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_7123871
_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 syn
_chemical_formula_moiety         'C160 H144 Cu4 N40 O8, 5(N O3), H2 O'
_chemical_formula_sum            'C160 H146 Cu4 N48 O33'
_chemical_formula_weight         3523.40
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_symmetry_space_group_name_Hall  'P 4cw'
_symmetry_space_group_name_H-M   'P 43'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-03-10
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.6571(7)
_cell_length_b                   23.6571(7)
_cell_length_c                   31.1834(11)
_cell_measurement_reflns_used    6039
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      64.96
_cell_measurement_theta_min      3.740
_cell_volume                     17452.1(10)
_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      100.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_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  0.0576
_diffrn_reflns_av_unetI/netI     0.0686
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            88981
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.417
_diffrn_reflns_theta_min         3.395
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.254
_exptl_absorpt_correction_T_max  0.7475
_exptl_absorpt_correction_T_min  0.4929
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0798 before and 0.0524 after correction. The Ratio of minimum to maximum transmission is 0.6594. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.341
_exptl_crystal_description       plate
_exptl_crystal_F_000             7288
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.623
_refine_diff_density_min         -0.714
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 8143 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.008(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2083
_refine_ls_number_reflns         31736
_refine_ls_number_restraints     112
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.1002
_refine_ls_R_factor_gt           0.0752
_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^)+(0.1428P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2006
_refine_ls_wR_factor_ref         0.2343
_reflns_Friedel_coverage         0.948
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                22806
_reflns_number_total             31736
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03316e2.cif
_cod_data_source_block           Cu4H214NO38
_cod_original_cell_volume        17452.1(12)
_cod_database_code               7123871
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.929
_shelx_estimated_absorpt_t_min   0.806
_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, All O(H,H) groups
2. Restrained distances
 C47-C53
 1.45 with sigma of 0.01
 H24D-O9
 2.004 with sigma of 0.01
 H24C-O21
 1.911 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C47) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C50)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C48) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C92, C91, C90, C89, C88, C87
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C47, C52, C51, C50, C49, C48
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5.a Free rotating group:
 O24(H24C,H24D)
5.b Ternary CH refined with riding coordinates:
 C79(H79), C159(H159), C7(H7), C133(H133), C53(H53), C93(H93), C33(H33),
 C119(H119)
5.c Secondary CH2 refined with riding coordinates:
 C70(H70A,H70B), C150(H15A,H15B), C143(H14A,H14B), C103(H10A,H10B), C17(H17A,
 H17B), C63(H63A,H63B), C24(H24A,H24B), C110(H11A,H11B)
5.d Me refined with riding coordinates:
 C54(H54A,H54B,H54C), C120(H12A,H12B,H12C)
5.e Aromatic/amide H refined with riding coordinates:
 N35(H35), N16(H16), N36(H36), N15(H15), N5(H5), N26(H26), N6(H6), C13(H13),
 C14(H14), N25(H25), C148(H148), C154(H154), C67(H67), C155(H155), C109(H109),
 C23(H23), C74(H74), C145(H145), C9(H9), C82(H82), C21(H21), C147(H147),
 C73(H73), C149(H149), C85(H85), C83(H83), C75(H75), C105(H105), C107(H107),
 C100(H100), C78(H78), C12(H12), C84(H84), C19(H19), C66(H66), C163(H163),
 C27(H27), C69(H69), C153(H153), C158(H158), C86(H86), C140(H140), C65(H65),
 C98(H98), C22(H22), C130(H130), C164(H164), C139(H139), C60(H60), C115(H115),
 C135(H135), C129(H129), C113(H113), C29(H29), C28(H28), C32(H32), C166(H166),
 C108(H108), C162(H162), C36(H36A), C114(H114), C38(H38), C37(H37), C58(H58),
 C165(H165), C55(H55), C59(H59), C138(H138), C118(H118), C124(H124), C123(H123),
  C95(H95), C91(H91), C90(H90), C89(H89), C88(H88), C87(H87), C40(H40),
 C122(H122), C39(H39), C126(H126), C128(H128), C125(H125), C52(H52), C51(H51),
 C50(H50), C49(H49), C48(H48), C127(H127), C99(H99), C5(H5A), C4(H4), C3(H3),
 C1(H1), C2(H2), C131(H131)
5.f Fitted hexagon refined as free rotating group:
 C92(C91,C90,C89,C88,C87), C47(C52,C51,C50,C49,C48)
5.g Idealised Me refined as rotating group:
 C160(H16A,H16B,H16C), C134(H13A,H13B,H13C), C8(H8A,H8B,H8C), C80(H80A,H80B,
 H80C), C34(H34A,H34B,H34C), C94(H94A,H94B,H94C)
;
_shelx_res_checksum              19077
_shelx_fab_checksum              19362
_olex2_submission_special_instructions 'No special instructions were received'