Synthesis and characterization of heterometallic rings templated through alkylammonium or imidazolium cations.
Alotaibi, Rajeh; Booth, Amy; Little, Edmund; Brookfield, Adam; Achari, Amritroop; Lockyer, Selena J.; Timco, Grigore A.; Whitehead, George F. S.; Vitórica-Yrezábal, Iñigo J; Chilton, Nicholas F.; Nair, Rahul R.; Collison, David; Winpenny, Richard E. P.; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d3dt00982c

data_7713060
_publ_section_title
;
 Synthesis and characterization of heterometallic rings templated through
 alkylammonium or imidazolium cations.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d3dt00982c
_journal_year                    2023
_chemical_formula_moiety
'C130 H234 Cr12 F16 O52 Zn2, 2(C10 H22 N), 3.772(C7 H8)'
_chemical_formula_sum            'C176.4 H308.17 Cr12 F16 N2 O52 Zn2'
_chemical_formula_weight         4347.94
_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   geom
_audit_creation_date             2023-05-04
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-05-04 deposited with the CCDC.	2023-05-11 downloaded from the CCDC.
;
_cell_angle_alpha                94.884(5)
_cell_angle_beta                 92.430(5)
_cell_angle_gamma                109.377(5)
_cell_formula_units_Z            1
_cell_length_a                   13.5561(7)
_cell_length_b                   20.1031(12)
_cell_length_c                   21.8278(12)
_cell_measurement_reflns_used    5069
_cell_measurement_temperature    150.02(10)
_cell_measurement_theta_max      26.9060
_cell_measurement_theta_min      4.2270
_cell_volume                     5575.4(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.02(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -23.00  20.00   1.00   15.00    --  -17.77 -93.00 -90.00   43
  2  \w    -16.00  39.00   1.00   15.00    --   18.86 -93.00 -90.00   55
  3  \w     57.00  95.00   1.00   15.00    --   18.86-178.00 -90.00   38
  4  \w     47.00  74.00   1.00   15.00    --   18.86-178.00  60.00   27
  5  \w    -52.00  24.00   1.00   15.00    --   18.86 -19.00-180.00   76
  6  \w     -3.00  72.00   1.00   15.00    --   18.86  19.00-150.00   75
  7  \w    -88.00  11.00   1.00   15.00    --  -17.77 -77.00  90.00   99
  8  \w    -86.00  -3.00   1.00   15.00    --  -17.77 -57.00 -30.00   83
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0289547000
_diffrn_orient_matrix_UB_12      -0.0247367000
_diffrn_orient_matrix_UB_13      -0.0248989000
_diffrn_orient_matrix_UB_21      0.0000714000
_diffrn_orient_matrix_UB_22      -0.0283304000
_diffrn_orient_matrix_UB_23      0.0172562000
_diffrn_orient_matrix_UB_31      -0.0474914000
_diffrn_orient_matrix_UB_32      0.0001982000
_diffrn_orient_matrix_UB_33      0.0123273000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0913
_diffrn_reflns_av_unetI/netI     0.3426
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            13733
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        21.967
_diffrn_reflns_theta_max         21.967
_diffrn_reflns_theta_min         2.744
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.851
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81009
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.54a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.295
_exptl_crystal_description       block
_exptl_crystal_F_000             2289
_exptl_crystal_size_max          0.296
_exptl_crystal_size_mid          0.161
_exptl_crystal_size_min          0.102
_refine_diff_density_max         0.696
_refine_diff_density_min         -0.511
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.880
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1486
_refine_ls_number_reflns         13733
_refine_ls_number_restraints     5044
_refine_ls_restrained_S_all      0.819
_refine_ls_R_factor_all          0.1315
_refine_ls_R_factor_gt           0.0580
_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^)+(0.0556P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1179
