Stars and stripes: hexatopic tris(3,2′:6′,3′′-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers
Manfroni, Giacomo; Prescimone, Alessandro; Constable, Edwin C.; Housecroft, Catherine E.; CrystEngComm 24 (2022) 491–503; doi:10.1039/D1CE01531A

data_7244015
_publ_section_title
;
 Stars and stripes: hexatopic
 tris(3,2&#x2032;:6&#x2032;,3&#x2032;&#x2032;-terpyridine) ligands that
 unexpectedly form one-dimensional coordination polymers
;
_journal_issue                   3
_journal_name_full               CrystEngComm
_journal_page_first              491
_journal_page_last               503
_journal_paper_doi               10.1039/D1CE01531A
_journal_volume                  24
_journal_year                    2022
_chemical_formula_moiety
'C102 H57.3 Cu3 F36 N9 O12, 2.2(C7 H8), 0.4(C H Cl3), 0.6[C7H8]'
_chemical_formula_sum            'C122 H80.1 Cl1.2 Cu3 F36 N9 O12'
_chemical_formula_weight         2781.21
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-05-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-13 deposited with the CCDC.	2021-12-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.32(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.889(4)
_cell_length_b                   21.178(4)
_cell_length_c                   34.375(7)
_cell_measurement_reflns_used    29003
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.0
_cell_measurement_theta_min      1.0
_cell_volume                     14029(5)
_computing_cell_refinement       'XDS (Wolfgang Kabsch, 2020)'
_computing_data_collection       'DA+ GUI (SLS, Switzerland, 2017)'
_computing_data_reduction        'XDS (Wolfgang Kabsch, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'PILATUS 2M-F'
_diffrn_detector_area_resol_mean 33.80
_diffrn_detector_type            'Dectris PILATUS 2M-F'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.942
_diffrn_measurement_device       'multi-axis PRIGo goniometer'
_diffrn_measurement_device_type  SLS
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_monochromator
;
Bartels Monochromator with dual channel cut crystals (DCCM)
in (+-+) geometry
;
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.72083
_diffrn_reflns_av_R_equivalents  0.0862
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            531703
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        25.626
_diffrn_reflns_theta_max         27.713
_diffrn_reflns_theta_min         1.097
_diffrn_source                   synchrotron
_diffrn_source_type
'2.9T superbend magnet, X06DA-PXIII beamline, SLS, (CH)'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.595
_exptl_absorpt_correction_T_max  0.954
_exptl_absorpt_correction_T_min  0.911
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.317
_exptl_crystal_description       block
_exptl_crystal_F_000             5610
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.154
_refine_diff_density_min         -1.865
_refine_diff_density_rms         0.198
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.177
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1623
_refine_ls_number_reflns         29721
_refine_ls_number_restraints     274
_refine_ls_restrained_S_all      1.197
_refine_ls_R_factor_all          0.2092
_refine_ls_R_factor_gt           0.1912
_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^)+(0.4200P)^2^+2.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4998
_refine_ls_wR_factor_ref         0.5408
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20415
_reflns_number_total             29721
