Mechanistic study of pyrazole synthesis <i>via</i> oxidation-induced N-N coupling of diazatitanacycles.
Cheng, Yukun; Huh, Daniel N.; Tonks, Ian A.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 9510–9515; doi:10.1039/d4dt01412j

data_7716072
_publ_section_title
;
 Mechanistic study of pyrazole synthesis <i>via</i> oxidation-induced N-N
 coupling of diazatitanacycles.
;
_journal_issue                   22
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9510
_journal_page_last               9515
_journal_paper_doi               10.1039/d4dt01412j
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C38 H40 Cl4 N4 Ti2'
_chemical_formula_sum            'C38 H40 Cl4 N4 Ti2'
_chemical_formula_weight         790.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-06
_audit_creation_method
; 
Olex2 1.3 
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408) 
;
_audit_update_record
;
2024-04-16 deposited with the CCDC.	2024-05-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.745(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.3405(9)
_cell_length_b                   9.3839(7)
_cell_length_c                   21.029(2)
_cell_measurement_reflns_used    9906
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      30.54
_cell_measurement_theta_min      2.18
_cell_volume                     1843.0(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0310
_diffrn_reflns_av_unetI/netI     0.0307
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            24849
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.617
_diffrn_reflns_theta_min         1.937
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.757
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6608
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.0811 before and 0.0512 after correction. 
The Ratio of minimum to maximum transmission is 0.8857. 
The \l/2 correction factor is Not present. 
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.424
_exptl_crystal_description       irregular
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.515
_refine_diff_density_min         -0.358
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         5655
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.130
_refine_ls_R_factor_all          0.0430
_refine_ls_R_factor_gt           0.0375
_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^)+(0.0221P)^2^+1.6128P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0838
_refine_ls_wR_factor_ref         0.0863
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5098
_reflns_number_total             5655
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01412j2.cif
_cod_data_source_block           22088a
_cod_depositor_comments          'Adding full bibliography for 7716072.cif.'
_cod_database_code               7716072
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.928
_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.a Secondary CH2 refined with riding coordinates: 
 C12(H12A,H12B) 
2.b Aromatic/amide H refined with riding coordinates: 
 C15(H15), C9(H9), C19(H19), C5(H5), C16(H16), C8(H8), C17(H17), C6(H6), 
 C18(H18) 
2.c Idealised Me refined as rotating group: 
 C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C10(H10A,H10B,H10C) 
;
_shelx_res_checksum              57265
_olex2_submission_special_instructions 'No special instructions were received'