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_7244785
_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
'2(C104 H130 Br2 Co3 Li7 N6 O14), C96 H116 Br2 Co3 Li7 N4 O16, 2(C2 H3 N), 26[CH3CN]'
_chemical_formula_sum            'C360 H460 Br6 Co9 Li21 N44 O44'
_chemical_formula_weight         7263.26
_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   geom
_audit_creation_date             2021-10-08
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6405)
;
_audit_update_record
;
2021-10-08 deposited with the CCDC.	2022-03-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.577(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.4262(2)
_cell_length_b                   57.4173(10)
_cell_length_c                   35.8800(8)
_cell_measurement_reflns_used    41591
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      28.1850
_cell_measurement_theta_min      2.2040
_cell_volume                     21338.0(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -86.00  94.00   0.50   30.00    --    4.00  18.00  30.00  360
  2  \w    -95.00  59.00   0.50   30.00    --  -31.00  72.00   0.00  308
  3  \w   -121.00  -6.00   0.50   30.00    --  -31.00 -72.00  90.00  230
  4  \w    -27.00  32.00   0.50   30.00    --  -31.00 -72.00 120.00  118
  5  \w    -95.00 -26.00   0.50   30.00    --  -31.00  36.00 -90.00  138
  6  \w    -98.00  13.00   0.50   30.00    --  -31.00  54.00   0.00  222
  7  \w    -39.00 -24.00   0.50   30.00    --  -31.00 -72.00-120.00   30
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0304616000
_diffrn_orient_matrix_UB_12      0.0050588000
_diffrn_orient_matrix_UB_13      -0.0167670000
_diffrn_orient_matrix_UB_21      -0.0220056000
_diffrn_orient_matrix_UB_22      0.0093500000
_diffrn_orient_matrix_UB_23      0.0105095000
_diffrn_orient_matrix_UB_31      0.0572408000
_diffrn_orient_matrix_UB_32      0.0062882000
_diffrn_orient_matrix_UB_33      -0.0021540000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0539
_diffrn_reflns_av_unetI/netI     0.0632
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       64
_diffrn_reflns_limit_k_min       -68
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            158602
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.090
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.964
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76528
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.130
_exptl_crystal_description       block
_exptl_crystal_F_000             7592
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.735
_refine_diff_density_min         -1.497
_refine_diff_density_rms         0.154
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.345
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1780
_refine_ls_number_reflns         37688
_refine_ls_number_restraints     2850
_refine_ls_restrained_S_all      1.310
_refine_ls_R_factor_all          0.1505
_refine_ls_R_factor_gt           0.1150
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3406
_refine_ls_wR_factor_ref         0.3653
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24480
_reflns_number_total             37688
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ra01009g2.cif
_cod_data_source_block           CoLi5
_cod_database_code               7244785
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Co (C88 H109 O8)2 (Li O)'
_shelx_estimated_absorpt_t_max   0.918
_shelx_estimated_absorpt_t_min   0.869
_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. Shared sites
{Co4, Li4A}
{Li5A, Co5}
{Co2, Li2A}
3. Restrained distances
 C18-C19A = C18-C20A = C18-C21A = C18-C19B = C18-C20B = C18-C21B
 1.50479 with sigma of 0.02
 C19A-C20A = C20A-C21A = C21A-C19A = C19B-C20B = C20B-C21B = C21B-C19B
 2.452808 with sigma of 0.02
 N3-C23A = N3-C23C = N13-C24A = N13-C24C
 1.18 with sigma of 0.02
 N7-C27A \\sim N7-C27B
 with sigma of 0.02
 C27A-C28A \\sim C27B-C28B
 with sigma of 0.02
 C24A-C24B \\sim C24C-C24D \\sim C23A-C23B \\sim C23C-C23D
