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_7708490
_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
'C207 H253 O29 Pb13, 3.5(C2 H3 N), [+ 7.5MeCN]'
_chemical_formula_sum            'C214 H263.5 N3.5 O29 Pb13'
_chemical_formula_weight         6042.24
_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                72.2187(11)
_cell_angle_beta                 82.1388(10)
_cell_angle_gamma                67.9805(11)
_cell_formula_units_Z            2
_cell_length_a                   19.2866(2)
_cell_length_b                   23.0573(3)
_cell_length_c                   29.8976(4)
_cell_measurement_reflns_used    64995
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.4190
_cell_measurement_theta_min      1.9740
_cell_volume                     11733.0(3)
_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_temperature      100(2)
_diffrn_detector                 'hybrid pixel detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.991
_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    -76.00  75.00   0.50    5.00    --  -14.40  36.00 -74.00  302
  2  \w   -104.00  47.00   0.50    5.00    --  -14.40 -36.00 128.00  302
  3  \w    -51.00  75.00   0.50    5.00    --  -14.40  57.00 -30.00  252
  4  \w   -104.00  22.00   0.50    5.00    --  -14.40 -60.00 120.00  252
  5  \w   -104.00  22.00   0.50    5.00    --  -14.40 -60.00-180.00  252
  6  \w   -103.00  21.00   0.50    5.00    --  -14.40 -60.00  60.00  248
  7  \w    -36.00  -9.00   0.50    5.00    --  -14.40 -60.00-150.00   54
  8  \w   -104.00  21.00   0.50    5.00    --  -14.40 -60.00 -30.00  250
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, AFC12 \k goniometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa 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      -0.0104284000
_diffrn_orient_matrix_UB_12      0.0261703000
_diffrn_orient_matrix_UB_13      0.0102339000
_diffrn_orient_matrix_UB_21      -0.0362578000
_diffrn_orient_matrix_UB_22      -0.0017993000
_diffrn_orient_matrix_UB_23      0.0052478000
_diffrn_orient_matrix_UB_31      0.0123038000
_diffrn_orient_matrix_UB_32      -0.0224563000
_diffrn_orient_matrix_UB_33      0.0221101000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0962
_diffrn_reflns_av_unetI/netI     0.1024
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            256697
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.283
_diffrn_reflns_theta_min         1.807
_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    9.349
_exptl_absorpt_correction_T_max  0.59537
_exptl_absorpt_correction_T_min  0.58678
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.89a (Rigaku Oxford Diffraction, 2020)
Spherical absorption correction
using equivalent radius and absorption coefficient.
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    1.710
_exptl_crystal_description       'block (cut)'
_exptl_crystal_F_000             5740
_exptl_crystal_size_max          0.104
_exptl_crystal_size_mid          0.061
_exptl_crystal_size_min          0.053
_exptl_crystal_size_rad          0.041
_refine_diff_density_max         5.049
_refine_diff_density_min         -1.882
_refine_diff_density_rms         0.264
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2358
_refine_ls_number_reflns         57728
_refine_ls_number_restraints     2583
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.1214
_refine_ls_R_factor_gt           0.0756
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0537P)^2^+195.8907P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1448
_refine_ls_wR_factor_ref         0.1628
_reflns_Friedel_coverage         0.000
