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_7244784
_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
'C188 H231 Br Co4 N6 Na O16, 4(C2 H3 N), 9[C2H3N]'
_chemical_formula_sum            'C214 H270 Br Co4 N19 Na O16'
_chemical_formula_weight         3703.09
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-14
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-02-15 deposited with the CCDC.	2022-03-14 downloaded from the CCDC.
;
_cell_angle_alpha                90.0
_cell_angle_beta                 94.9104(12)
_cell_angle_gamma                90.0
_cell_formula_units_Z            4
_cell_length_a                   21.7315(2)
_cell_length_b                   31.5316(5)
_cell_length_c                   29.9771(5)
_cell_measurement_reflns_used    20511
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      68.5350
_cell_measurement_theta_min      2.9290
_cell_volume                     20465.8(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.114a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.114a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.114a (Rigaku OD, 2021)'
_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)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000HE'
_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    -84.00  -9.00   0.50   12.19    --    0.00  30.00-150.00  150
  2  \w     -3.00  54.00   0.50   12.19    --    0.00  30.00-150.00  114
  3  \w   -178.00-118.00   0.50   47.50    --  -90.00  59.00  99.67  120
  4  \w   -145.00 -18.00   0.50   47.50    --  -90.00  58.00 -63.41  254
  5  \w   -179.00  -2.00   0.50   47.50    --  -90.00  59.00-125.54  354
  6  \w   -109.00 -84.00   0.50   47.50    --  -90.00  59.00  99.67   50
  7  \w    -49.00 -23.00   0.50   47.50    --  -90.00  59.00 132.51   52
  8  \w   -178.00 -59.00   0.50   47.50    --  -90.00  30.00  30.00  238
  9  \w   -127.00 -76.00   0.50   47.50    --  -90.00  49.00  90.00  102
 10  \w   -165.00 -46.00   0.50   47.50    --  -90.00  59.00 -33.96  238
 11  \w   -153.00 -82.00   0.50   47.50    --  -90.00  30.00 -60.00  142
 12  \w   -177.00-151.00   0.50   47.50    --  -90.00  59.00 125.83   52
 13  \w   -164.00 -99.00   0.50   47.50    --  -90.00  59.00 132.51  130
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, AFC11 quarter \c goniometer'
_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_measurement_specimen_support 'MiTeGen loops'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0009466000
_diffrn_orient_matrix_UB_12      -0.0371934000
_diffrn_orient_matrix_UB_13      0.0333549000
_diffrn_orient_matrix_UB_21      0.0024085000
_diffrn_orient_matrix_UB_22      0.0316801000
_diffrn_orient_matrix_UB_23      0.0392497000
_diffrn_orient_matrix_UB_31      -0.0711057000
_diffrn_orient_matrix_UB_32      0.0006025000
_diffrn_orient_matrix_UB_33      -0.0026151000
_diffrn_radiation_collimation    'HF Varimax focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0874
_diffrn_reflns_av_unetI/netI     0.0615
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            126916
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        55.991
_diffrn_reflns_theta_max         55.991
_diffrn_reflns_theta_min         2.416
_diffrn_source                   'Rotating anode'
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_target            Cu
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_diffrn_source_voltage           40.0
_exptl_absorpt_coefficient_mu    3.200
_exptl_absorpt_correction_T_max  0.859
_exptl_absorpt_correction_T_min  0.615
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.114a (Rigaku Oxford Diffraction, 2021)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.202
_exptl_crystal_description       needle