 with sigma of 0.02
 C29-C30 \\sim C29-C30A
 with sigma of 0.02
 C29-C32 \\sim C29-C32A
 with sigma of 0.02
 C29-C31 \\sim C29-C31A
 with sigma of 0.02
 C40-C43 \\sim C40-C43A
 with sigma of 0.02
 C40-C41 \\sim C40-C41A
 with sigma of 0.02
 C40-C42 \\sim C40-C42A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.1 and sigma
for terminal atoms of 0.2
Uanis(C281) \\sim Ueq, Uanis(C282) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uiso(Li5) = Uiso(Co4) = Uiso(Li4A)
Uiso(Li8) = Uiso(Li5A) = Uiso(Co5)
Uiso(Co2) = Uiso(Li2A)
Uiso(C30A) = Uiso(C30) = Uiso(C31A) = Uiso(C31) = Uiso(C32A) = Uiso(C32)
Uiso(C43) = Uiso(C43A) = Uiso(C41) = Uiso(C41A) = Uiso(C42A) = Uiso(C42)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 1(DFIX)=FVAR(1)
 1(DFIX)=1.63*FVAR(2)
 Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21B)=Sof(H21D)=Sof(H21E)=
 Sof(H21F)=Sof(C19B)=Sof(H19D)=Sof(H19E)=Sof(H19F)=1-FVAR(2)
 Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20A)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(2)
 Uiso(C19A)=Uiso(C20A)=Uiso(C21A)=Uiso(C20B)=Uiso(C21B)=Uiso(C19B)=FVAR(3)
 Sof(C28B)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C27B)=1-FVAR(4)
 Sof(C27A)=Sof(C28A)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(4)
 Uiso(C27A)=Uiso(C28A)=Uiso(C28B)=Uiso(C27B)=FVAR(5)
 Uiso(C24A)=Uiso(C24B)=Uiso(C24C)=Uiso(C24D)=Uiso(C23A)=Uiso(C23B)=Uiso(C23C)=
 Uiso(C23D)=FVAR(6)
 Sof(C24C)=Sof(C24D)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(7)
 Sof(C24A)=Sof(C24B)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(7)
 Sof(C23C)=Sof(C23D)=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(8)
 Sof(C23A)=Sof(C23B)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(8)
 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(9)
 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(9)
 Sof(C43A)=Sof(H43D)=Sof(H43E)=Sof(H43F)=Sof(C42A)=Sof(H42D)=Sof(H42E)=
 Sof(H42F)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=1-FVAR(10)
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=FVAR(10)
 Fixed Sof: Co4(0.5) Li4A(0.5) Co5(0.5) Li5A(0.5) Co2(0.5) Li2A(0.5)
7.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), C111(H11F,H11G),
 C122(H12D,H12E), C133(H13J,H13K), C144(H14G,H14H), C151(H15A,H15B), C152(H15C,
 H15D), C153(H15E,H15F), C154(H15G,H15H)
7.b Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C19A(H19A,H19B,H19C),
 C20A(H20A,H20B,H20C), C21A(H21A,H21B,H21C), C20B(H20D,H20E,H20F), C21B(H21D,
 H21E,H21F), C19B(H19D,H19E,H19F), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C),
 C32(H32A,H32B,H32C), 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), C108(H10D,H10E,H10F), C109(H10G,H10H,H10I),
 C110(H11C,H11D,H11E), C119(H11H,H11I,H11J), C120(H12A,H12B,H12C), C130(H13A,
 H13B,H13C), C132(H13D,H13E,H13F), C131(H13G,H13H,H13I), C141(H14A,H14B,H14C),
 C142(H14D,H14E,H14F), C121(H12F,H12G,H12H), C143(H14I,H14J,H14K), C30A(H30D,
 H30E,H30F), C31A(H31D,H31E,H31F), C32A(H32D,H32E,H32F), C43A(H43D,H43E,H43F),
 C42A(H42D,H42E,H42F), C41A(H41D,H41E,H41F)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), 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),
  C103(H103), C105(H105), C114(H114), C116(H116), C125(H125), C127(H127),
 C136(H136), C138(H138)
7.d Idealised Me refined as rotating group:
 C212(H21G,H21H,H21I), C222(H22C,H22D,H22E), C252(H25A,H25B,H25C), C262(H26A,
 H26B,H26C), C28A(H28A,H28B,H28C), C28B(H28D,H28E,H28F), C282(H28G,H28H,H28I),
 C240(H24G,H24H,H24I), C24B(H24A,H24B,H24C), C24D(H24D,H24E,H24F), C23B(H23A,
 H23B,H23C), C23D(H23D,H23E,H23F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 1167 electrons were 
found in a volume of 7047\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
26[CH3CN] per Asymmetric Unit 
which account for 1144 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              82614
_shelx_fab_checksum              73608
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.235
_oxdiff_exptl_absorpt_empirical_full_min 0.475