Dipole Fluctuation and Structural Phase Transition in Hydrogen-Bonding Molecular Assemblies of Mononuclear CuII Complexes with Polar Fluorobenzoate Ligands
Takahashi, Kiyonori; Miyazaki, Yuji; Noro, Shin-ichiro; Nakano, Motohiro; Nakamura, Takayoshi; Akutagawa, Tomoyuki; Dalton Transactions  (2021) –; doi:10.1039/D1DT02118D

data_7708086
_publ_section_title
;
 Dipole Fluctuation and Structural Phase Transition in Hydrogen-Bonding
 Molecular Assemblies of Mononuclear CuII Complexes with Polar
 Fluorobenzoate Ligands
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT02118D
_journal_year                    2021
_chemical_formula_moiety         'C24 H19 Cu F2 N2 O5'
_chemical_formula_sum            'C24 H19 Cu F2 N2 O5'
_chemical_formula_weight         516.95
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-05 deposited with the CCDC.	2021-08-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.2320(10)
_cell_angle_gamma                90
_cell_formula_units_Z            20
_cell_length_a                   15.8640(3)
_cell_length_b                   29.7886(6)
_cell_length_c                   23.6221(4)
_cell_measurement_reflns_used    18378
_cell_measurement_temperature    160
_cell_measurement_theta_max      68.21
_cell_measurement_theta_min      2.96
_cell_volume                     11154.5(4)
_computing_cell_refinement       'RAPID AUTO'
_computing_data_collection       'RAPID AUTO (Rigaku, ????)'
_computing_data_reduction        'RAPID AUTO'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      160
_diffrn_detector_area_resol_mean 10.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       \w
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.0974
_diffrn_reflns_av_unetI/netI     0.0818
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            62172
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.687
_diffrn_reflns_theta_max         68.257
_diffrn_reflns_theta_min         2.967
_exptl_absorpt_coefficient_mu    1.883
_exptl_absorpt_correction_T_max  0.828
_exptl_absorpt_correction_T_min  0.562
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'ABSCOR (Rigaku, 1995)'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.539
_exptl_crystal_description       block
_exptl_crystal_F_000             5280
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.758
_refine_diff_density_min         -0.929
_refine_diff_density_rms         0.137
_refine_ls_extinction_coef       0.000078(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/1 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     839
_refine_ls_number_reflns         10209
_refine_ls_number_restraints     331
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.1951
_refine_ls_R_factor_gt           0.1481
_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^)+512.1298P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2804
_refine_ls_wR_factor_ref         0.2981
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6563
_reflns_number_total             10209
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02118d2.cif
_cod_data_source_block           shelxl_trans
_cod_database_code               7708086
_shelx_shelxl_version_number     2018/1
_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 O(H) groups
2. Restrained distances
 C52-C53
 1.4 with sigma of 0.001
 C50-C51
 1.4 with sigma of 0.001
 C50A-C49B
 1.53 with sigma of 0.01
 F5A-C52
 2.24 with sigma of 0.04
 F5A-C54A
 2.24 with sigma of 0.04
 C52-F5
 2.24 with sigma of 0.01
 C38-C39 \\sim C38-C39A
 with sigma of 0.02
 C50A-C49A \\sim C50A-C49B
 with sigma of 0.02
 C50-C49A \\sim C50-C49B
 with sigma of 0.02
 O13-C49A \\sim O13-C49B
 with sigma of 0.02
 C39-C40 \\sim C39A-C40A
 with sigma of 0.02
 C38-C40 \\sim C38-C40A
 with sigma of 0.04
 C40-C41 \\sim C40A-C41
 with sigma of 0.02
 C39-C41 \\sim C39A-C41
 with sigma of 0.04
 C41-C43 \\sim C41-C43A
 with sigma of 0.04
 C38-C43 \\sim C38-C43A
 with sigma of 0.02
 C38-C42 \\sim C38-C42A
 with sigma of 0.04
 C42-C43 \\sim C42A-C43A
 with sigma of 0.02
 C41-C42 \\sim C41-C42A
 with sigma of 0.02
3. Restrained planarity
 C50A, C49B, O13, O14A
 with sigma of 0.05
4. Rigid bond restraints
 C53A, F5A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
5. Uiso/Uaniso restraints and constraints
C34 \\sim C35 \\sim C36: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O14A \\sim C49A \\sim C50A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
F2 \\sim C17: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C50 \\sim O13: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
F5A \\sim C53A \\sim C52 \\sim C51 \\sim C50A \\sim C55A \\sim C54A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C41 \\sim C42A \\sim C43A \\sim C38: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C41 \\sim C42 \\sim C43 \\sim C38 \\sim C39 \\sim C40: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O13 \\sim C49B \\sim C50A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C49B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
C51 \\sim C50 \\sim C55: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
6. Rigid body (RIGU) restrains
 F2, O4, O5, C13, C15, C16, C17, C18, C19, C56
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O14A, C49A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F5, C53, C54, C55, C50, C51, C52
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F5, C53
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C38, C43A, C42A, C41, C40A, C39A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22, C21, C20
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
7. Others
 Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(H43A)=Sof(C39A)=Sof(H39A)=Sof(C40A)=
 Sof(H40A)=1-FVAR(1)
 Sof(C39)=Sof(H39)=Sof(C40)=Sof(H40)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43)=FVAR(1)
 Fixed Sof: H3(0.5) F5(0.7) H6A(0.5) H9A(0.5) H12(0.5) H15(0.5) C50(0.7)
 C53(0.7) C54(0.7) H54(0.7) C55(0.7) H55(0.7) F5A(0.3) C50A(0.3) H51(0.7)
 H51A(0.3) H52(0.7) H52A(0.3) C53A(0.3) C54A(0.3) H54A(0.3) C55A(0.3) H55A(0.3)
 C49A(0.7) C49B(0.3)
8.a Aromatic/amide H refined with riding coordinates:
 C3(H3A), C4(H4), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12A), C15(H15A), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21),
 C22(H22), C23(H23), C24(H24), C27(H27), C28(H28), C30(H30), C31(H31), C32(H32),
  C33(H33), C34(H34), C35(H35), C36(H36), C39(H39), C40(H40), C42(H42),
 C43(H43), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C54(H54), C55(H55),
  C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), C42A(H42A), C43A(H43A),
 C39A(H39A), C40A(H40A), C51(H51), C51(H51A), C52(H52), C52(H52A), C54A(H54A),
 C55A(H55A)
8.b Fitted hexagon refined as free rotating group:
 C38(C39,C40,C41,C42,C43), C50A(C51,C52,C53A,C54A,C55A)
8.c Tetrahedral OH refined with riding coordinates:
 O3(H3), O6(H6A), O9(H9A), O12(H12), O15(H15)
;
_shelx_res_checksum              10600
_shelx_hkl_checksum              52905
_olex2_submission_special_instructions 'No special instructions were received'