_reflns_number_gt                37456
_reflns_number_total             57728
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02790e2.cif
_cod_data_source_block           2020ncs0338r1z
_cod_original_cell_volume        11733.0(2)
_cod_original_formula_sum        'C214 H263.50 N3.50 O29 Pb13'
_cod_database_code               7708490
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C52 H48 O8 Pb3'
_chemical_oxdiff_usercomment     oxocalix(6)aren+4Pb(OiPr)2
_cell_oxdiff_angle_alpha         72.2187(11)
_cell_oxdiff_angle_beta          82.1388(10)
_cell_oxdiff_angle_gamma         67.9805(11)
_cell_oxdiff_length_a            19.2866(2)
_cell_oxdiff_length_b            23.0573(3)
_cell_oxdiff_length_c            29.8976(4)
_cell_oxdiff_measurement_reflns_used 64995
_cell_oxdiff_volume              11733.0(2)
_shelx_estimated_absorpt_t_max   0.637
_shelx_estimated_absorpt_t_min   0.443
_reflns_odcompleteness_completeness 99.09
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_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
 O29-H29
 0.85 with sigma of 0.01
 C210-H29
 1.865544 with sigma of 0.02
 Pb11-H29
 2.951214 with sigma of 0.02
 C99-C102 \\sim C99-C69
 with sigma of 0.02
 C100-C102 \\sim C1B-C69
 with sigma of 0.02
 C99-C101 \\sim C99-C1A
 with sigma of 0.02
 C99-C100 \\sim C99-C1B
 with sigma of 0.04
 C100-C101 \\sim C100-C102 \\sim C101-C102 \\sim C69-C1A \\sim C69-C1B \\sim
C1A-C1B
 with sigma of 0.04
 C99-C96 \\sim C99-C100 \\sim C99-C101 \\sim C99-C102 \\sim C99-C69 \\sim
C99-C1A \\sim C99-C1B
 with sigma of 0.02
 C77-C79 \\sim C77-C79A
 with sigma of 0.02
 C77-C78 \\sim C77-C78A
 with sigma of 0.02
 C77-C80 \\sim C77-C80A
 with sigma of 0.02
 C77-C74 \\sim C77-C78 \\sim C77-C79 \\sim C77-C80 \\sim C77-C79A \\sim
C77-C78A \\sim C77-C80A
 with sigma of 0.02
 C78-C79 \\sim C78-C80 \\sim C79A-C78A \\sim C78A-C80A
 with sigma of 0.04
 C7-C9 \\sim C7-C9A
 with sigma of 0.02
 C7-C10 \\sim C7-C10A
 with sigma of 0.02
 C7-C8 \\sim C7-C8A
 with sigma of 0.02
 C7-C4 \\sim C7-C8 \\sim C7-C9 \\sim C7-C10 \\sim C7-C8A \\sim C7-C9A \\sim
C7-C10A
 with sigma of 0.02
 C8-C9 \\sim C8-C10 \\sim C9-C10 \\sim C8A-C9A \\sim C8A-C10A
 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
 C29-C30 \\sim C29-C31 \\sim C29-C32 \\sim C29-C32A \\sim C29-C31A \\sim
C29-C30A \\sim C29-C26
 with sigma of 0.02
 C30-C31 \\sim C31-C32 \\sim C32A-C31A \\sim C31A-C30A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C80 \\sim C78A \\sim C78 \\sim C79A \\sim C79 \\sim C80A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
C10 \\sim C10A \\sim C8 \\sim C9 \\sim C9A \\sim C8A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C30A \\sim C31 \\sim C32A \\sim C32 \\sim C31A \\sim C29 \\sim C30: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C30 \\sim C32A \\sim C32 \\sim C31A \\sim C31 \\sim C30A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(N1) \\sim Ueq, Uanis(C251) \\sim Ueq, Uanis(C252) \\sim Ueq, Uanis(N2)
\\sim Ueq, Uanis(C253) \\sim Ueq, Uanis(C254) \\sim Ueq, Uanis(N3) \\sim Ueq,
Uanis(C255) \\sim Ueq, Uanis(C256) \\sim Ueq, : with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C126) \\sim Ueq, Uanis(C71) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
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(C69)=Sof(H69a)=Sof(H69b)=Sof(H69c)=Sof(C1A)=Sof(H1Aa)=Sof(H1Ab)=Sof(H1Ac)=
 Sof(C1B)=Sof(H1Ba)=Sof(H1Bb)=Sof(H1Bc)=1-FVAR(1)
 Sof(C100)=Sof(H10d)=Sof(H10e)=Sof(H10f)=Sof(C101)=Sof(H10g)=Sof(H10h)=
 Sof(H10i)=Sof(C102)=Sof(H10j)=Sof(H10k)=Sof(H10l)=FVAR(1)
 Sof(C79A)=Sof(H79d)=Sof(H79e)=Sof(H79f)=Sof(C78A)=Sof(H78d)=Sof(H78e)=
 Sof(H78f)=Sof(C80A)=Sof(H80d)=Sof(H80e)=Sof(H80f)=1-FVAR(2)
