Reversal of magnetic exchange coupling between copper(II) and Blatter radical depending on the coordination environment
Sidharth, Thulaseedharan Nair Sailaja; Nasani, Rajendar; Gupta, Arindam; Sooraj, Bhuvanachandran Nair Sreekala; Roy, Subhadip; Mondal, Arpan; Konar, Sanjit; Inorganica Chimica Acta 503 (2020) 119395–; doi:10.1016/j.ica.2019.119395

data_1565356
_publ_section_title
;
 Reversal of magnetic exchange coupling between copper(II) and Blatter
 radical depending on the coordination environment
;
_journal_name_full               'Inorganica Chimica Acta'
_journal_page_first              119395
_journal_paper_doi               10.1016/j.ica.2019.119395
_journal_volume                  503
_journal_year                    2020
_chemical_formula_moiety         'C38 H24 Cu F6 N8, 2(Cl O4), C H4 O'
_chemical_formula_sum            'C39 H28 Cl2 Cu F6 N8 O9'
_chemical_formula_weight         1001.13
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_cell_angle_alpha                90
_cell_angle_beta                 92.042(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.4593(6)
_cell_length_b                   28.734(2)
_cell_length_c                   16.6377(12)
_cell_measurement_reflns_used    9692
_cell_measurement_temperature    140(2)
_cell_measurement_theta_max      26.47
_cell_measurement_theta_min      2.41
_cell_volume                     4041.5(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      140.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1043
_diffrn_reflns_av_unetI/netI     0.0504
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            72404
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.409
_exptl_absorpt_coefficient_mu    0.768
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6530
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.645
_exptl_crystal_description       0.4mm*0.05mm*0.005mm
_exptl_crystal_F_000             2028
_exptl_crystal_size_max          0.89
_exptl_crystal_size_mid          0.71
_exptl_crystal_size_min          0.59
_refine_diff_density_max         0.955
_refine_diff_density_min         -0.817
_refine_diff_density_rms         0.096
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     705
_refine_ls_number_reflns         7109
_refine_ls_number_restraints     290
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.0936
_refine_ls_R_factor_gt           0.0637
_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^)+(0.0602P)^2^+16.2022P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1437
_refine_ls_wR_factor_ref         0.1596
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5247
_reflns_number_total             7109
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ICA-2020-503-119395.cif
_cod_data_source_block           mo_cu_1bl2_0m
_cod_database_code               1565356
_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, All O(H) groups
2. Restrained distances
 Cl2-O5 \\sim Cl2-O8 \\sim Cl2-O7 \\sim Cl2-O6
 with sigma of 0.02
 O5-O7 \\sim O8-O6 \\sim O5-O6 \\sim O8-O7 \\sim O5-O8 \\sim O7-O6
 with sigma of 0.04
 O6'-O5' \\sim O7'-O8' \\sim O6'-O8' \\sim O7'-O5' \\sim O6'-O7' \\sim O5'-O8'
 with sigma of 0.04
 C29A-C32A \\sim C29A-C1
 with sigma of 0.02
 F22A-C32A \\sim F1-C1
 with sigma of 0.02
 F20A-C32A \\sim F2-C1
 with sigma of 0.02
 C32A-F21A \\sim C1-F3
 with sigma of 0.02
 C29A-F22A \\sim C29A-F1
 with sigma of 0.04
 C29A-F20A \\sim C29A-F2
 with sigma of 0.04
 C29A-F21A \\sim C29A-F3
 with sigma of 0.04
 F22A-F20A \\sim F1-F2
 with sigma of 0.04
 F22A-F21A \\sim F1-F3
 with sigma of 0.04
 F20A-F21A \\sim F2-F3
 with sigma of 0.04
 F21B-C32B \\sim F4-C2
 with sigma of 0.02
 F20B-C32B \\sim F5-C2
 with sigma of 0.02
 F22B-C32B \\sim F6-C2
 with sigma of 0.02
 C29B-C32B \\sim C29B-C2
 with sigma of 0.02
 F21B-F20B \\sim F4-F5
 with sigma of 0.04
 F21B-F22B \\sim F4-F6
 with sigma of 0.04
 F21B-C29B \\sim F4-C29B
 with sigma of 0.04
 F20B-F22B \\sim F5-F6
 with sigma of 0.04
 F20B-C29B \\sim F5-C29B
 with sigma of 0.04
 F22B-C29B \\sim F6-C29B
 with sigma of 0.04
 Cl2'-O6' \\sim Cl2'-O7' \\sim Cl2'-O5' \\sim Cl2'-O8'
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl2 \\sim O5 \\sim O8 \\sim O7 \\sim O6: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Cl2' \\sim O6' \\sim O7' \\sim O5' \\sim O8': within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 C29A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cl2, O5, O8, O7, O6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5, Cl2, O8, O7, O6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F22A, F20A, C32A, F21A, C29A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F1, F2, C1, F3, C29A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F21B, F20B, F22B, C32B, C29B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F4, F5, F6, C2, C29B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cl2', O6', O7', O5', O8'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5', Cl2', O6', O7', O8'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: F21B(0.7) F20B(0.7) F22B(0.7) C32B(0.7) Cl2(0.7) O5(0.7) O8(0.7)
 O7(0.7) O6(0.7) Cl2'(0.3) O6'(0.3) O7'(0.3) O5'(0.3) O8'(0.3) F22A(0.7)
 F20A(0.7) C32A(0.7) F21A(0.7) F1(0.3) F2(0.3) C1(0.3) F3(0.3) F4(0.3) F5(0.3)
 F6(0.3) C2(0.3)
6.a Aromatic/amide H refined with riding coordinates:
 C30B(H30B), C23B(H23B), C20A(H20A), C22B(H22B), C28B(H28B), C27B(H27B),
 C30A(H30A), C27A(H27A), C23A(H23A), C34A(H34A), C20B(H20B), C21B(H21B),
 C21A(H21A), C28A(H28A), C22A(H22A), C35A(H35A), C36A(H36A), C38B(H38B),
 C34B(H34B), C38A(H38A), C36B(H36B), C37A(H37A), C35B(H35B), C37B(H37B)
6.b Idealised Me refined as rotating group:
 C1S(H1SA,H1SB,H1SC)
6.c Idealised tetrahedral OH refined as rotating group:
 O1S(H1S)
;