Ring-opening polymerization of ε-caprolactone with a macrocyclic tetracarbene indium complex.
Brothers, Henry R.; Chambenahalli, Raju; Nichol, Gary S.; Garden, Jennifer A.; Jenkins, David M.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 487–491; doi:10.1039/d4dt03198a

data_7717679
_publ_section_title
;
 Ring-opening polymerization of &#x3b5;-caprolactone with a macrocyclic
 tetracarbene indium complex.
;
_journal_issue                   2
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              487
_journal_page_last               491
_journal_paper_doi               10.1039/d4dt03198a
_journal_volume                  54
_journal_year                    2025
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C28 H40 B2 Br In N8'
_chemical_formula_sum            'C28 H40 B2 Br In N8'
_chemical_formula_weight         705.03
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-09-09
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-11 deposited with the CCDC.	2024-12-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.1187(5)
_cell_length_b                   18.2532(5)
_cell_length_c                   19.0483(6)
_cell_measurement_reflns_used    20500
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      76.5170
_cell_measurement_theta_min      4.6480
_cell_volume                     6299.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector_area_resol_mean 5.2792
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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     -1.00  45.00   1.00    5.00    --    0.00 -92.00  22.00   46
  2  \w    -46.00  23.00   1.00    5.00    --    0.00  92.00 135.00   69
  3  \w    -80.00  23.00   1.00   15.00    --  -67.05  92.00 135.00  103
  4  \w   -161.00 -83.00   1.00   15.00    --  -67.05 -92.00  22.00   78
  5  \w     -2.00 106.00   1.00   15.00    --   67.05 -92.00  22.00  108
  6  \w    105.00 160.00   1.00   15.00    --   67.05  92.00 135.00   55
  7  \w     27.00 106.00   1.00   15.00    --  121.00 -92.00  22.00   79
  8  \w    139.00 166.00   1.00   15.00    --  121.00  92.00 135.00   27
  9  \w    -95.00 -39.00   1.00    5.00    --    0.00 178.00-120.00   56
 10  \w    -18.00  37.00   1.00    5.00    --    0.00 -77.00 -90.00   55
 11  \w    -19.00  20.00   1.00    5.00    --    0.00 -77.00 -60.00   39
 12  \w    119.00 159.00   1.00   15.00    --   67.05  77.00   0.00   40
 13  \w    101.00 137.00   1.00   15.00    --   67.05 125.00  30.00   36
 14  \w    100.00 149.00   1.00   15.00    --   67.05 125.00  90.00   49
 15  \w     33.00 155.00   1.00   15.00    --   67.05  45.00 120.00  122
 16  \w     39.00  93.00   1.00   15.00    --  121.00 -91.00  90.00   54
 17  \w    121.00 148.00   1.00   15.00    --  121.00 111.00  60.00   27
 18  \w    105.00 162.00   1.00   15.00    --  121.00  77.00-180.00   57
 19  \w    135.00 176.00   1.00   15.00    --  121.00  77.00  30.00   41
 20  \w     28.00  76.00   1.00   15.00    --  121.00 -91.00-150.00   48
 21  \w     29.00  64.00   1.00   15.00    --  121.00 -91.00 150.00   35
 22  \w    135.00 162.00   1.00   15.00    --  121.00 111.00-180.00   27
 23  \w     38.00  99.00   1.00   15.00    --  121.00 -91.00   0.00   61
 24  \w     39.00 108.00   1.00   15.00    --  121.00-111.00-180.00   69
 25  \w     83.00 109.00   1.00   15.00    --  121.00-111.00-150.00   26
 26  \w    106.00 133.00   1.00   15.00    --  121.00 111.00  30.00   27
 27  \w    127.00 153.00   1.00   15.00    --  121.00  49.00 110.94   26
 28  \w    112.00 177.00   1.00   15.00    --  121.00  70.00  88.97   65
 29  \w     82.00 117.00   1.00   15.00    --  121.00  70.00 105.99   35
 30  \w    150.00 177.00   1.00   15.00    --  121.00  70.00 105.99   27
 31  \w     94.00 122.00   1.00   15.00    --  121.00  49.00 110.94   28
 32  \w     53.00 102.00   1.00   15.00    --  121.00 -50.00   0.00   49
 33  \w    125.00 150.00   1.00   15.00    --  121.00 -50.00   0.00   25
 34  \w     36.00 108.00   1.00   15.00    --  121.00-111.00 -30.00   72
 35  \w     83.00 178.00   1.00   15.00    --  121.00  53.00 165.46   95
 36  \w     66.00 105.00   1.00   15.00    --  121.00 -63.00  30.00   39
 37  \w    107.00 134.00   1.00   15.00    --  121.00  77.00-120.00   27
 38  \w    148.00 173.00   1.00   15.00    --  121.00 111.00   0.00   25
 39  \w    114.00 141.00   1.00   15.00    --  121.00 111.00  90.00   27
 40  \w     45.00 103.00   1.00   15.00    --  121.00-108.00 -86.75   58
 41  \w     29.00  54.00   1.00   15.00    --  121.00 -91.00  60.00   25
 42  \w     60.00  99.00   1.00   15.00    --  121.00 -91.00  60.00   39