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ce01531a2.cif
_cod_data_source_block           total
_cod_depositor_comments
'Adding full bibliography for 7244014--7244015.cif.'
_cod_original_formula_sum        'C122 H80.10 Cl1.20 Cu3 F36 N9 O12'
_cod_database_code               7244015
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.954
_shelx_estimated_absorpt_t_min   0.900
_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 C(H,H,H) groups
2. Restrained distances
 F32-F40 \\sim F32-F42 \\sim F40-F42
 with sigma of 0.04
 C87-F32 \\sim C87-F40 \\sim C87-F42 \\sim C87-C86
 with sigma of 0.02
 Cl1-C145 \\sim Cl2-C145 \\sim Cl3-C145
 with sigma of 0.02
 C122-F30 \\sim C122-F26 \\sim C122-F28 \\sim C122-C121
 with sigma of 0.02
 F30-F26 \\sim F30-F28 \\sim F30-C121 \\sim F26-F28 \\sim F26-C121 \\sim
F28-C121
 with sigma of 0.04
 C97-C96 \\sim C97-F52 \\sim C97-F54 \\sim C97-F7
 with sigma of 0.02
 C96-F52 \\sim C96-F54 \\sim C96-F7 \\sim F52-F54 \\sim F52-F7 \\sim F54-F7
 with sigma of 0.04
 C99-F29 \\sim C99-F15 \\sim C99-F33 \\sim F29-F15 \\sim F29-F33 \\sim F15-F33
 with sigma of 0.04
 C103-F27 \\sim C103-F31 \\sim C103-F17 \\sim F27-F31 \\sim F27-F17 \\sim
F31-F17
 with sigma of 0.04
 C100-C99 \\sim C100-F29 \\sim C100-F15 \\sim C100-F33
 with sigma of 0.02
 C107-C103 \\sim C107-F27 \\sim C107-F31 \\sim C107-F17
 with sigma of 0.02
 C111-C110 \\sim C111-F35 \\sim C111-F9 \\sim C111-F37
 with sigma of 0.02
 C110-F35 \\sim C110-F9 \\sim C110-F37 \\sim F35-F9 \\sim F35-F37 \\sim F9-F37
 with sigma of 0.04
 C87-F40 \\sim C87-F42 \\sim C87-C86 \\sim C87-F32
 with sigma of 0.02
 F19-F39 \\sim F19-F5
 with sigma of 0.04
 C87-F19 \\sim C87-F39 \\sim C87-F5 \\sim C87-C86
 with sigma of 0.02
 F40-F42 \\sim F40-F32 \\sim F42-F32
 with sigma of 0.04
 C113-C112 \\sim C113-F2 \\sim C113-F41
 with sigma of 0.02
 C113-F46 \\sim C113-C112 \\sim C113-F2 \\sim C113-F41
 with sigma of 0.02
 C112-F2 \\sim C112-F41 \\sim F2-F41
 with sigma of 0.04
 F44-F21 \\sim F44-F43
 with sigma of 0.04
 C101-F48 \\sim C101-F50 \\sim C101-F11
 with sigma of 0.02
 C106-F44 \\sim C106-C105 \\sim C106-F21 \\sim C106-F43
 with sigma of 0.02
 F48-F50 \\sim F48-F11 \\sim F50-F11
 with sigma of 0.04
 C102-C94 \\sim C102-F45 \\sim C102-F23 \\sim C102-F47
 with sigma of 0.02
 C94-F23 \\sim C94-F47 \\sim F45-F23 \\sim F23-F47
 with sigma of 0.04
 Cl6-C153 \\sim Cl5-C153 \\sim Cl4-C153
 with sigma of 0.02
 C135-C137 \\sim C138-C139 \\sim C157-C158 \\sim C124-C125
 with sigma of 0.02
 F3-F49 \\sim F3-F25
 with sigma of 0.04
 C120-C121 \\sim C120-C119
 with sigma of 0.02
 C98-C94 \\sim C108-C94 \\sim C96-C108 \\sim C98-C99
 with sigma of 0.02
 C102-C94 \\sim C101-C94
 with sigma of 0.02
 O6-C105 \\sim O6-C112 \\sim O5-C103 \\sim O5-C96 \\sim O8-C94 \\sim O7-C99
 with sigma of 0.02
 C117-C116 \\sim C114-C118 \\sim C123-C119 \\sim C122-C121
 with sigma of 0.02
 O12-C121 \\sim O11-C119 \\sim O10-C116 \\sim O9-C114
 with sigma of 0.02
 C115-C116 \\sim C114-C115 \\sim C120-C121 \\sim C120-C119
 with sigma of 0.02
 C116-F51 \\sim C116-F13 \\sim C116-F53 \\sim F51-F13 \\sim F51-F53 \\sim
F13-F53
 with sigma of 0.04
 C117-C116 \\sim C117-F51 \\sim C117-F13 \\sim C117-F53
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C145) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uiso(C143) = Uiso(C142) = Uiso(C141) = Uiso(C140) = Uiso(C139) = Uiso(C144) =
Uiso(C138)
Uanis(C45) = Uanis(C44) = Uanis(C43) = Uanis(C41) = Uanis(C40) = Uanis(C39)
Uiso(F28) = Uiso(F30) = Uiso(F49) = Uiso(F25) = Uiso(F26) = Uiso(F3)
4. Others