_refine_ls_wR_factor_ref         0.1307
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6456
_reflns_number_total             13733
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 0.8211\% 
around [-0.65 -0.03 0.76] (reciprocal) or [-0.92 -0.19 0.34] (direct)
;
_cod_data_source_file            d3dt00982c2.cif
_cod_data_source_block           arep767_twin1_hklf4
_cod_original_formula_sum        'C176.40 H308.17 Cr12 F16 N2 O52 Zn2'
_cod_database_code               7713060
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Cr9Ni1F10C60O40N2H60
_shelx_estimated_absorpt_t_max   0.918
_shelx_estimated_absorpt_t_min   0.787
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.77949
 0.22051
2. Restrained distances
 C89-C83
 1.54 with sigma of 0.02
 C89A-C83A
 1.54 with sigma of 0.02
 C2-C1 \\sim C2A-C1
 with sigma of 0.02
 C27-C26 \\sim C27A-C26
 with sigma of 0.02
 C47A-C46 \\sim C47-C46
 with sigma of 0.02
 C12A-C11 \\sim C12-C11
 with sigma of 0.02
 C88-C89 \\sim C89-C84
 with sigma of 0.02
 C84A-C89A \\sim C89A-C88A
 with sigma of 0.02
3. Restrained planarity
 C83, C84, C85, C88, C89, C86, C87
 with sigma of 0.01
 C83A, C84A, C88A, C89A, C85A, C87A, C86A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
F8 \\sim C47A \\sim C2 \\sim C12A \\sim C3 \\sim C53A \\sim C4 \\sim C2A \\sim
C5 \\sim C27A \\sim C12 \\sim O22A \\sim C13 \\sim C14 \\sim C74A \\sim C15
\\sim C4A \\sim C27 \\sim C14A \\sim C28 \\sim C29A \\sim C29 \\sim C49A \\sim
C30 \\sim C51A \\sim C47 \\sim C55A \\sim C48 \\sim C49 \\sim C50 \\sim C75A
\\sim O21 \\sim C3A \\sim O22 \\sim C5A \\sim C51 \\sim C13A \\sim C52 \\sim
C15A \\sim C53 \\sim C28A \\sim C54 \\sim C30A \\sim C55 \\sim C48A \\sim C70
\\sim C50A \\sim C71 \\sim O21A \\sim C72 \\sim C52A \\sim C73 \\sim C54A \\sim
C74 \\sim F9 \\sim C75 \\sim C70A \\sim C71A \\sim C72A \\sim C73A: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
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
 F8, C47A, C2, C12A, C3, C53A, C4, C2A, C5, C27A, C12, O22A, C13, C14, C74A,
 C15, C4A, C27, C14A, C28, C29A, C29, C49A, C30, C51A, C47, C55A, C48, C49, C50,
  C75A, O21, C3A, O22, C5A, C51, C13A, C52, C15A, C53, C28A, C54, C30A, C55,
 C48A, C70, C50A, C71, O21A, C72, C52A, C73, C54A, C74, F9, C75, C70A, C71A,
 C72A, C73A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Same fragment restrains
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O3, O4, C6, C7, C8, C9, C10}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O7, O8, C16, C17, C18, C19, C20}
{C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C47A, C48A, C49A, C50A}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O5, O6, C11, C12, C13, C14, C15}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O13, O14, C31, C32, C33, C34, C35}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O9, O10, C21, C22, C23, C24, C25}
{C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C12A, C13A, C14A, C15A}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O11, O12, C26, C27, C28, C29, C30}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O22A, O21A, C51A, C52A, C53A, C54A, C55A}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O15, O16, C36, C37, C38, C39, C40}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O25, O26, C61, C62, C63, C64, C65}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O17, O18, C41, C42, C43, C44, C45}
{C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C2A, C3A, C4A, C5A}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O21, O22, C51, C52, C53, C54, C55}
{C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C27A, C28A, C29A, C30A}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O23, O24, C56, C57, C58, C59, C60}
{O1, O2, C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O19, O20, C46, C47, C48, C49, C50}
{C70, C71, C72, C73, C74, C75} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C70A, C71A, C72A, C73A, C74A, C75A}
