Dinuclear zinc(II) pyrazolates with different degrees of ring-fluorination and their use in zinc(II) mediated olefin aziridination
Ponduru, Tharun Teja; Dias, H. V. Rasika; Dalton Trans.  (2017) –; doi:10.1039/C7DT02951A

data_7044198
_publ_section_title
;
 Dinuclear zinc(II) pyrazolates with different degrees of
 ring-fluorination and their use in zinc(II) mediated olefin aziridination
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT02951A
_journal_year                    2017
_chemical_formula_moiety         'C18 H20 F12 N4 O Zn2'
_chemical_formula_sum            'C18 H20 F12 N4 O Zn2'
_chemical_formula_weight         667.12
_chemical_name_common            '[{(3,5-(CF3)2Pz)ZnEt}2(\m-THF)]'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-12-07
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_audit_update_record
;
2017-08-02 deposited with the CCDC.
2017-09-11 downloaded from the CCDC.
;
_cell_angle_alpha                74.364(2)
_cell_angle_beta                 84.584(2)
_cell_angle_gamma                88.954(2)
_cell_formula_units_Z            4
_cell_length_a                   12.5728(8)
_cell_length_b                   14.0025(8)
_cell_length_c                   14.2851(8)
_cell_measurement_reflns_used    9930
_cell_measurement_temperature    102(2)
_cell_measurement_theta_max      35.70
_cell_measurement_theta_min      2.97
_cell_volume                     2411.0(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      101.82
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type
'Bruker D8 Quest with a Photon 100 CMOS detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0279
_diffrn_reflns_av_unetI/netI     0.0427
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            22618
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.000
_diffrn_reflns_theta_min         2.951
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    2.102
_exptl_absorpt_correction_T_max  0.7470
_exptl_absorpt_correction_T_min  0.5164
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0897 before and 0.0469 after correction.
The Ratio of minimum to maximum transmission is 0.6913.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.838
_exptl_crystal_description       plates
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.51
_exptl_crystal_size_mid          0.43
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.757
_refine_diff_density_min         -0.818
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.166
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     709
_refine_ls_number_reflns         10459
_refine_ls_number_restraints     34
_refine_ls_restrained_S_all      1.165
_refine_ls_R_factor_all          0.0494
_refine_ls_R_factor_gt           0.0443
_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^)+11.0736P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1115
_refine_ls_wR_factor_ref         0.1141
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9505
_reflns_number_total             10459
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt02951a2.cif
_cod_data_source_block           rad430_0m_a
_cod_database_code               7044198
_shelx_estimated_absorpt_t_max   0.817
_shelx_estimated_absorpt_t_min   0.414
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C36-C35 \\sim C36-C35A \\sim C34-C33 \\sim C34A-C33 \\sim C18-C17 \\sim
C18-C17A \\sim C16A-C15 \\sim C16-
 C15
 with sigma of 0.008
 C35A-C34A \\sim C35-C34 \\sim C17A-C16A \\sim C17-C16
 with sigma of 0.008
3. Others
 Sof(H15C)=Sof(H15D)=Sof(H18C)=Sof(H18D)=Sof(C16A)=Sof(H16C)=Sof(H16D)=
 Sof(C17A)=Sof(H17C)=Sof(H17D)=1-FVAR(1)
 Sof(H15A)=Sof(H15B)=Sof(H18A)=Sof(H18B)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=
 Sof(H17A)=Sof(H17B)=FVAR(1)
 Sof(H33C)=Sof(H33D)=Sof(H36C)=Sof(H36D)=Sof(C34A)=Sof(H34C)=Sof(H34D)=
 Sof(C35A)=Sof(H35C)=Sof(H35D)=1-FVAR(2)
 Sof(H33A)=Sof(H33B)=Sof(H36A)=Sof(H36B)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=
 Sof(H35A)=Sof(H35B)=FVAR(2)
4.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C13(H13A,H13B), C15(H15A,H15B), C15(H15C,H15D), C18(H18A,
 H18B), C18(H18C,H18D), C16(H16A,H16B), C17(H17A,H17B), C16A(H16C,H16D),
 C17A(H17C,H17D), C29(H29A,H29B), C31(H31A,H31B), C33(H33A,H33B), C33(H33C,
 H33D), C36(H36A,H36B), C36(H36C,H36D), C34(H34A,H34B), C35(H35A,H35B),
 C34A(H34C,H34D), C35A(H35C,H35D)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C20(H20), C25(H25)
4.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C30(H30A,H30B,H30C), C32(H32A,H32B,
 H32C)
;
_shelx_res_checksum              66626
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'