_exptl_crystal_F_000             7876
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.626
_refine_diff_density_min         -0.520
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2013
_refine_ls_number_reflns         26621
_refine_ls_number_restraints     57
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.1079
_refine_ls_R_factor_gt           0.0938
_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^)+(0.1205P)^2^+109.3300P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2560
_refine_ls_wR_factor_ref         0.2651
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21440
_reflns_number_total             26621
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ra01009g2.cif
_cod_data_source_block           2021ncs0514_ljm1b
_cod_database_code               7244784
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C203H258BrCo4N11NaO16
_chemical_oxdiff_usercomment     '[8]NaCo'
_cell_oxdiff_angle_alpha         90.025(2)
_cell_oxdiff_angle_beta          94.880(2)
_cell_oxdiff_angle_gamma         89.970(2)
_cell_oxdiff_length_a            21.7301(6)
_cell_oxdiff_length_b            31.5295(9)
_cell_oxdiff_length_c            29.9796(8)
_cell_oxdiff_measurement_reflns_used 20556
_cell_oxdiff_volume              20465.8(10)
_shelx_estimated_absorpt_t_max   0.855
_shelx_estimated_absorpt_t_min   0.433
_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 C(H,H,H,H) groups, All O(H) groups
2. Restrained distances
 H12-O13
 1.55 with sigma of 0.02
 C29-C30A = C29-C31A = C29-C32A
 1.5262 with sigma of 0.02
 C29-C30 = C29-C31 = C29-C32
 1.5262 with sigma of 0.02
 C30A-C31A = C31A-C32A = C32A-C30A
 2.494992 with sigma of 0.02
 C30-C31 = C31-C32 = C32-C30
 2.487706 with sigma of 0.02
 C17A-C17B = C17A-C17C = C17A-C17D
 1.5262 with sigma of 0.02
 C18A-C18B = C18A-C18C = C18A-C18D
 1.53067 with sigma of 0.02
 C17B-C17C = C17C-C17D = C17D-C17B
 2.487706 with sigma of 0.02
 C18B-C18C = C18C-C18D = C18D-C18B
 2.494992 with sigma of 0.02
 O11-H11 = O12-H12
 0.87 with sigma of 0.01
 C111-H11
 1.879187 with sigma of 0.02
 Co4-H11
 2.573016 with sigma of 0.02
 C168-C17A \\sim C1F-C17A
 with sigma of 0.04
 C29-C31 \\sim C29-C31A
 with sigma of 0.02
 C29-C32 \\sim C29-C32A
 with sigma of 0.02
 C29-C30 \\sim C29-C30A
 with sigma of 0.02
 C170-C17A \\sim C189-C17A
 with sigma of 0.04
 C128-C131 \\sim C128-C174
 with sigma of 0.02
 C169-C17A \\sim C1E-C17A
 with sigma of 0.02
 C128-C130 \\sim C128-C1B
 with sigma of 0.02
 C128-C129 \\sim C128-C1A
 with sigma of 0.02
 C1E-C18A \\sim C17A-C169
 with sigma of 0.02
 C139-C140 \\sim C139-C1D
 with sigma of 0.02
 C142-C139 \\sim C1C-C139
 with sigma of 0.02
 C141-C139 \\sim C175-C139
 with sigma of 0.02
 C73-C75 \\sim C73-C75A
 with sigma of 0.02
 C73-C76 \\sim C73-C76A
 with sigma of 0.02
 C73-C74 \\sim C73-C74A
 with sigma of 0.02
 C168-C170 \\sim C1F-C189
 with sigma of 0.04
 C167-C169 \\sim C167-C1E
 with sigma of 0.04
 C167-C168 \\sim C167-C1F
 with sigma of 0.02
 C168-C169 \\sim C1F-C1E
 with sigma of 0.02
 C169-C171 \\sim C1E-C171
 with sigma of 0.04
 C170-C169 \\sim C189-C1E
 with sigma of 0.02
 C170-C171 \\sim C189-C171
 with sigma of 0.02
3. Restrained planarity
 H1BB, C1E, C1F, C18A, C166, C167, C171, C189
 with sigma of 0.1
 C17A, C167, C168, C169, C170, C171
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uiso(C17A) = Uiso(C17C)
Uiso(C31A) = Uiso(C31) = Uiso(C32A) = Uiso(C32) = Uiso(C30A) = Uiso(C30)
Uiso(C18A) = Uiso(C17A)
Uiso(C17C) = Uiso(C17D)
Uiso(C129) = Uiso(C1A) = Uiso(C130) = Uiso(C1B) = Uiso(C131) = Uiso(C174)
Uiso(C1D) = Uiso(C140) = Uiso(C141) = Uiso(C175) = Uiso(C1C) = Uiso(C142)
Uiso(C76A) = Uiso(C75) = Uiso(C75A) = Uiso(C74) = Uiso(C74A) = Uiso(C76)
Uiso(C168) = Uiso(C1F)
Uiso(C1E) = Uiso(C169)
