Heterometallic cobalt(ii) calix[6 and 8]arenes: synthesis, structure and electrochemical activity
Ignaszak, Anna; Patterson, Nigel; O'Brien, Connor; True, Allison; Elsegood, Mark R. J.; Prior, Timothy J.; Redshaw, Carl; RSC Advances 12 (2022) 11672–11685; doi:10.1039/D2RA01009G

data_7244783
_publ_section_title
;
 Heterometallic cobalt(ii) calix[6 and 8]arenes: synthesis, structure and
 electrochemical activity
;
_journal_issue                   19
_journal_name_full               'RSC Advances'
_journal_page_first              11672
_journal_page_last               11685
_journal_paper_doi               10.1039/D2RA01009G
_journal_volume                  12
_journal_year                    2022
_chemical_formula_moiety         'C144 H176 Br Co6 N6 Na O13, 7[CH3CN]'
_chemical_formula_sum            'C158 H197 Br Co6 N13 Na O13'
_chemical_formula_weight         2942.75
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-02-15 deposited with the CCDC.	2022-03-14 downloaded from the CCDC.
;
_cell_angle_alpha                88.4380(10)
_cell_angle_beta                 85.3530(10)
_cell_angle_gamma                68.1970(10)
_cell_formula_units_Z            2
_cell_length_a                   16.9279(2)
_cell_length_b                   21.3316(3)
_cell_length_c                   24.0984(4)
_cell_measurement_reflns_used    46074
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      69.9980
_cell_measurement_theta_min      3.4480
_cell_volume                     8052.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_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)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'hybrid pixel array detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -89.00  89.00   0.50    3.00    --    0.00   0.00-180.00  356
  2  \w    -84.00  94.00   0.50    3.00    --    5.00  55.00-108.36  356
  3  \w   -179.00  -1.00   0.50   15.00    --  -90.00  56.00 -71.42  356
  4  \w   -178.00-146.00   0.50   15.00    --  -90.00  59.00 -83.35   64
  5  \w   -179.00  -1.00   0.50   15.00    --  -90.00  58.00 -17.65  356
  6  \w   -179.00  -1.00   0.50   15.00    --  -90.00  59.00-119.01  356
  7  \w   -179.00  -1.00   0.50   15.00    --  -90.00  59.00 105.28  356
  8  \w   -179.00  -1.00   0.50   15.00    --  -90.00  58.00 147.90  356
  9  \w   -179.00  -1.00   0.50   15.00    --  -90.00  39.00-120.00  356
 10  \w   -179.00  -1.00   0.50   15.00    --  -90.00  10.00 -30.00  356
 11  \w   -179.00  -1.00   0.50   15.00    --  -90.00  59.00-164.02  356
 12  \w   -179.00  -1.00   0.50   15.00    --  -90.00  59.00  63.40  356
 13  \w   -179.00  -1.00   0.50   15.00    --  -90.00  59.00 -55.83  356
 14  \w   -179.00  -1.00   0.50   15.00    --  -90.00  57.00  31.20  356
 15  \w   -178.00 -40.00   0.50   15.00    --  -90.00  59.00 -83.35  276
 16  \w    -66.00 -40.00   0.50   15.00    --  -90.00  59.00 -83.35   52
 17  \w   -161.00-123.00   0.50   15.00    --  -90.00  59.00 -23.04   76
 18  \w   -117.00 -92.00   0.50   15.00    --  -90.00  59.00 -23.04   50
 19  \w    -82.00 -35.00   0.50   15.00    --  -90.00  59.00-174.93   94
 20  \w   -131.00-105.00   0.50   15.00    --  -90.00  59.00-174.93   52
 21  \w   -178.00 -26.00   0.50   15.00    --  -90.00  59.00 170.02  304
 22  \w    -89.00  89.00   0.50    3.00    --    0.00  30.00 120.00  356
 23  \w   -179.00-154.00   0.50   15.00    --  -90.00  59.00 131.63   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Rigaku 007HF equipped with HF Varimax confocal mirrors and an AFC11 goniometer and HyPix 6000HE detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0002708000
_diffrn_orient_matrix_UB_12      -0.0053127000
_diffrn_orient_matrix_UB_13      0.0638931000
_diffrn_orient_matrix_UB_21      -0.0884642000
_diffrn_orient_matrix_UB_22      -0.0054688000
_diffrn_orient_matrix_UB_23      0.0029281000
_diffrn_orient_matrix_UB_31      0.0428732000
_diffrn_orient_matrix_UB_32      -0.0774095000
_diffrn_orient_matrix_UB_33      -0.0047891000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0878
