Lead calix[n]arenes (n=4, 6, 8): Structures and ring opening homo-/co-polymerization capability for cyclic esters
Xing, Tian; Prior, Timothy J.; Redshaw, Carl; Dalton Transactions  (2021) –; doi:10.1039/D1DT02790E

data_7708487
_publ_section_title
;
 Lead calix[n]arenes (n=4, 6, 8): Structures and ring opening
 homo-/co-polymerization capability for cyclic esters
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT02790E
_journal_year                    2021
_chemical_formula_moiety         'C176 H206 O20 Pb12, 12(C2 H3 N), 7.5[CH3CN]'
_chemical_formula_sum            'C215 H264.5 N19.5 O20 Pb12'
_chemical_formula_weight         5928.23
_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             2021-08-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6257)
;
_audit_update_record
;
2021-08-10 deposited with the CCDC.	2021-09-30 downloaded from the CCDC.
;
_cell_angle_alpha                66.654(2)
_cell_angle_beta                 73.896(2)
_cell_angle_gamma                89.9500(10)
_cell_formula_units_Z            1
_cell_length_a                   18.0913(3)
_cell_length_b                   18.1443(3)
_cell_length_c                   19.6341(3)
_cell_measurement_reflns_used    45700
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      31.5240
_cell_measurement_theta_min      3.5030
_cell_volume                     5641.5(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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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     18.00  79.00   0.50    4.00    --   20.24-127.00  94.00  122
  2  \w    -80.00 -12.00   0.50    4.00    --  -20.71 127.00 170.00  136
  3  \w    -33.00  -5.00   0.50    4.00    --   20.24 116.00-133.42   56
  4  \w    -39.00 -12.00   0.50    4.00    --   20.24 127.00-100.35   54
  5  \w    -37.00 -10.00   0.50    4.00    --   20.24 124.00-124.32   54
  6  \w     22.00 103.00   0.50    4.00    --   20.24  19.00  30.00  162
  7  \w    -33.00  -5.00   0.50    4.00    --   20.24 116.00 108.50   56
  8  \w    -30.00  -2.00   0.50    4.00    --   20.24 112.00 156.26   56
  9  \w    -25.00   4.00   0.50    4.00    --   20.24 103.00-176.34   58
 10  \w    -26.00   3.00   0.50    4.00    --   20.24 104.00-157.38   58
 11  \w     22.00 103.00   0.50    4.00    --   20.24  19.00 120.00  162
 12  \w    -25.00   4.00   0.50    4.00    --   20.24 102.00 -82.80   58
 13  \w    -27.00   2.00   0.50    4.00    --   20.24 105.00 -12.80   58
 14  \w    -40.00 -13.00   0.50    4.00    --   20.24 129.00  18.88   54
 15  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00  30.00   80
 16  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00 120.00   80
 17  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00-180.00   80
 18  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00 -60.00   80
 19  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00 -90.00   80
 20  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00 -30.00   80
 21  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00-150.00   80
 22  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00 150.00   80
 23  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00-120.00   80
 24  \w    -24.00   5.00   0.50    4.00    --   20.24 101.00 -48.09   58
 25  \w    -18.00  53.00   0.50    4.00    --   20.24 -77.00   0.00  142
 26  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00   0.00   80
 27  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00  60.00   80
 28  \w    -64.00 -30.00   0.50    4.00    --  -20.71  98.00 116.90   68
 29  \w     22.00  62.00   0.50    4.00    --  -20.71  19.00  90.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0277078000
_diffrn_orient_matrix_UB_12      0.0304619000
_diffrn_orient_matrix_UB_13      -0.0043751000
_diffrn_orient_matrix_UB_21      -0.0302814000
_diffrn_orient_matrix_UB_22      0.0186746000
_diffrn_orient_matrix_UB_23      0.0160796000
_diffrn_orient_matrix_UB_31      0.0025431000
_diffrn_orient_matrix_UB_32      -0.0237563000
_diffrn_orient_matrix_UB_33      0.0377571000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0701
_diffrn_reflns_av_unetI/netI     0.0496
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            107191
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.682
_diffrn_reflns_theta_min         3.386
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    8.978
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72009
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.745
