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_7708485
_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
'C182 H223 Li2 N3 O17 Pb4, 2(C2 H3 N), 2.5[CH3CN]'
_chemical_formula_sum            'C186 H229 Li2 N5 O17 Pb4'
_chemical_formula_weight         3649.37
_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             2021-03-30
_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                97.3001(15)
_cell_angle_beta                 100.2859(17)
_cell_angle_gamma                102.8843(16)
_cell_formula_units_Z            1
_cell_length_a                   13.7079(3)
_cell_length_b                   15.0694(2)
_cell_length_c                   22.7536(4)
_cell_measurement_reflns_used    14827
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      70.0290
_cell_measurement_theta_min      3.0130
_cell_volume                     4439.47(15)
_computing_cell_refinement       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.975
_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    0.75    --    0.00  20.00-150.00  356
  2  \w    -84.00  94.00   0.50    3.00    --    5.00  39.00  60.00  356
  3  \w   -179.00  -1.00   0.50    3.00    --  -90.00  59.00   3.80  356
  4  \w   -179.00  -1.00   0.50    3.00    --  -90.00  59.00-108.33  356
  5  \w   -179.00  -1.00   0.50    3.00    --  -90.00  57.00 128.04  356
  6  \w   -179.00  -1.00   0.50    3.00    --  -90.00  20.00  60.00  356
  7  \w   -179.00  -5.00   0.50    3.00    --  -90.00  59.00  58.60  348
  8  \w   -150.00 -77.00   0.50    3.00    --  -90.00  55.00-178.78  146
  9  \w    -35.00  -9.00   0.50    3.00    --  -90.00  55.00-178.78   52
 10  \w   -178.00-103.00   0.50    3.00    --  -90.00  59.00 -54.23  150
 11  \w    -94.00 -68.00   0.50    3.00    --  -90.00  59.00 -54.23   52
 12  \w    -61.00 -26.00   0.50    3.00    --  -90.00  59.00 -54.23   70
 13  \w    -60.00 -28.00   0.50    3.00    --  -90.00  59.00-159.92   64
 14  \w   -137.00-112.00   0.50    3.00    --  -90.00  59.00  58.60   50
 15  \w   -178.00  -2.00   0.50    3.00    --  -90.00  10.00-150.00  352
 16  \w   -172.00 -94.00   0.50    3.00    --  -90.00  59.00  89.68  156
 17  \w    -84.00 -58.00   0.50    3.00    --  -90.00  59.00  89.68   52
 18  \w    -34.00  -8.00   0.50    3.00    --  -90.00  59.00  89.68   52
 19  \w   -178.00 -11.00   0.50    3.00    --  -90.00  49.00  30.00  334
 20  \w   -168.00-143.00   0.50    3.00    --  -90.00  59.00 145.68   50
 21  \w   -128.00-101.00   0.50    3.00    --  -90.00  59.00 145.68   54
 22  \w    -79.00 -53.00   0.50    3.00    --  -90.00  59.00 145.68   52
 23  \w   -165.00-110.00   0.50    3.00    --  -90.00  59.00  29.17  110
 24  \w   -173.00-148.00   0.50    3.00    --  -90.00  59.00 -17.95   50
 25  \w   -170.00-144.00   0.50    3.00    --  -90.00  10.00 -30.00   52
 26  \w   -178.00 -66.00   0.50    3.00    --  -90.00  59.00-159.92  224
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, AFC12 \k goniometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0700326000
_diffrn_orient_matrix_UB_12      0.0650717000
_diffrn_orient_matrix_UB_13      0.0097795000
_diffrn_orient_matrix_UB_21      -0.0423328000
_diffrn_orient_matrix_UB_22      -0.0161786000
_diffrn_orient_matrix_UB_23      -0.0689693000
_diffrn_orient_matrix_UB_31      -0.0850424000
_diffrn_orient_matrix_UB_32      -0.0827365000
_diffrn_orient_matrix_UB_33      0.0055285000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0948
_diffrn_reflns_av_unetI/netI     0.0778
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            74814
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.367
_diffrn_reflns_theta_min         3.055
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FRE+'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    7.706
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82841
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.89a (Rigaku Oxford Diffraction, 2020)
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    1.365
_exptl_crystal_description       plate
_exptl_crystal_F_000             1850
