Triple dehydrofluorination as a route to amidine-functionalized, aromatic phosphorus heterocycles
Coles, Nathan Thomas; Groth, Lucie; Dettling, Lea; Frost, Daniel Sebastian; Rigo, Massimo; Neale, Samuel E.; Muller, Christian; Chemical Communications  (2022) –; doi:10.1039/D2CC05178H

data_7130947
_publ_section_title
;
 Triple dehydrofluorination as a route to amidine-functionalized, aromatic
 phosphorus heterocycles
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC05178H
_journal_year                    2022
_chemical_formula_moiety         'C13 H25 P Si2'
_chemical_formula_sum            'C13 H25 P Si2'
_chemical_formula_weight         268.48
_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             2020-06-29
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2022-06-03 deposited with the CCDC.	2022-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                85.5620(10)
_cell_angle_beta                 79.3630(10)
_cell_angle_gamma                86.7690(10)
_cell_formula_units_Z            5
_cell_length_a                   10.5114(3)
_cell_length_b                   13.5050(3)
_cell_length_c                   14.7354(3)
_cell_measurement_reflns_used    9894
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      32.62
_cell_measurement_theta_min      2.435
_cell_volume                     2047.79(9)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.910
_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  0.0554
_diffrn_reflns_av_unetI/netI     0.0517
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.910
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            54129
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.910
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.875
_diffrn_reflns_theta_min         1.997
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.292
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.6453
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.1320 before and 0.0629 after correction. The Ratio 
of minimum to maximum transmission is 0.8644. The \l/2 correction 
factor is Not present.'
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.089
_exptl_crystal_description       Plate
_exptl_crystal_F_000             730
_exptl_crystal_size_max          0.53
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.636
_refine_diff_density_min         -0.329
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     457
_refine_ls_number_reflns         13897
_refine_ls_number_restraints     35
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0756
_refine_ls_R_factor_gt           0.0453
_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^)+(0.0379P)^2^+1.1544P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0981
_refine_ls_wR_factor_ref         0.1166
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10137
_reflns_number_total             13897
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc05178h2.cif
_cod_data_source_block           ntc043_1
_cod_database_code               7130947
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.861
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P3-C27 = P3-C31
 1.74 with sigma of 0.02
 C27-Si5 = C31-Si6
 1.9 with sigma of 0.02
3. Rigid body (RIGU) restrains
 P3, C31, Si6, C27, Si5, C28, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: P3(0.5) Si5(0.5) Si6(0.5) C27(0.5) C28(0.5) C29(0.5) H29(0.5)
 C30(0.5) C31(0.5) C32(0.5) H32A(0.5) H32B(0.5) H32C(0.5) C33(0.5) H33A(0.5)
 H33B(0.5) H33C(0.5) C34(0.5) H34A(0.5) H34B(0.5) H34C(0.5) C35(0.5) H35A(0.5)
 H35B(0.5) H35C(0.5) C36(0.5) H36A(0.5) H36B(0.5) H36C(0.5) C37(0.5) H37A(0.5)
 H37B(0.5) H37C(0.5) C38(0.5) H38A(0.5) H38B(0.5) H38C(0.5) C39(0.5) H39A(0.5)
 H39B(0.5) H39C(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C16(H16), C29(H29)
5.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C39(H39A,H39B,H39C)
;
_shelx_res_checksum              76058
_shelx_hkl_checksum              41037
_olex2_submission_original_sample_id 'NTC 043'
_olex2_submission_special_instructions 'No special instructions were received'