Unexpected linkage isomerism in chiral tetranuclear bis-tridentate (1,2,3-triazol-4-yl)-picolinamide (tzpa) grids
Hegarty, Isabel; Dalton, Hannah L.; Henwood, Adam; Hawes, Chris Samuel; Gunnlaugsson, Thorfinnur; Chemical Communications  (2019) –; doi:10.1039/C9CC03316E

data_7123873
_publ_section_title
;
 Unexpected linkage isomerism in chiral tetranuclear bis-tridentate
 (1,2,3-triazol-4-yl)-picolinamide (tzpa) grids
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC03316E
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C80 H70 Cu2 N20 O4), 4(F6 P), 4(C7 H8)'
_chemical_formula_sum            'C188 H172 Cu4 F24 N40 O8 P4'
_chemical_formula_weight         3953.69
_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'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-09-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-03-24 deposited with the CCDC.    2019-07-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 131.776(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   36.3689(12)
_cell_length_b                   30.0761(11)
_cell_length_c                   26.1089(9)
_cell_measurement_reflns_used    9039
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      67.92
_cell_measurement_theta_min      3.71
_cell_volume                     21297.9(14)
_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)'
_diffrn_ambient_temperature      99.99
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0481
_diffrn_reflns_av_unetI/netI     0.0544
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            114816
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.437
_diffrn_reflns_theta_min         3.259
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.422
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6655
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0878 before and 0.0704 after correction. The Ratio of minimum to maximum transmission is 0.8837. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.233
_exptl_crystal_description       block
_exptl_crystal_F_000             8144
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.807
_refine_diff_density_min         -0.377
_refine_diff_density_rms         0.083
_refine_ls_abs_structure_details
;
 Flack x determined using 14443 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2551
_refine_ls_number_reflns         38707
_refine_ls_number_restraints     412
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0747
_refine_ls_R_factor_gt           0.0671
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1547P)^2^+1.2739P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1880
_refine_ls_wR_factor_ref         0.1998
_reflns_Friedel_coverage         0.943
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                33716
_reflns_number_total             38707
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03316e2.cif
_cod_data_source_block           Cu4H14PF64
_cod_database_code               7123873
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.727
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C174-C173
 1.45 with sigma of 0.02
 C167-C166
 1.45 with sigma of 0.02
 C166-C165 = C165-C164 = C164-C163 = C163-C162 = C162-C161 = C166-C161
 1.4 with sigma of 0.01
 C176-C175 = C177-C176 = C178-C177 = C179-C178 = C180-C179 = C180-C175
 1.4 with sigma of 0.01
 C188-C187
 1.45 with sigma of 0.02
 C169-C168 \\sim C169-C170 \\sim C170-C171 \\sim C171-C172 \\sim C172-C173
\\sim C168-C173
 with sigma of 0.01
 C200-C201 \\sim C199-C200 \\sim C199-C198 \\sim C197-C198 \\sim C197-C196
\\sim C201-C196
 with sigma of 0.01
 C39-C40 \\sim C39-C38 \\sim C38-C37 \\sim C37-C36
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C78) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(C195) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(C159) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C73, C75, C76, C77, C78, C79, C80
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C196, C197, C198, C199, C200, C201, C202
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C168, C169, C170, C171, C172, C173, C174
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C34, C35, C36, C37, C38, C39, C40
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C189, C190, C191, C192, C193, C194
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C161, C162, C163, C164, C165, C166, C167
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C175, C176, C177, C178, C179, C180
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C153, C155, C156, C157, C158, C159, C160
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: C161(0.5) H161(0.5) C162(0.5) H162(0.5) C163(0.5) H163(0.5)
 C164(0.5) H164(0.5) C165(0.5) H165(0.5) C166(0.5) C167(0.5) H16A(0.5)
 H16B(0.5) H16C(0.5) C168(0.5) H168(0.5) C169(0.5) H169(0.5) C170(0.5)
 H170(0.5) C171(0.5) H171(0.5) C172(0.5) H172(0.5) C173(0.5) C174(0.5)
 H17C(0.5) H17D(0.5) H17E(0.5) C175(0.5) H175(0.5) C176(0.5) H176(0.5)
 C177(0.5) H177(0.5) C178(0.5) H178(0.5) C179(0.5) H179(0.5) C180(0.5)
 C181(0.5) H18D(0.5) H18E(0.5) H18F(0.5) C196(0.5) H196(0.5) C197(0.5)
 H197(0.5) C198(0.5) H198(0.5) C199(0.5) H199(0.5) C200(0.5) H200(0.5)
 C201(0.5) C202(0.5) H20A(0.5) H20B(0.5) H20C(0.5)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C34(H34), C47(H47), C73(H73), C87(H87), C113(H113), C127(H127),
 C153(H153)
6.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C24(H24A,H24B), C57(H57A,H57B), C64(H64A,H64B), C97(H97A,
 H97B), C104(H10A,H10B), C137(H13A,H13B), C144(H14A,H14B)
6.c Me refined with riding coordinates:
 C167(H16A,H16B,H16C), C174(H17C,H17D,H17E)
6.d Aromatic/amide H refined with riding coordinates:
 N6(H6), N15(H15), C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C12(H12),
 C13(H13), C14(H14), C19(H19), C21(H21), C22(H22), C23(H23), C27(H27), C28(H28),
  C29(H29), C32(H32), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40),
 C41(H41), C42(H42), C43(H43), C44(H44), C45(H45), C49(H49), C52(H52), C53(H53),
  C54(H54), C59(H59), C60(H60), C61(H61), C63(H63), C67(H67), C68(H68),
 C69(H69), C72(H72), C76(H76), C77(H77), C78(H78), C79(H79), C80(H80), N26(H26),
  N35(H35), C81(H81), C82(H82), C83(H83), C84(H84), C85(H85), C89(H89),
 C92(H92), C93(H93), C94(H94), C99(H99), C100(H100), C101(H101), C103(H103),
 C107(H107), C108(H108), C109(H109), C112(H112), C116(H116), C117(H117),
 C118(H118), C119(H119), C120(H120), C121(H121), C122(H122), C123(H123),
 C124(H124), C125(H125), C129(H129), C132(H132), C133(H133), C134(H134),
 C139(H139), C140(H140), C141(H141), C143(H143), C147(H147), C148(H148),
 C149(H149), C152(H152), C156(H156), C157(H157), C158(H158), C159(H159),
 C160(H160), C161(H161), C162(H162), C163(H163), C164(H164), C165(H165),
 C189(H189), C190(H190), C191(H191), C192(H192), C193(H193), C182(H182),
 C183(H183), C184(H184), C185(H185), C186(H186), C168(H168), C169(H169),
 C170(H170), C171(H171), C172(H172), C175(H175), C176(H176), C177(H177),
 C178(H178), C179(H179), C196(H196), C197(H197), C198(H198), C199(H199),
 C200(H200)
6.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C33(H33A,H33B,H33C), C48(H48A,H48B,H48C), C74(H74A,H74B,
 H74C), C88(H88A,H88B,H88C), C114(H11A,H11B,H11C), C128(H12A,H12B,H12C),
 C154(H15A,H15B,H15C), C195(H19A,H19B,H19C), C188(H18A,H18B,H18C), C181(H18D,
 H18E,H18F), C202(H20A,H20B,H20C)
;
_shelx_res_checksum              336
_shelx_fab_checksum              90764
_olex2_submission_special_instructions 'No special instructions were received'