_exptl_crystal_description       prism
_exptl_crystal_F_000             2835
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         5.457
_refine_diff_density_min         -3.099
_refine_diff_density_rms         0.313
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1101
_refine_ls_number_reflns         21322
_refine_ls_number_restraints     995
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0713
_refine_ls_R_factor_gt           0.0571
_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^)+(0.1065P)^2^+33.6877P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1533
_refine_ls_wR_factor_ref         0.1623
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17119
_reflns_number_total             21322
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02790e2.cif
_cod_data_source_block           2021ncs0341s
_cod_original_cell_volume        5641.51(18)
_cod_original_formula_sum        'C215 H264.50 N19.50 O20 Pb12'
_cod_database_code               7708487
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C80 H80 O8 Pb (NSi2C6H16)2'
_chemical_oxdiff_usercomment     '[8]distilled Pb'
_shelx_estimated_absorpt_t_max   0.615
_shelx_estimated_absorpt_t_min   0.412
_reflns_odcompleteness_completeness 99.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.64
_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
 C62-C63 \\sim C62-C63A
 with sigma of 0.02
 C63-C64 \\sim C64-C65 \\sim C63A-C64A \\sim C64A-C65A
 with sigma of 0.04
 C62-C64 \\sim C62-C64A
 with sigma of 0.02
 C62-C65 \\sim C62-C65A
 with sigma of 0.02
 C62-C63 \\sim C62-C64 \\sim C62-C65 \\sim C62-C63A \\sim C62-C64A \\sim
C62-C65A \\sim C62-C59
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C63A \\sim C63: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C65 \\sim C65A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C64A \\sim C64: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(C52) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C45) \\sim Ueq: with sigma of
0.0001 and sigma for terminal atoms of 0.0002
4. Rigid body (RIGU) restrains
 C51, Pb4, O5, O9, O10, O4, Pb2, Pb1, Pb5, C45, Pb3, C56, O3, O1, O8, O7, C50,
 C46, O2, C61, C57, C67, C1, C12, C23, C49, C44, C47, C55, C78, C60, C66, C58,
 C68, C72, C6, C2, C17, C13, C24, C28, C48, C35, C83, C79, C59, C69, C77, C71,
 C88, C5, C3, C11, C16, C22, C14, C33, C25, C27, C36, C34, C82, C80, C62, C70,
 C4, C15, C39, C26, C52, C54, C53, C37, O6, C81, C63, C64, C65, C63A, C64A,
 C65A, C73, C7, C18, C38, C29, C40, Pb6, C84, C75, C76, C74, C9, C8, C10, C20,
 C21, C19, C32, C30, C31, C41, C43, C42, C87, C86, C85
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C51, C53, C54, C52
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C63A)=Sof(H63D)=Sof(H63E)=Sof(H63F)=Sof(C64A)=Sof(H64D)=Sof(H64E)=
 Sof(H64F)=Sof(C65A)=Sof(H65D)=Sof(H65E)=Sof(H65F)=1-FVAR(1)
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C33(H33A,H33B), C55(H55A,H55B), C88(H88A,H88B), C22(H22A,
 H22B), C66(H66A,H66B), C77(H77A,H77B), C44(H44A,H44B)
6.b Me refined with riding coordinates:
 C87(H87A,H87B,H87C), C32(H32A,H32B,H32C), C9(H9A,H9B,H9C), C52(H52A,H52B,
 H52C), C86(H86A,H86B,H86C), C30(H30A,H30B,H30C), C75(H75A,H75B,H75C), C76(H76A,
 H76B,H76C), C85(H85A,H85B,H85C), C20(H20A,H20B,H20C), C8(H8A,H8B,H8C),
 C74(H74A,H74B,H74C), C54(H54A,H54B,H54C), C10(H10A,H10B,H10C), C31(H31A,H31B,
 H31C), C21(H21A,H21B,H21C), C19(H19A,H19B,H19C), C53(H53A,H53B,H53C), C41(H41A,
 H41B,H41C), C43(H43A,H43B,H43C), C42(H42A,H42B,H42C), C63(H63A,H63B,H63C),
 C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C63A(H63D,H63E,H63F), C64A(H64D,H64E,
 H64F), C65A(H65D,H65E,H65F)
6.c Aromatic/amide H refined with riding coordinates:
 C47(H47), C3(H3), C60(H60), C16(H16), C71(H71), C14(H14), C49(H49), C80(H80),
 C25(H25), C5(H5), C27(H27), C38(H38), C82(H82), C36(H36)
6.d Idealised Me refined as rotating group:
 C99(H99A,H99B,H99C), C93(H93A,H93B,H93C), C97(H97A,H97B,H97C), C95(H95A,H95B,
 H95C), C91(H91A,H91B,H91C), C101(H10D,H10E,H10F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 160 electrons were 
found in a volume of 1145\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
3[CH3CN], 0.75[CH3CN] per Unit Cell 
which account for 165 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              42616
_shelx_hkl_checksum              9733
_shelx_fab_checksum              12973
_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 2.423
_oxdiff_exptl_absorpt_empirical_full_min 0.573