_diffrn_reflns_av_unetI/netI     0.0541
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            173441
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.245
_diffrn_reflns_theta_min         3.247
_diffrn_source                   'Rotating anode'
_diffrn_source_type              'Rigaku 007 HF'
_exptl_absorpt_coefficient_mu    5.510
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56663
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'intense blue'
_exptl_crystal_density_diffrn    1.214
_exptl_crystal_description       plate
_exptl_crystal_F_000             3096
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.015
_refine_diff_density_max         1.329
_refine_diff_density_min         -0.631
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1516
_refine_ls_number_reflns         29268
_refine_ls_number_restraints     118
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0872
_refine_ls_R_factor_gt           0.0700
_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^)+(0.1210P)^2^+4.9245P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1987
_refine_ls_wR_factor_ref         0.2111
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22098
_reflns_number_total             29268
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ra01009g2.cif
_cod_data_source_block           2021ncs0516r1s
_cod_database_code               7244783
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C70 H70 O6 N4 Na2 Co4 Br2'
_chemical_oxdiff_usercomment     '[6]CoNa recollection due to power cut'
_shelx_estimated_absorpt_t_max   0.922
_shelx_estimated_absorpt_t_min   0.405
_reflns_odcompleteness_completeness 99.26
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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, All O(H) groups
2. Restrained distances
 H4-O4
 0.95 with sigma of 0.02
 H4-O5
 1.6 with sigma of 0.02
 C18-C19 \\sim C18-C19A
 with sigma of 0.02
 N2-C135 \\sim N2-C13A
 with sigma of 0.02
 C26-C29 \\sim C26-C29A
 with sigma of 0.02
 C18-C21 \\sim C18-C21A
 with sigma of 0.02
 C18-C20 \\sim C18-C20A
 with sigma of 0.02
 C8-C9 \\sim C9-C10 \\sim C10-C8 \\sim C8A-C9A \\sim C9A-C10A \\sim C8A-C10A
 with sigma of 0.04
 C29-C30 \\sim C29-C31 \\sim C29-C32 \\sim C29A-C31A \\sim C29A-C30A \\sim
C29A-C32A
 with sigma of 0.02
 C19-C20 \\sim C19-C21 \\sim C20-C21 \\sim C20A-C19A \\sim C19A-C21A \\sim
C20A-C21A
 with sigma of 0.04
 C30-C31 \\sim C30-C32 \\sim C32-C30 \\sim C30A-C31A \\sim C30A-C32A \\sim
C32A-C30A
 with sigma of 0.04
 N4-C140 \\sim N4-C14A
 with sigma of 0.04
 C7-C4 \\sim C7-C8 \\sim C7-C9 \\sim C7-C10 \\sim C7A-C8A \\sim C7A-C9A \\sim
C7A-C10A
 with sigma of 0.02
 C117-C120 \\sim C153-C1B
 with sigma of 0.02
 C114-C117 \\sim C114-C153
 with sigma of 0.02
 N2-C136 \\sim N2-C13B
 with sigma of 0.04
 C118-C119 \\sim C1C-C1A
 with sigma of 0.04
 C114-C120 \\sim C114-C1B
 with sigma of 0.04
 C117-C119 \\sim C153-C1A
 with sigma of 0.02
 C118-C120 \\sim C1C-C1B
 with sigma of 0.04
 C119-C120 \\sim C1A-C1B
 with sigma of 0.04
 C117-C118 \\sim C153-C1C
 with sigma of 0.02
 C114-C118 \\sim C114-C1C
 with sigma of 0.04
 C114-C119 \\sim C114-C1A
 with sigma of 0.04
 N4-C139 \\sim N4-C13C
 with sigma of 0.02
 C135-C136 \\sim C13A-C13B
 with sigma of 0.02
 C139-C140 \\sim C13C-C14A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C13C \\sim C14A \\sim C139 \\sim C140: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
C13A \\sim C13B \\sim C135 \\sim C136: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
C13E \\sim C13F \\sim C133 \\sim C134: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
C144 \\sim C143 \\sim N6 \\sim N6A \\sim C154 \\sim C14B: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uiso(C21A) = Uiso(C21) = Uiso(C19A) = Uiso(C19) = Uiso(C20A) = Uiso(C20)
Uiso(C29) = Uiso(C29A)
Uiso(C30A) = Uiso(C31) = Uiso(C31A) = Uiso(C32A) = Uiso(C30) = Uiso(C32)
Uiso(C8) = Uiso(C8A) = Uiso(C9) = Uiso(C9A) = Uiso(C10) = Uiso(C10A)
Uiso(C7) = Uiso(C7A)
