Coordination isomerism in dioxophosphorane cyanides
Nasrullah, Ayu Afiqah; Zander, Edgar; Dankert, Fabian; Petrov, Andrey; Surkau, Jonas; Baráth, Eszter; Hering-Junghans, Christian; Chemical Science 16 (2025) 6909–6917; doi:10.1039/D4SC07636B

data_1574154
_publ_section_title
;
 Coordination isomerism in dioxophosphorane cyanides
;
_journal_issue                   16
_journal_name_full               'Chemical Science'
_journal_page_first              6909
_journal_page_last               6917
_journal_paper_doi               10.1039/D4SC07636B
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '2(C43 H61 N Na O6 P)'
_chemical_formula_sum            'C86 H122 N2 Na2 O12 P2'
_chemical_formula_weight         1483.77
_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             2024-10-14
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-11-07 deposited with the CCDC.	2025-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                82.9090(10)
_cell_angle_beta                 83.6580(10)
_cell_angle_gamma                77.7760(10)
_cell_formula_units_Z            2
_cell_length_a                   14.5215(4)
_cell_length_b                   18.3696(5)
_cell_length_c                   20.0346(6)
_cell_measurement_reflns_used    9931
_cell_measurement_temperature    149.99
_cell_measurement_theta_max      66.64
_cell_measurement_theta_min      2.47
_cell_volume                     5163.6(3)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      149.99
_diffrn_measured_fraction_theta_full 0.998
_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           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0319
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            68325
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.690
_diffrn_reflns_theta_max         66.690
_diffrn_reflns_theta_min         2.231
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.846
_exptl_absorpt_correction_T_max  0.913
_exptl_absorpt_correction_T_min  0.798
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2014/5'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.954
_exptl_crystal_description       needle
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.632
_refine_diff_density_min         -0.809
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1195
_refine_ls_number_reflns         18231
_refine_ls_number_restraints     499
_refine_ls_restrained_S_all      1.144
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0565
_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^)+(0.0960P)^2^+2.4373P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1609
_refine_ls_wR_factor_ref         0.1684
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15856
_reflns_number_total             18231
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07636b3.cif
_cod_data_source_block           ax2664_DippTerPCN_Na_18-c-6_cmpd3
_cod_depositor_comments
'Adding full bibliography for 1574150--1574157.cif.'
_cod_database_code               1574154
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.913
_shelx_estimated_absorpt_t_min   0.798
_olex2_refinement_description
;
1. Restrained distances
 O5-C39 \\sim O5A-C39
 with sigma of 0.001
 C61-C60 \\sim C60A-C61A
 with sigma of 0.001
 C60A-C62A \\sim C62-C60
 with sigma of 0.001
 O6-C42A \\sim O6A-C42A
 with sigma of 0.001
 C60-C56 \\sim C60A-C56
 with sigma of 0.001
 C80-C79 \\sim C77-C78 \\sim C75-C76 \\sim C86-C85 \\sim C83-C84 \\sim C81-C82
 with sigma of 0.001
 C40-C41 \\sim C41A-C40A
 with sigma of 0.001
 O5A-C39 \\sim O5-C39
 with sigma of 0.001
 O7-C75 \\sim O7-C86 \\sim O12-C85 \\sim O12-C84 \\sim O11-C83 \\sim O11-C82
\\sim O10-C81 \\sim O9-C79 ~
 O9-C78 \\sim O8-C77 \\sim O8-C76
 with sigma of 0.001
 O5-C40 \\sim O5A-C40A
 with sigma of 0.001
 C79-O10 \\sim C85A-O1A
 with sigma of 0.001
 O5-C39 \\sim O5A-C39 \\sim O5A-C40A \\sim O5-C40
 with sigma of 0.001
 C39-C38 \\sim C39A-C38 \\sim C43-C42A \\sim C42-C43
 with sigma of 0.001
 O9-C79 \\sim O13-C85A
 with sigma of 0.02
 O6A-C42A \\sim O6-C42 \\sim O5A-C39A \\sim O5-C39
 with sigma of 0.001
 C78-C79 \\sim C84A-C85A
 with sigma of 0.001
 C79-C80 \\sim C85A-C86A
 with sigma of 0.02
 C85-C84 \\sim C79A-C78A
 with sigma of 0.001
 O12-C85 \\sim O2A-C79A
 with sigma of 0.02
 O7-C85 \\sim O7A-C79A
 with sigma of 0.001