 43  \w     44.00  71.00   1.00   15.00    --  121.00-111.00-150.00   27
 44  \w    138.00 177.00   1.00   15.00    --  121.00  38.00-120.00   39
 45  \w     75.00 102.00   1.00   15.00    --  121.00 -63.00   0.00   27
 46  \w    100.00 127.00   1.00   15.00    --  121.00  38.00-120.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0477
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            30447
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.236
_diffrn_reflns_theta_min         3.353
_exptl_absorpt_coefficient_mu    7.722
_exptl_absorpt_correction_T_max  0.657
_exptl_absorpt_correction_T_min  0.189
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.487
_exptl_crystal_description       plate
_exptl_crystal_F_000             2864
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of hexane and benzene  by vapour diffusion'
_exptl_crystal_size_max          0.338
_exptl_crystal_size_mid          0.218
_exptl_crystal_size_min          0.064
_refine_diff_density_max         2.979
_refine_diff_density_min         -1.425
_refine_diff_density_rms         0.235
_refine_ls_abs_structure_details
;
 Flack x determined using 4893 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.039(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     730
_refine_ls_number_reflns         30447
_refine_ls_number_restraints     1316
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.1048
_refine_ls_R_factor_gt           0.0858
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1066P)^2^+71.2240P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2180
_refine_ls_wR_factor_ref         0.2362
_reflns_Friedel_coverage         0.816
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.973
_reflns_number_gt                25602
_reflns_number_total             30447
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 87.0939\% 
around [0.00 1.00 0.00] (reciprocal) or [0.00 1.00 -0.00] (direct)
;
_cod_data_source_file            d4dt03198a2.cif
_cod_data_source_block           jg23010
_cod_depositor_comments
'Adding full bibliography for 7717679--7717680.cif.'
_cod_database_code               7717679
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.638
_shelx_estimated_absorpt_t_min   0.180
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.519(2)
 0.481(2)
2. 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
3. Uiso/Uaniso restraints and constraints
In1 \\sim C2 \\sim C4 \\sim C1 \\sim C3 \\sim Br1 \\sim N3 \\sim N4 \\sim N7
\\sim N8 \\sim N1 \\sim N2 \\sim N5 \\sim N6 \\sim C7 \\sim B1 \\sim C8 \\sim
C15 \\sim C11 \\sim B2 \\sim C12 \\sim C13 \\sim C14 \\sim C5 \\sim C6 \\sim
C16 \\sim C9 \\sim C10 \\sim C18 \\sim C17 \\sim C25 \\sim C19 \\sim C20 \\sim
C21 \\sim C24 \\sim C28 \\sim C26 \\sim C22 \\sim C23 \\sim C27: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
In51 \\sim Br51 \\sim C53 \\sim C62 \\sim C65 \\sim C74 \\sim N51 \\sim N52
\\sim N53 \\sim N54 \\sim N56 \\sim N55 \\sim N57 \\sim N58 \\sim C51 \\sim B51
\\sim C52 \\sim C54 \\sim C59 \\sim C60 \\sim C61 \\sim B52 \\sim C64 \\sim C66
\\sim C63 \\sim C71 \\sim C72 \\sim C73 \\sim C75 \\sim C76 \\sim C55 \\sim C58
\\sim C77 \\sim C78 \\sim C67 \\sim C70 \\sim C56 \\sim C57 \\sim C68 \\sim
C69: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C2) \\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 In51, C65, C53, C74, C62, Br51, N55, N56, N52, N51, N57, N58, N53, N54, C63,
 B52, C64, C66, C52, C54, C51, B51, C71, C72, C73, C59, C60, C61, C77, C78, C67,
  C55, C75, C76, C70, C58, C68, C56, C69, C57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 In1, C4, C2, C3, C1, Br1, N7, N8, N3, N4, N5, N6, N1, N2, C11, B2, C12, C13,
 C7, B1, C8, C15, C16, C9, C10, C14, C5, C6, C19, C20, C21, C18, C17, C25, C28,
 C24, C22, C26, C27, C23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Ternary CH refined with riding coordinates:
 C15(H15), C16(H16), C13(H13), C14(H14), C54(H54), C59(H59), C66(H66), C71(H71)
5.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C21(H21A,
 H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C55(H55A,H55B),
 C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C67(H67A,H67B), C68(H68A,H68B),
  C69(H69A,H69B), C70(H70A,H70B)
5.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C5(H5), C6(H6),
 C51(H51), C52(H52), C60(H60), C61(H61), C63(H63), C64(H64), C72(H72), C73(H73)
5.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C78(H78A,
 H78B,H78C)
;
_shelx_res_checksum              71170
_shelx_hkl_checksum              81098
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_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
;