Uiso(C1A) = Uiso(C119) = Uiso(C1C) = Uiso(C118) = Uiso(C120) = Uiso(C1B)
Uiso(C153) = Uiso(C117)
4. Others
 Sof(N6A)=Sof(C14B)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C154)=1-FVAR(1)
 Sof(N6)=Sof(C143)=Sof(C144)=Sof(H14M)=Sof(H14N)=Sof(H14O)=FVAR(1)
 Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C20A)=Sof(H20D)=Sof(H20E)=
 Sof(H20F)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(2)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(2)
 Sof(C7A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=
 Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(3)
 Sof(C7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(3)
 Sof(C29A)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31A)=Sof(H31D)=
 Sof(H31E)=Sof(H31F)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(4)
 Sof(C29)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=
 Sof(H31C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(4)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=
 Sof(C1C)=Sof(H1CA)=Sof(H1CB)=Sof(H1CC)=Sof(C153)=1-FVAR(5)
 Sof(C117)=Sof(C118)=Sof(H11E)=Sof(H11F)=Sof(H11G)=Sof(C119)=Sof(H11H)=
 Sof(H11I)=Sof(H11J)=Sof(C120)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(5)
 Sof(C13A)=Sof(C13B)=Sof(H13A)=Sof(H13B)=Sof(H13C)=1-FVAR(6)
 Sof(C135)=Sof(C136)=Sof(H13R)=Sof(H13S)=Sof(H13T)=FVAR(6)
 Sof(C13C)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=1-FVAR(7)
 Sof(C139)=Sof(C140)=Sof(H14G)=Sof(H14H)=Sof(H14I)=FVAR(7)
 Sof(C13E)=Sof(C13F)=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(8)
 Sof(C133)=Sof(C134)=Sof(H13O)=Sof(H13P)=Sof(H13Q)=FVAR(8)
5.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C22(H22A,H22B), C33(H33A,H33B), C44(H44A,H44B), C55(H55A,
 H55B), C66(H66A,H66B), C77(H77A,H77B), C88(H88A,H88B), C99(H99A,H99B),
 C110(H11C,H11D), C121(H12D,H12E), C132(H13M,H13N)
5.b Me refined with riding coordinates:
 C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,H1BC), C1C(H1CA,H1CB,H1CC), C8(H8A,H8B,
 H8C), C8A(H8AA,H8AB,H8AC), C9(H9A,H9B,H9C), C9A(H9AA,H9AB,H9AC), C10(H10A,H10B,
 H10C), C10A(H10D,H10E,H10F), C19(H19A,H19B,H19C), C19A(H19D,H19E,H19F),
 C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F), C21(H21A,H21B,H21C), C21A(H21D,H21E,
 H21F), C30(H30A,H30B,H30C), C30A(H30D,H30E,H30F), C31(H31A,H31B,H31C),
 C31A(H31D,H31E,H31F), C32(H32A,H32B,H32C), C32A(H32D,H32E,H32F), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C52(H52A,H52B,H52C), C53(H53A,
 H53B,H53C), C54(H54A,H54B,H54C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C),
 C65(H65A,H65B,H65C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,
 H76C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C96(H96A,
 H96B,H96C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C), C107(H10G,H10H,H10I),
 C108(H10J,H10K,H10L), C109(H10M,H10N,H10O), C118(H11E,H11F,H11G), C119(H11H,
 H11I,H11J), C120(H12A,H12B,H12C), C129(H12F,H12G,H12H), C130(H13G,H13H,H13I),
 C131(H13J,H13K,H13L)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5A), C14(H14), C16(H16), C25(H25), C27(H27), C36(H36), C38(H38),
 C47(H47), C49(H49), C58(H58), C60(H60), C69(H69), C71(H71), C80(H80), C82(H82),
  C91(H91), C93(H93), C102(H102), C104(H104), C113(H113), C115(H115),
 C124(H124), C126(H126)
5.d Idealised Me refined as rotating group:
 C13B(H13A,H13B,H13C), C13F(H13D,H13E,H13F), C14A(H14A,H14B,H14C), C14B(H14D,
 H14E,H14F), C134(H13O,H13P,H13Q), C136(H13R,H13S,H13T), C138(H13U,H13V,H13W),
 C140(H14G,H14H,H14I), C142(H14J,H14K,H14L), C144(H14M,H14N,H14O)
5.e Idealised tetrahedral OH refined as rotating group:
 O5(H5)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 315 electrons were 
found in a volume of 1571\%A^3^ in 4 voids per unit cell. 
This is consistent with the presence of 
7[CH3CN] per Unit Cell 
which account for 308 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              11516
_shelx_fab_checksum              8966
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 3.791
_oxdiff_exptl_absorpt_empirical_full_min 0.344