 Fixed Sof: F26(0.5) F28(0.5) F30(0.5) C25(0.7) H25(0.7) C16(0.5) H16(0.5)
 F32(0.5) C17(0.5) H17(0.5) C26(0.7) H26(0.7) C50(0.7) H50(0.7) C81(0.5)
 H81(0.5) C40(0.7) H40(0.7) C51(0.7) H51(0.7) C82(0.5) H82(0.5) C39(0.7)
 H39(0.7) C41(0.7) H41(0.7) C108(0.5) H108(0.5) C77(0.5) H77(0.5) C78(0.5)
 H78(0.5) F40(0.5) F42(0.5) C110(0.5) C79(0.5) H79(0.5) C80(0.5) H80(0.5)
 C135(0.4) C134(0.4) HH(0.4) C133(0.4) HI(0.4) C132(0.4) HJ(0.4) C131(0.4)
 HK(0.4) C136(0.4) HL(0.4) C154(0.25) HM(0.25) C159(0.25) HN(0.25) C157(0.25)
 C155(0.25) HO(0.25) C156(0.25) HP(0.25) C95(0.25) HQ(0.25) C158(0.25) HR(0.25)
 HS(0.25) HT(0.25) Cl1(0.2) Cl2(0.2) Cl3(0.2) C145(0.2) HU(0.2) C150(0.3)
 HV(0.3) C149(0.3) C148(0.3) HW(0.3) C147(0.3) HX(0.3) C146(0.3) HY(0.3)
 C151(0.3) HZ(0.3) C143(0.25) H4(0.25) C142(0.25) H5(0.25) C141(0.25) H7(0.25)
 C140(0.25) H9(0.25) C139(0.25) C144(0.25) H10(0.25) C138(0.25) H15(0.25)
 H18(0.25) H19(0.25) F44(0.5) C98(0.5) H98(0.5) C99(0.5) F46(0.5) C103(0.5)
 C104(0.5) H104(0.5) Cl6(0.2) C100(0.5) C46(0.3) H46(0.3) C47(0.3) H47A(0.3)
 H47B(0.3) C48(0.3) H48(0.3) C49(0.3) H49(0.3) C96(0.5) C112(0.5) F48(0.5)
 F50(0.5) C101(0.5) F52(0.5) F54(0.5) C97(0.5) F27(0.5) C107(0.5) F7(0.5)
 F29(0.5) F15(0.5) F31(0.5) F2(0.5) F33(0.5) C109(0.5) H109(0.5) C113(0.5)
 F17(0.5) C105(0.5) F35(0.5) F9(0.5) F37(0.5) C111(0.5) F19(0.5) F39(0.5)
 F5(0.5) F41(0.5) F21(0.5) F43(0.5) C106(0.5) F11(0.5) F45(0.5) F23(0.5)
 F47(0.5) C102(0.5) C44(0.3) H44(0.3) C43(0.3) H43(0.3) C45(0.3) H45(0.3)
 Cl5(0.2) Cl4(0.2) C153(0.2) H20(0.2) C152(0.3) H21(0.3) H22(0.3) H23(0.3)
 C137(0.4) H24(0.4) H27(0.4) H28(0.4) F3(0.5) F49(0.5) F25(0.5)
 Fixed Uiso: F34(0.21) F36(0.21) C118(0.21) F38(0.21)
5.a Riding coordinates:
 C108(H108), C124(HE,HF,HG), C158(HR,HS,HT), C138(H15,H18,H19), C98(H98),
 C104(H104), C153(H20), C152(H21,H22,H23), C137(H24,H27,H28)
5.b Ternary CH refined with riding coordinates:
 C145(HU)
5.c Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B)
5.d Aromatic/amide H refined with riding coordinates:
 C35(H35), C42(H42), C70(H70), C83(H83), C14(H14), C6(H6), C65(H65), C8(H8),
 C63(H63), C73(H73), C11(H11), C29(H29), C60(H60), C67(H67), C64(H64), C90(H90),
  C66(H66), C36(H36), C13(H13), C12(H12), C57(H57), C56(H56), C75(H75),
 C72(H72), C74(H74), C1(H1), C71(H71), C85(H85), C128(H), C34(H34), C127(HA),
 C129(HB), C3(H3), C120(H120), C25(H25), C16(H16), C32(H32), C126(HC), C130(HD),
  C17(H17), C2(H2), C33(H33), C26(H26), C50(H50), C81(H81), C40(H40), C51(H51),
 C82(H82), C39(H39), C41(H41), C77(H77), C78(H78), C79(H79), C80(H80), C134(HH),
  C133(HI), C132(HJ), C131(HK), C136(HL), C154(HM), C159(HN), C155(HO),
 C156(HP), C95(HQ), C150(HV), C148(HW), C147(HX), C146(HY), C151(HZ), C143(H4),
 C142(H5), C141(H7), C140(H9), C144(H10), C46(H46), C48(H48), C49(H49),
 C109(H109), C44(H44), C43(H43), C45(H45), C115(H115)
5.e Fitted hexagon refined as free rotating group:
 C135(C134,C133,C132,C131,C136), C154(C159,C157,C155,C156,C95), C150(C149,C148,
 C147,C146,C151), C143(C142,C141,C140,C139,C144)
5.f Idealised Me refined as rotating group:
 C76(H76A,H76B,H76C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              60328
_shelx_hkl_checksum              72932
_shelx_fab_checksum              69882
_olex2_date_sample_data_collection 2021-01-24
_olex2_date_sample_submission    2021-01-07
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
;
The crystal was mounted on a mylar loop in perfluoroether oil
;
_olex2_submission_original_sample_id MAG_tristpyCu
_olex2_submission_special_instructions 'No special instructions were received'