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.897
_refine_diff_density_min         -2.420
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.228
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     961
_refine_ls_number_reflns         16536
_refine_ls_number_restraints     902
_refine_ls_restrained_S_all      1.202
_refine_ls_R_factor_all          0.0963
_refine_ls_R_factor_gt           0.0795
_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^)+(0.0068P)^2^+35.4697P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1226
_refine_ls_wR_factor_ref         0.1279
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14151
_reflns_number_total             16536
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02790e2.cif
_cod_data_source_block           1platon_sq
_cod_original_cell_volume        4439.47(14)
_cod_database_code               7708485
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C44 H52 O4 Pb'
_chemical_oxdiff_usercomment     Pb(4)
_cell_oxdiff_angle_alpha         97.3001(15)
_cell_oxdiff_angle_beta          100.2859(17)
_cell_oxdiff_angle_gamma         102.8843(16)
_cell_oxdiff_length_a            13.7079(3)
_cell_oxdiff_length_b            15.0694(2)
_cell_oxdiff_length_c            22.7536(4)
_cell_oxdiff_measurement_reflns_used 14827
_cell_oxdiff_volume              4439.47(14)
_reflns_odcompleteness_completeness 99.11
_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
 H8-O8
 0.85 with sigma of 0.02
 H8-O5
 1.85 with sigma of 0.02
 C7-C10 \\sim C7-C10A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C17) \\sim Ueq, Uanis(C21) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(N2) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C103) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
Uiso(N1) = Uiso(O1W)
Uiso(C10A) = Uiso(C10)
4. 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
5. Others
 Sof(C71B)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C69B)=Sof(H69D)=Sof(H69E)=
 Sof(H69F)=Sof(C70B)=Sof(H70D)=Sof(H70E)=Sof(H70F)=1-FVAR(1)
 Sof(C69A)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70A)=Sof(H70A)=Sof(H70B)=
 Sof(H70C)=Sof(C71A)=Sof(H71A)=Sof(H71B)=Sof(H71C)=FVAR(1)
 Uiso(C69A)=Uiso(C70A)=Uiso(C71A)=Uiso(C71B)=Uiso(C69B)=Uiso(C70B)=FVAR(2)
 Sof(C10A)=Sof(H10G)=Sof(H10H)=Sof(H10I)=1-FVAR(3)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(3)
 Fixed Sof: N1(0.5) C96(0.5) H96A(0.5) H96B(0.5) H96C(0.5) C95(0.5) O1W(0.5)
 Fixed Uiso: H8(0.032)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C22(H22A,H22B), C33(H33A,H33B), C44(H44A,H44B), C61(H61A,
 H61B), C72(H72A,H72B), C83(H83A,H83B), C94(H94A,H94B)
6.b Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C),
 C21(H21A,H21B,H21C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C58(H58A,
 H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C69A(H69A,H69B,H69C),
 C70A(H70A,H70B,H70C), C71A(H71A,H71B,H71C), C71B(H71D,H71E,H71F), C69B(H69D,
 H69E,H69F), C70B(H70D,H70E,H70F), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C),
 C82(H82A,H82B,H82C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C93(H93A,H93B,
 H93C)
6.c Me refined as rotating group:
 C10(H10A,H10B,H10C), C10A(H10G,H10H,H10I)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C14(H14), C16(H16), C25(H25), C27(H27), C36(H36), C38(H38),
 C53(H53), C55(H55), C64(H64), C66(H66), C75(H75), C77(H77), C86(H86), C88(H88)
6.e Tetrahedral OH refined with riding coordinates:
 O6(H6), O7(H7)
6.f Idealised Me refined as rotating group:
 C104(H10D,H10E,H10F), C106(H10J,H10K,H10L), C96(H96A,H96B,H96C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 58 electrons were 
found in a volume of 446\%A^3^ in 4 voids per unit cell. 
This is consistent with the presence of 
2.5[CH3CN] per Asymmetric Unit 
which account for 58 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              46274
_shelx_hkl_checksum              31310
_shelx_fab_checksum              940
_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 1.715
_oxdiff_exptl_absorpt_empirical_full_min 0.670