.935889)
6.a Riding coordinates:
 C54B(H54D,H54E,H54F)
6.b Aromatic/amide H refined with riding coordinates:
 C57(H57), C58(H58), C59(H59), C3(H3), C5(H5), C17(H17), C19(H19), C3A(H3A),
 C5A(H5A), C17A(H17A), C19A(H19A), C29(H29), C31(H31), C33(H33), C43(H43),
 C45(H45), C47(H47)
6.c Fitted hexagon refined as free rotating group:
 C1A(C2A,C3A,C4A,C5A,C6A)
6.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12A(H12A,H12B,H12C),
 C13A(H13A,H13B,H13C), C14A(H14A,H14B,H14C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C26A(H26A,H26B,H26C), C27A(H27A,H27B,H27C),
 C28A(H28A,H28B,H28C), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC), C10A(H10D,H10E,
 H10F), C12B(H12D,H12E,H12F), C13B(H13D,H13E,H13F), C14B(H14D,H14E,H14F),
 C22A(H22D,H22E,H22F), C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F), C26B(H26D,
 H26E,H26F), C27B(H27D,H27E,H27F), C28B(H28D,H28E,H28F), C36(H36A,H36B,H36C),
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40A(H40A,H40B,H40C), C41A(H41A,H41B,
 H41C), C42A(H42A,H42B,H42C), C40B(H40D,H40E,H40F), C41B(H41D,H41E,H41F),
 C42B(H42D,H42E,H42F), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,
 H52C), C54A(H54A,H54B,H54C), C55A(H55A,H55B,H55C), C56A(H56A,H56B,H56C),
 C55B(H55D,H55E,H55F), C56B(H56D,H56E,H56F)
6.e Idealised tetrahedral OH refined as rotating group:
 O5(H5B), O6(H6), O6B(H6B), O7(H7), O8(H8), O8B(H8BA)
;
_shelx_res_checksum              1541
_olex2_submission_special_instructions 'No special instructions were received'