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_7708491
_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         'C94 H122 O10 Pb6 Si2, 2(Cl), 2[CH3CN] 2[OH]'
_chemical_formula_sum            'C94 H122 Cl2 O10 Pb6 Si2'
_chemical_formula_weight         2782.13
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-10 deposited with the CCDC.	2021-09-30 downloaded from the CCDC.
;
_cell_angle_alpha                66.795(5)
_cell_angle_beta                 67.082(4)
_cell_angle_gamma                88.389(3)
_cell_formula_units_Z            1
_cell_length_a                   14.3597(5)
_cell_length_b                   15.8609(8)
_cell_length_c                   15.8791(6)
_cell_measurement_reflns_used    18588
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.4380
_cell_measurement_theta_min      2.4910
_cell_volume                     3027.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HG Saturn724+ (2x2 bin mode)'
_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   -106.00  21.00   1.00   34.00    --  -16.90 -72.00 -60.00  127
  2  \w   -106.00  18.00   1.00   34.00    --  -16.90 -57.00  30.00  124
  3  \w    -50.00  72.00   1.00   34.00    --  -16.90  38.00 -90.00  122
  4  \w   -106.00  21.00   1.00   34.00    --  -16.90 -72.00  90.00  127
  5  \w   -106.00  21.00   1.00   34.00    --  -16.90 -72.00  90.00  127
  6  \w   -106.00  18.00   1.00   34.00    --  -16.90 -57.00 -60.00  124
  7  \w   -106.00  18.00   1.00   34.00    --  -16.90 -57.00 150.00  124
  8  \w    -55.00  54.00   1.00   34.00    --  -16.90  72.00  60.00  109
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with HF Varimax confocal mirrors and an AFC12 goniometer and HG Saturn 724+ detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0187850000
_diffrn_orient_matrix_UB_12      -0.0031767000
_diffrn_orient_matrix_UB_13      -0.0340332000
_diffrn_orient_matrix_UB_21      0.0088266000
_diffrn_orient_matrix_UB_22      -0.0467697000
_diffrn_orient_matrix_UB_23      0.0132441000
_diffrn_orient_matrix_UB_31      -0.0500963000
_diffrn_orient_matrix_UB_32      -0.0149326000
_diffrn_orient_matrix_UB_33      0.0388673000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  mirror
_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  0.0600
_diffrn_reflns_av_unetI/netI     0.0509
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            57186
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.028
_diffrn_reflns_theta_max         25.028
_diffrn_reflns_theta_min         2.252
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    8.376
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62851
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.34b (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.526
_exptl_crystal_description       plate
_exptl_crystal_F_000             1320
_exptl_crystal_size_max          0.090
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.025
_refine_diff_density_max         4.359
_refine_diff_density_min         -2.198
_refine_diff_density_rms         0.240
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     582
_refine_ls_number_reflns         10657
_refine_ls_number_restraints     569
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.1246
_refine_ls_R_factor_gt           0.0816
_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^)+(0.0978P)^2^+84.1792P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2000
_refine_ls_wR_factor_ref         0.2366
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6953
_reflns_number_total             10657
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02790e2.cif
_cod_data_source_block           20017ncs0856
_cod_original_cell_volume        3027.9(2)
_cod_database_code               7708491
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C49 H54 O5 Pb3 N Si'
_chemical_oxdiff_usercomment     '[8]PbTMS'
_cell_oxdiff_angle_alpha         66.795(5)
_cell_oxdiff_angle_beta          67.082(4)
_cell_oxdiff_angle_gamma         88.389(3)
_cell_oxdiff_length_a            14.3597(5)
_cell_oxdiff_length_b            15.8609(8)
_cell_oxdiff_length_c            15.8791(6)
_cell_oxdiff_measurement_reflns_used 18588
_cell_oxdiff_volume              3027.9(2)
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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
 C40-C41 \\sim C40-C41A
 with sigma of 0.02
 C40-C42 \\sim C40-C42A
 with sigma of 0.02
