Multi-site reduction of hexachlorophosphazene to low-valent PN heterocycles and extension to the reduction of poly-chlorophosphazene
LaPierre, Etienne A.; Suvinen, Roope A.; Patrick, Brian O.; Tuononen, Heikki M.; Manners, Ian; Chemical Science 16 (2025) 9820–9832; doi:10.1039/D4SC07559E

data_1574494
_publ_section_title
;
 Multi-site reduction of hexachlorophosphazene to low-valent PN
 heterocycles and extension to the reduction of poly-chlorophosphazene
;
_journal_issue                   22
_journal_name_full               'Chemical Science'
_journal_page_first              9820
_journal_page_last               9832
_journal_paper_doi               10.1039/D4SC07559E
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C20 H31 Cl4 N4 P3 Se'
_chemical_formula_sum            'C20 H31 Cl4 N4 P3 Se'
_chemical_formula_weight         641.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2018/3
_audit_update_record
;
2024-09-11 deposited with the CCDC.	2025-04-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.842(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.298(3)
_cell_length_b                   14.467(4)
_cell_length_c                   15.947(4)
_cell_measurement_reflns_used    9980
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.12
_cell_measurement_theta_min      2.38
_cell_volume                     2776.8(12)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'LinXTL v. 5.9.9 (Spasyuk, 2009)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0624
_diffrn_reflns_av_unetI/netI     0.0556
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            23611
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.144
_diffrn_reflns_theta_min         2.201
_exptl_absorpt_coefficient_mu    1.927
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6353
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Sadabs (Sheldrick, 1996)'
_exptl_crystal_colour            Yellow
_exptl_crystal_density_diffrn    1.534
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1304
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.841
_refine_diff_density_min         -0.293
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 2166 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     297
_refine_ls_number_reflns         5533
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0445
_refine_ls_R_factor_gt           0.0356
_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^)+(0.0419P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0751
_refine_ls_wR_factor_ref         0.0783
_reflns_Friedel_coverage         0.990
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                4962
_reflns_number_total             5533
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07559e2.cif
_cod_data_source_block           im041_a
_cod_depositor_comments
'Adding full bibliography for 1574493--1574501.cif.'
_cod_original_cell_volume        2777.0(13)
_cod_original_sg_symbol_H-M      'C c'
_cod_database_code               1574494
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.748
_shelx_estimated_absorpt_t_max   0.927
_shelx_res_checksum              6434