Ligand isomerism fine-tunes structure and stability in zinc complexes of fused pyrazolopyridines
Swarbrook, Amelia M.; Weekes, Rohan J.; Goodwin, Jack W.; Hawes, Chris S.; Dalton Transactions  (2022) –; doi:10.1039/D1DT04007C

data_7709164
_publ_section_title
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 Ligand isomerism fine-tunes structure and stability in zinc complexes of
 fused pyrazolopyridines
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT04007C
_journal_year                    2022
_chemical_formula_moiety         'C55 H44 N22 O8 Zn2, 2(N O3), 2(C2 H3 N)'
_chemical_formula_sum            'C59 H50 N26 O14 Zn2'
_chemical_formula_weight         1477.99
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2021-11-10 deposited with the CCDC.	2021-12-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.652(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.5157(9)
_cell_length_b                   23.5974(16)
_cell_length_c                   10.2149(7)
_cell_measurement_reflns_used    6475
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      22.17
_cell_measurement_theta_min      2.78
_cell_volume                     3068.1(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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  0.1566
_diffrn_reflns_av_unetI/netI     0.0974
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            61152
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.286
_diffrn_source_current           20.0
_diffrn_source_power             1.0
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.873
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6729
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0782 before and 0.0701 after correction.
The Ratio of minimum to maximum transmission is 0.9027.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.600
_exptl_crystal_description       plate
_exptl_crystal_F_000             1516
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.391
_refine_diff_density_min         -0.399
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     574
_refine_ls_number_reflns         6257
_refine_ls_number_restraints     187
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.1628
_refine_ls_R_factor_gt           0.0939
_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^)+(0.0099P)^2^+13.2189P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1304
_refine_ls_wR_factor_ref         0.1515
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3772
_reflns_number_total             6257
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt04007c2.cif
_cod_data_source_block           5beta
_cod_database_code               7709164
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.727
_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,H) groups
2. Restrained distances
 C34-C35 = C37-C36
 1.5 with sigma of 0.02
 Zn1-H1A \\sim Zn1-H1B
 with sigma of 0.02
 O6-N14 \\sim O5-N14 \\sim O5A-N14A \\sim O6A-N14A \\sim O7A-N14A \\sim O7-N14
 with sigma of 0.02
 N15A-C37 \\sim N15-C34
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C27) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C35) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(N15) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(N15A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 O5, O6, O7, N14, O5A, O6A, O7A, N14A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N9, N10, N11, N12, C23, C24, C25, C26, C27, C28, C29, C33
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: Zn1(0.5) Zn2(0.5) O5(0.5) O6(0.5) O7(0.5) N14(0.5) O5A(0.5)
 O6A(0.5) O7A(0.5) N14A(0.5) N10(0.5) N11(0.5) N12(0.5) C33(0.5) H33(0.5)
 C32(0.5) H32(0.5) C31(0.5) H31(0.5) C30(0.5) H30(0.5) C29(0.5) C25(0.5)
 C24(0.5) C23(0.5) H23(0.5) N9(0.5) C27(0.5) H27(0.5) C26(0.5) H26(0.5)
 C28(0.5) H28(0.5) N15A(0.33333) C36(0.33333) H36A(0.33333) H36B(0.33333)
 H36C(0.33333) C37(0.33333) N15(0.6667) C34(0.6667) C35(0.6667) H35A(0.6667)
 H35B(0.6667) H35C(0.6667)
6.a Free rotating group:
 O1(H1A,H1B)
6.b Me refined with riding coordinates:
 C36(H36A,H36B,H36C), C35(H35A,H35B,H35C)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C16(H16), C17(H17), C19(H19), C20(H20), C21(H21), C22(H22), C33(H33),
  C32(H32), C31(H31), C30(H30), C23(H23), C27(H27), C26(H26), C28(H28)
6.d Fitted hexagon refined as free rotating group:
 N12(C33,C32,C31,C30,C29), C25(C24,C23,N9,C27,C26)
;
_shelx_res_checksum              49258
_olex2_submission_special_instructions 'No special instructions were received'