Ring opening polymerization of d,l-lactide and ε-caprolactone catalysed by (pyrazol-1-yl)copper(ii) carboxylate complexes
Appavoo, Divambal; Spencer, Lara C.; Guzei, Ilia A.; Gómez-García, Carlos J.; van Wyk, Juanita L.; Darkwa, James; RSC Advances 11 (2021) 13475–13485; doi:10.1039/D1RA00339A

data_7242648
_publ_section_title
;
 Ring opening polymerization of d,l-lactide and \e-caprolactone catalysed
 by (pyrazol-1-yl)copper(ii) carboxylate complexes
;
_journal_issue                   22
_journal_name_full               'RSC Advances'
_journal_page_first              13475
_journal_page_last               13485
_journal_paper_doi               10.1039/D1RA00339A
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C46 H38 Cl4 Cu2 N4 O8'
_chemical_formula_sum            'C46 H38 Cl4 Cu2 N4 O8'
_chemical_formula_weight         1043.68
_space_group_crystal_system      tetragonal
_space_group_IT_number           86
_space_group_name_Hall           '-P 4bc'
_space_group_name_H-M_alt        'P 42/n :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-12-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2020-12-17 deposited with the CCDC.	2021-03-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.2772(2)
_cell_length_b                   16.2772(2)
_cell_length_c                   17.3126(2)
_cell_measurement_reflns_used    999
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      70.67
_cell_measurement_theta_min      3.84
_cell_volume                     4586.93(10)
_computing_cell_refinement       'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker APEX II'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX II'
_diffrn_measurement_method       '0.60\ \w and 0.6\ \f scans'
_diffrn_radiation_collimation    '0.5 mm double-pinhole'
_diffrn_radiation_detector       'Bruker APEX II'
_diffrn_radiation_monochromator  'equatorially mounted graphite'
_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  0.0374
_diffrn_reflns_av_unetI/netI     0.0151
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            73846
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.701
_diffrn_reflns_theta_min         2.552
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'Siemens, K FFCU 2K 90'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.766
_exptl_absorpt_correction_T_max  0.6402
_exptl_absorpt_correction_T_min  0.3881
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.511
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2128
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.668
_refine_diff_density_min         -0.786
_refine_diff_density_rms         0.151
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     322
_refine_ls_number_reflns         4450
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0659
_refine_ls_R_factor_gt           0.0648
_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^)+(0.1313P)^2^+3.4860P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1729
_refine_ls_wR_factor_ref         0.1745
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4331
_reflns_number_total             4450
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ra00339a2.cif
_cod_data_source_block           darkwa133
_cod_original_cell_volume        4586.93(12)
_cod_original_sg_symbol_H-M      'P 42/n'
_cod_database_code               7242648
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.640
_shelx_estimated_absorpt_t_min   0.388
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.537(2)
 0.463(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. Restrained distances
 C9A-C9A_$1 = C7A-C7A_$1 = C9A-C8A = C8A-C7A
 1.39 with sigma of 0.005
 Cu1-N1 \\sim Cu1-N1A
 with sigma of 0.02
 Cl1A-C12A \\sim Cl1-C12 \\sim Cl2-C19 \\sim Cl2A-C19A
 with sigma of 0.005
 C11A-C10 \\sim C11-C10 \\sim C18-C17 \\sim C18A-C17
 with sigma of 0.005
4. Uiso/Uaniso restraints and constraints
Uanis(N1) = Uanis(N1A)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(N2) = Uanis(N2A)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(C1) = Uanis(C1A)
Uanis(C2) = Uanis(C2A)
Uanis(C3) = Uanis(C3A)
Uanis(C4) = Uanis(C4A)
Uanis(C5) = Uanis(C5A)
Uanis(C6) = Uanis(C6A)
Uanis(C7) = Uanis(C7A)
Uanis(C8) = Uanis(C8A)
Uanis(C9) = Uanis(C9A)
Uanis(C11) = Uanis(C11A)
Uanis(C12) = Uanis(C12A)
Uanis(C13) = Uanis(C13A)
Uanis(C14) = Uanis(C14A)
Uanis(C15) = Uanis(C15A)
Uanis(C16) = Uanis(C16A)
Uanis(C18) = Uanis(C18A)
Uanis(C19) = Uanis(C19A)
Uanis(C20) = Uanis(C20A)
Uanis(C21) = Uanis(C21A)
Uanis(C22) = Uanis(C22A)
Uanis(C23) = Uanis(C23A)
5. Same fragment restrains
{N1A, N2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A} sigma for 1-2: 0.02,
1-3: 0.005
as in
{N1, N2, C1, C2, C3, C4, C5, C6, C7, C8, C9}
6. Others
 Sof(N1A)=Sof(N2A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C2A)=Sof(C3A)=
 Sof(H3A)=Sof(C4A)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C6A)=Sof(H6AA)=
 Sof(H6AB)=Sof(C7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(Cl1A)=Sof(C11A)=
 Sof(C12A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=
 Sof(C16A)=Sof(H16A)=Sof(Cl2A)=Sof(C18A)=Sof(C23A)=Sof(H23A)=Sof(C22A)=
 Sof(H22A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=Sof(H20A)=Sof(C19A)=1-FVAR(1)
 Sof(N1)=Sof(N2)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=Sof(C3)=Sof(H3)=
 Sof(C4)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C7)=
 Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(Cl1)=Sof(C11)=Sof(C12)=Sof(C13)=Sof(H13)=
 Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=Sof(Cl2)=Sof(C18)=
 Sof(C19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=
 Sof(H23)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C6A(H6AA,H6AB)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C9(H9), C3A(H3A), C8A(H8A), C9A(H9A), C13(H13), C14(H14),
 C15(H15), C16(H16), C13A(H13A), C14A(H14A), C15A(H15A), C16A(H16A), C20(H20),
 C21(H21), C22(H22), C23(H23), C23A(H23A), C22A(H22A), C21A(H21A), C20A(H20A)
7.c Fitted hexagon refined as free rotating group:
 C11(C12,C13,C14,C15,C16), C11A(C12A,C13A,C14A,C15A,C16A), C18(C19,C20,C21,C22,
 C23), C18A(C23A,C22A,C21A,C20A,C19A)
7.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C5(H5A,H5B,H5C), C1A(H1AA,H1AB,H1AC), C5A(H5AA,H5AB,H5AC)
;
_shelx_res_checksum              77909
_olex2_submission_special_instructions 'No special instructions were received'