5. Others
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=
 Sof(C174)=Sof(H17J)=Sof(H17K)=Sof(H17L)=1-FVAR(1)
 Sof(C129)=Sof(H12F)=Sof(H12G)=Sof(H12H)=Sof(C130)=Sof(H13A)=Sof(H13B)=
 Sof(H13C)=Sof(C131)=Sof(H13D)=Sof(H13E)=Sof(H13F)=FVAR(1)
 Sof(C1C)=Sof(H1CA)=Sof(H1CB)=Sof(H1CC)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(H1DC)=
 Sof(C175)=Sof(H17M)=Sof(H17N)=Sof(H17O)=1-FVAR(2)
 Sof(C140)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C141)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=Sof(C142)=Sof(H14G)=Sof(H14H)=Sof(H14I)=FVAR(2)
 Sof(C74A)=Sof(H74D)=Sof(H74E)=Sof(H74F)=Sof(C75A)=Sof(H75D)=Sof(H75E)=
 Sof(H75F)=Sof(C76A)=Sof(H76D)=Sof(H76E)=Sof(H76F)=1-FVAR(3)
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=FVAR(3)
 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(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(C1E)=Sof(C1F)=Sof(H1F)=Sof(C18A)=Sof(C18B)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 Sof(C18C)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C18D)=Sof(H18G)=Sof(H18H)=
 Sof(H18I)=Sof(C189)=Sof(H189)=1-FVAR(5)
 Sof(C17A)=Sof(C17B)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C17C)=Sof(H17D)=
 Sof(H17E)=Sof(H17F)=Sof(C17D)=Sof(H17G)=Sof(H17H)=Sof(H17I)=Sof(C168)=
 Sof(H168)=Sof(C169)=Sof(C170)=Sof(H170)=FVAR(5)
 1(DFIX)=1(DFIX)=1(DFIX)=FVAR(6)
 1(DFIX)=1(DFIX)=1.63*FVAR(7)
 Uiso(C17A)=Uiso(C17C)=Uiso(C17D)=Uiso(C18A)=Uiso(C18B)=Uiso(C18C)=Uiso(C18D)=
 FVAR(7)
6.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(H13G,H13H), C143(H14J,H14K), C154(H15J,
 H15K), C165(H16J,H16K), C176(H17P,H17Q)
6.b Me refined with riding coordinates:
 C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,H1BC), C1C(H1CA,H1CB,H1CC), C1D(H1DA,H1DB,
 H1DC), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C17B(H17A,H17B,
 H17C), C17C(H17D,H17E,H17F), C17D(H17G,H17H,H17I), C18B(H18A,H18B,H18C),
 C18C(H18D,H18E,H18F), C18D(H18G,H18H,H18I), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), 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), C74A(H74D,H74E,
 H74F), C75(H75A,H75B,H75C), C75A(H75D,H75E,H75F), C76(H76A,H76B,H76C),
 C76A(H76D,H76E,H76F), 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(H10D,H10E,H10F), C108(H10G,H10H,H10I), C109(H10J,H10K,H10L), C118(H11E,
 H11F,H11G), C119(H11H,H11I,H11J), C120(H12A,H12B,H12C), C129(H12F,H12G,H12H),
 C130(H13A,H13B,H13C), C131(H13D,H13E,H13F), C140(H14A,H14B,H14C), C141(H14D,
 H14E,H14F), C142(H14G,H14H,H14I), C151(H15A,H15B,H15C), C152(H15D,H15E,H15F),
 C153(H15G,H15H,H15I), C162(H16A,H16B,H16C), C163(H16D,H16E,H16F), C164(H16G,
 H16H,H16I), C174(H17J,H17K,H17L), C175(H17M,H17N,H17O)
6.c Aromatic/amide H refined with riding coordinates:
 C1F(H1F), 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), C91(H91), C93(H93), C102(H102), C104(H104), C113(H113), C115(H115),
 C124(H124), C126(H126), C135(H135), C137(H137), C146(H146), C148(H148),
 C157(H157), C159(H159), C168(H168), C170(H170), C189(H189)
6.d Tetrahedral OH refined with riding coordinates:
 O4(H4), O6(H6), O7(H7)
6.e Idealised Me refined as rotating group:
 C178(H17R,H17S,H17T), C180(H18J,H18K,H18L), C182(H18M,H18N,H18O), C184(H18P,
 H18Q,H18R), C186(H18S,H18T,H18U), C188(H18V,H18W,H18X), C204(H20D,H20E,H20F),
 C206(H20G,H20H,H20I), C202(H20J,H20K,H20L), C208(H20M,H20N,H20O)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 778 electrons were 
found in a volume of 3712\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
9[CH3CN] per Asymmetric Unit 
which account for 792 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              5489
_shelx_fab_checksum              71006
_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 2.938
_oxdiff_exptl_absorpt_empirical_full_min 0.471