 C40-C43 \\sim C40-C43A
 with sigma of 0.02
 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
 C8A-C9A \\sim C9A-C10A \\sim C10A-C8A
 with sigma of 0.02
 C46-Si1 \\sim C46A-Si1A
 with sigma of 0.02
 C45-C47 \\sim C45A-C47A
 with sigma of 0.04
 C47-Si1 \\sim C47A-Si1A
 with sigma of 0.02
 C46-C47 \\sim C46A-C47A
 with sigma of 0.04
 C45-O3 \\sim C45A-O3
 with sigma of 0.04
 C45-Si1 \\sim C45A-Si1A
 with sigma of 0.02
 C47-O3 \\sim C47A-O3
 with sigma of 0.04
 O3-Si1 \\sim O3-Si1A
 with sigma of 0.02
 C46-O3 \\sim C46A-O3
 with sigma of 0.04
 C45-C46 \\sim C45A-C46A
 with sigma of 0.04
 Si1A-C46A \\sim Si1A-C47A \\sim Si1A-C45A \\sim Si1-C45 \\sim Si1-C46 \\sim
Si1-C47
 with sigma of 0.02
 C41-C42 \\sim C41-C43 \\sim C42-C43 \\sim C43A-C42A \\sim C43A-C41A \\sim
C42A-C41A
 with sigma of 0.04
 C7-C4 \\sim C7-C8 \\sim C7-C9 \\sim C7-C10 \\sim C7-C9A \\sim C7-C8A \\sim
C7-C10A
 with sigma of 0.02
 C40-C37 \\sim C40-C41 \\sim C40-C42 \\sim C40-C43 \\sim C40-C43A \\sim
C40-C42A \\sim C40-C41A
 with sigma of 0.02
 C45-C46 \\sim C45-C47 \\sim C46-C47
 with sigma of 0.04
 C8-C9 \\sim C8-C10 \\sim C9-C10 \\sim C9A-C8A \\sim C9A-C10A \\sim C8A-C10A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C9 \\sim C9A \\sim C8 \\sim C8A \\sim C10 \\sim C10A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C45A \\sim C45 \\sim C47A \\sim C47 \\sim C46A \\sim C46: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
C46 \\sim C46A \\sim C47 \\sim C47A \\sim C45 \\sim C45A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
C8 \\sim C8A \\sim C9A \\sim C9 \\sim C10A \\sim C10: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C47 \\sim C47A \\sim C45A \\sim C45 \\sim C46A \\sim C46: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C23) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uiso(Cl1C) = Uiso(Cl1A) = Uiso(Cl1B)
Uanis(Si1) = Uanis(Si1A)
Uiso(C45) = Uiso(C45A) = Uiso(C47A) = Uiso(C47) = Uiso(C46) = Uiso(C46A)
4. Rigid body (RIGU) restrains
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C15, C16, C17, C18,
 C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34,
  C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46, C47, C43A, C42A,
 C41A, C9A, C8A, C10A, C46A, C47A, C45A, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40, C42, C41A, C43A, C42A, C41, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, C8, C9, C10, C9A, C8A, C10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C24, C33, C28, C23, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23, C27, C28, C24, C25, C33, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C36, C38, C39, C34, C35, C44, C33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(Cl1A)]+1*[Sof(Cl1B)]+1*[Sof(Cl1C)]=1 with esd of 0.0001
 Sof(C43A)=Sof(H43D)=Sof(H43E)=Sof(H43F)=Sof(C42A)=Sof(H42D)=Sof(H42E)=
 Sof(H42F)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=1-FVAR(1)
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=FVAR(1)
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=
 Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(2)
 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(2)
 Sof(C46A)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C47A)=Sof(H47D)=Sof(H47E)=
 Sof(H47F)=Sof(Si1A)=Sof(C45A)=Sof(H45D)=Sof(H45E)=Sof(H45F)=1-FVAR(3)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(Si1)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C22(H22A,H22B), C33(H33A,H33B), C44(H44A,H44B)
6.b Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C9A(H9AA,H9AB,H9AC), C8A(H8AA,H8AB,
 H8AC), C10A(H10D,H10E,H10F), C46A(H46D,H46E,H46F), C47A(H47D,H47E,H47F),
 C45A(H45D,H45E,H45F)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C16(H16), C25(H25), C27(H27), C36(H36), C38(H38), C14(H14)
6.d Idealised Me refined as rotating group:
 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), C43A(H43D,H43E,H43F), C42A(H42D,H42E,H42F),
 C41A(H41D,H41E,H41F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 62 electrons were 
found in a volume of 814\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[CH3CN] and 2{OH-] per Asymmetric Unit 
which account for 62 electrons 
per unit cell. The [OH-} is needed for charge balancing. 
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              46050
_shelx_hkl_checksum              3022
_shelx_fab_checksum              68865
_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 1.872
_oxdiff_exptl_absorpt_empirical_full_min 0.600