 Sof(C78)=Sof(H78a)=Sof(H78b)=Sof(H78c)=Sof(C79)=Sof(H79a)=Sof(H79b)=Sof(H79c)=
 Sof(C80)=Sof(H80a)=Sof(H80b)=Sof(H80c)=FVAR(2)
 Sof(C8A)=Sof(H8Aa)=Sof(H8Ab)=Sof(H8Ac)=Sof(C9A)=Sof(H9Aa)=Sof(H9Ab)=Sof(H9Ac)=
 Sof(C10A)=Sof(H10q)=Sof(H10r)=Sof(H10s)=1-FVAR(3)
 Sof(C8)=Sof(H8a)=Sof(H8b)=Sof(H8c)=Sof(C9)=Sof(H9a)=Sof(H9b)=Sof(H9c)=
 Sof(C10)=Sof(H10a)=Sof(H10b)=Sof(H10c)=FVAR(3)
 Sof(C32A)=Sof(H32d)=Sof(H32e)=Sof(H32f)=Sof(C31A)=Sof(H31d)=Sof(H31e)=
 Sof(H31f)=Sof(C30A)=Sof(H30d)=Sof(H30e)=Sof(H30f)=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)
 Fixed Sof: N4(0.5) C257(0.5) C258(0.5) H25j(0.5) H25k(0.5) H25l(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11a,H11b), C22(H22a,H22b), C33(H33a,H33b), C34(H34a,H34b), C45(H45a,
 H45b), C56(H56a,H56b), C67(H67a,H67b), C68(H68a,H68b), C81(H81a,H81b),
 C92(H92a,H92b), C103(H10m,H10n), C104(H10o,H10p), C115(H11l,H11m), C126(H12j,
 H12k), C137(H13j,H13k), C138(H13l,H13m), C151(H15d,H15e), C162(H16g,H16h),
 C173(H17j,H17k), C174(H17l,H17m), C185(H18j,H18k), C196(H19m,H19n), C207(H20m,
 H20n), C208(H20o,H20p)
6.b Me refined with riding coordinates:
 C8(H8a,H8b,H8c), C9(H9a,H9b,H9c), C10(H10a,H10b,H10c), C30(H30a,H30b,H30c),
 C31(H31a,H31b,H31c), C32(H32a,H32b,H32c), C78(H78a,H78b,H78c), C79(H79a,H79b,
 H79c), C80(H80a,H80b,H80c), C100(H10d,H10e,H10f), C101(H10g,H10h,H10i),
 C102(H10j,H10k,H10l), C69(H69a,H69b,H69c), C1A(H1Aa,H1Ab,H1Ac), C1B(H1Ba,H1Bb,
 H1Bc), C79A(H79d,H79e,H79f), C78A(H78d,H78e,H78f), C80A(H80d,H80e,H80f),
 C8A(H8Aa,H8Ab,H8Ac), C9A(H9Aa,H9Ab,H9Ac), C10A(H10q,H10r,H10s), C32A(H32d,H32e,
 H32f), C31A(H31d,H31e,H31f), C30A(H30d,H30e,H30f)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C14(H14), C16(H16), C25(H25), C27(H27), C37(H37), C39(H39),
 C48(H48), C50(H50), C59(H59), C61(H61), C73(H73), C75(H75), C84(H84), C86(H86),
  C95(H95), C97(H97), C107(H107), C109(H109), C118(H118), C120(H120),
 C129(H129), C131(H131), C143(H143), C145(H145), C154(H154), C156(H156),
 C165(H165), C167(H167), C177(H177), C179(H179), C188(H188), C190(H190),
 C199(H199), C201(H201)
6.d Idealised Me refined as rotating group:
 C19(H19a,H19b,H19c), C20(H20a,H20b,H20c), C21(H21a,H21b,H21c), C42(H42a,H42b,
 H42c), C43(H43a,H43b,H43c), C44(H44a,H44b,H44c), C53(H53a,H53b,H53c), C54(H54a,
 H54b,H54c), C55(H55a,H55b,H55c), C64(H64a,H64b,H64c), C65(H65a,H65b,H65c),
 C66(H66a,H66b,H66c), C89(H89a,H89b,H89c), C90(H90a,H90b,H90c), C91(H91a,H91b,
 H91c), C112(H11c,H11d,H11e), C113(H11f,H11g,H11h), C114(H11i,H11j,H11k),
 C123(H12a,H12b,H12c), C124(H12d,H12e,H12f), C125(H12g,H12h,H12i), C134(H13a,
 H13b,H13c), C135(H13d,H13e,H13f), C136(H13g,H13h,H13i), C148(H14a,H14b,H14c),
 C149(H14d,H14e,H14f), C150(H15a,H15b,H15c), C159(H15f,H15g,H15h), C160(H16a,
 H16b,H16c), C161(H16d,H16e,H16f), C170(H17a,H17b,H17c), C171(H17d,H17e,H17f),
 C172(H17g,H17h,H17i), C182(H18a,H18b,H18c), C183(H18d,H18e,H18f), C184(H18g,
 H18h,H18i), C193(H19d,H19e,H19f), C194(H19g,H19h,H19i), C195(H19j,H19k,H19l),
 C204(H20d,H20e,H20f), C205(H20g,H20h,H20i), C206(H20j,H20k,H20l), C211(H21d,
 H21e,H21f), C212(H21g,H21h,H21i), C252(H25a,H25b,H25c), C254(H25d,H25e,H25f),
 C256(H25g,H25h,H25i), C258(H25j,H25k,H25l)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 328 electrons were 
found in a volume of 2331\%A^3^ in 4 voids per unit cell. 
This is consistent with the presence of 
[15 MeCN] per Unit Cell 
which account for 330 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              46364
_shelx_hkl_checksum              27698
_shelx_fab_checksum              82759
_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 3.299
_oxdiff_exptl_absorpt_empirical_full_min 0.522