7. Others
 Sof(H1BC)=Sof(H1BD)=Sof(C70A)=Sof(H70A)=Sof(C71A)=Sof(H71C)=Sof(H71D)=
 Sof(C72A)=Sof(H72C)=Sof(H72D)=Sof(C73A)=Sof(H73C)=Sof(H73D)=Sof(C74A)=
 Sof(H74C)=Sof(H74D)=Sof(C75A)=Sof(H75C)=Sof(H75D)=1-FVAR(1)
 Sof(H1AA)=Sof(H1AB)=Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(C72)=
 Sof(H72A)=Sof(H72B)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=FVAR(1)
 Sof(C2A)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=
 Sof(H4AC)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=1-FVAR(2)
 Sof(C2)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(2)
 Sof(C12A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(3)
 Sof(C12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(3)
 Sof(C27A)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(4)
 Sof(C27)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=
 Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(4)
 Sof(C47A)=Sof(C48A)=Sof(H48D)=Sof(H48E)=Sof(H48F)=Sof(C49A)=Sof(H49D)=
 Sof(H49E)=Sof(H49F)=Sof(C50A)=Sof(H50D)=Sof(H50E)=Sof(H50F)=1-FVAR(5)
 Sof(C47)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C49)=Sof(H49A)=Sof(H49B)=
 Sof(H49C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=FVAR(5)
 Sof(O22A)=Sof(O21A)=Sof(C51A)=Sof(C52A)=Sof(C53A)=Sof(H53D)=Sof(H53E)=
 Sof(H53F)=Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C55A)=Sof(H55D)=
 Sof(H55E)=Sof(H55F)=Sof(F9)=1-FVAR(6)
 Sof(F8)=Sof(O21)=Sof(O22)=Sof(C51)=Sof(C52)=Sof(C53)=Sof(H53A)=Sof(H53B)=
 Sof(H53C)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55)=Sof(H55A)=Sof(H55B)=
 Sof(H55C)=FVAR(6)
 Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(H89C)=Sof(C83)=Sof(C84)=Sof(H84)=Sof(C85)=
 Sof(H85)=Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87)=Sof(C88)=Sof(H88)=FVAR(7)
 Sof(C83A)=Sof(C84A)=Sof(H84A)=Sof(C85A)=Sof(H85A)=Sof(C86A)=Sof(H86A)=
 Sof(C87A)=Sof(H87A)=Sof(C88A)=Sof(H88A)=Sof(C89A)=Sof(H89D)=Sof(H89E)=
 Sof(H89F)=FVAR(8)
8.a Ternary CH refined with riding coordinates:
 C70(H70), C70A(H70A)
8.b Secondary CH2 refined with riding coordinates:
 N1(H1AA,H1AB), N1(H1BC,H1BD), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B),
 C74(H74A,H74B), C75(H75A,H75B), C71A(H71C,H71D), C72A(H72C,H72D), C73A(H73C,
 H73D), C74A(H74C,H74D), C75A(H75C,H75D)
8.c Me refined with riding coordinates:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C28(H28A,
 H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C33(H33A,H33B,H33C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C38(H38A,H38B,H38C), C39(H39A,H39B,
 H39C), C40(H40A,H40B,H40C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,
 H45B,H45C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C),
 C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C58(H58A,H58B,
 H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C63(H63A,H63B,H63C), C64(H64A,
 H64B,H64C), C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C),
 C69(H69A,H69B,H69C), C82(H82A,H82B,H82C), C3A(H3AA,H3AB,H3AC), C4A(H4AA,H4AB,
 H4AC), C5A(H5AA,H5AB,H5AC), C13A(H13D,H13E,H13F), C14A(H14D,H14E,H14F),
 C15A(H15D,H15E,H15F), C28A(H28D,H28E,H28F), C29A(H29D,H29E,H29F), C30A(H30D,
 H30E,H30F), C48A(H48D,H48E,H48F), C49A(H49D,H49E,H49F), C50A(H50D,H50E,H50F),
 C89(H89A,H89B,H89C), C53A(H53D,H53E,H53F), C54A(H54D,H54E,H54F), C55A(H55D,
 H55E,H55F), C89A(H89D,H89E,H89F)
8.d Aromatic/amide H refined with riding coordinates:
 C80(H80), C79(H79), C78(H78), C77(H77), C81(H81), C84(H84), C85(H85),
 C86(H86), C87(H87), C88(H88), C84A(H84A), C85A(H85A), C86A(H86A), C87A(H87A),
 C88A(H88A)
8.e Fitted hexagon refined as free rotating group:
 C80(C79,C78,C77,C76,C81), C83(C84,C85,C86,C87,C88), C83A(C84A,C85A,C86A,C87A,
 C88A)
;
_shelx_res_checksum              91663
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.203
_oxdiff_exptl_absorpt_empirical_full_min 0.798
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2