 Na2-C79 \\sim Na2-C85A
 with sigma of 0.001
 Na2-O11 \\sim Na2-O3A
 with sigma of 0.02
 Na2-C85 \\sim Na2-C79A
 with sigma of 0.001
 C85-C86 \\sim C79A-C80A
 with sigma of 0.02
 C77-C76 \\sim C83A-C82A
 with sigma of 0.002
 Na2-O10 \\sim Na2-O1A
 with sigma of 0.02
 Na2-O12 \\sim Na2-O2A
 with sigma of 0.02
 O8-C77 \\sim O14_$1-C83A
 with sigma of 0.02
 O8-C76 \\sim O14_$1-C82A
 with sigma of 0.02
 Na2-O7 \\sim Na2-O7A
 with sigma of 0.02
 O9-C78 \\sim O13-C84A
 with sigma of 0.02
 O11-C84 \\sim O3A-C78A
 with sigma of 0.002
 O7-C75 \\sim O7A-C81A
 with sigma of 0.02
 O7-C86 \\sim O7A-C80A
 with sigma of 0.02
 O11-C83 \\sim O3A-C77A
 with sigma of 0.02
 O8-C75 \\sim O14_$1-C81A
 with sigma of 0.002
 O12-C84 \\sim O2A-C78A
 with sigma of 0.02
 O7-C76 \\sim O7A-C82A
 with sigma of 0.002
 C83-C84 \\sim C77A-C78A
 with sigma of 0.02
 O12-C86 \\sim O2A-C80A
 with sigma of 0.002
 C78-C77 \\sim C84A-C83A
 with sigma of 0.02
 C81-C82 \\sim C75A-C76A
 with sigma of 0.02
 C81-O10 \\sim C75A-O1A
 with sigma of 0.02
 C75-C86 \\sim C81A-C80A
 with sigma of 0.002
 O11-C82 \\sim O3A-C76A
 with sigma of 0.02
 O8-C78 \\sim O14_$1-C84A
 with sigma of 0.002
 C76-C75 \\sim C82A-C81A
 with sigma of 0.02
 O11-C81 \\sim O3A-C75A
 with sigma of 0.002
 O12-C83 \\sim O2A-C77A
 with sigma of 0.002
 C83-C82 \\sim C77A-C76A
 with sigma of 0.002
 O10-C80 \\sim O1A-C86A
 with sigma of 0.02
 C81-C80 \\sim C75A-C86A
 with sigma of 0.002
 Na2-C83 \\sim Na2-C77A
 with sigma of 0.002
 Na2-C78 \\sim Na2-C84A
 with sigma of 0.002
 Na2-C81 \\sim Na2-C75A
 with sigma of 0.002
 Na2-C77 \\sim Na2-C83A
 with sigma of 0.002
 Na2-C76 \\sim Na2-C82A
 with sigma of 0.002
 Na2-C75 \\sim Na2-C81A
 with sigma of 0.002
 Na2-C86 \\sim Na2-C80A
 with sigma of 0.002
 Na2-C84 \\sim Na2-C78A
 with sigma of 0.002
 Na2-C82 \\sim Na2-C76A
 with sigma of 0.002
 Na2-C80 \\sim Na2-C86A
 with sigma of 0.002
 C82-O10 \\sim C76A-O1A
 with sigma of 0.002
 O9-C77 \\sim O13-C83A
 with sigma of 0.002
 O9-C80 \\sim O13-C86A
 with sigma of 0.002
 Na2-O9 \\sim Na2-O13
 with sigma of 0.02
 Na2-O8 \\sim Na2-O14_$1
 with sigma of 0.02
2. Rigid bond restraints
 C61, C60, C62
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C62A, C60A, C61A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O5, O5A, C39
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O9, O8, O7, O11, O12, C83, C78, C79, C81, C77, C85, C76, C75, C86, C84, C82,
 O10, C80, O14, O7A, O3A, O2A, C77A, C82A, C81A, C78A, C76A, O13, C85A, C75A,
 O1A, C86A, C84A, C83A, C79A, C80A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
3. Uiso/Uaniso restraints and constraints
Uanis(C61A) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C62A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C62A) \\sim Ueq, Uanis(C61A) \\sim Ueq, Uanis(C60A) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(O5A) \\sim Ueq, Uanis(O5) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O6) \\sim Ueq, Uanis(O6A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Na2) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(O7) \\sim
Ueq, Uanis(O11) \\sim Ueq, Uanis(O12) \\sim Ueq, Uanis(C83) \\sim Ueq,
Uanis(C78) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C77)
\\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C75) \\sim Ueq,
Uanis(C86) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(O10)
\\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(O14) \\sim Ueq, Uanis(O7A) \\sim Ueq,
Uanis(O3A) \\sim Ueq, Uanis(O2A) \\sim Ueq, Uanis(C77A) \\sim Ueq, Uanis(C79A)
\\sim Ueq, Uanis(C82A) \\sim Ueq, Uanis(C81A) \\sim Ueq, Uanis(C80A) \\sim Ueq,
Uanis(C78A) \\sim Ueq, Uanis(C76A) \\sim Ueq, Uanis(O13) \\sim Ueq, Uanis(C85A)
\\sim Ueq, Uanis(C75A) \\sim Ueq, Uanis(O1A) \\sim Ueq, Uanis(C86A) \\sim Ueq,
Uanis(C84A) \\sim Ueq, Uanis(C83A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C79A) \\sim Ueq, Uanis(C79) \\sim Ueq: with sigma of 0.004 and sigma for
terminal atoms of 0.008
Uanis(C79A) = Uanis(C79)
4. Others
 Sof(O14)=Sof(O7A)=Sof(O3A)=Sof(O2A)=Sof(C77A)=Sof(H77C)=Sof(H77D)=Sof(C79A)=
 Sof(H79C)=Sof(H79D)=Sof(C82A)=Sof(H82C)=Sof(H82D)=Sof(C81A)=Sof(H81C)=
 Sof(H81D)=Sof(C80A)=Sof(H80C)=Sof(H80D)=Sof(C78A)=Sof(H78C)=Sof(H78D)=
 Sof(C76A)=Sof(H76C)=Sof(H76D)=Sof(O13)=Sof(C85A)=Sof(H85C)=Sof(H85D)=Sof(C75A)=
 Sof(H75C)=Sof(H75D)=Sof(O1A)=Sof(C86A)=Sof(H86C)=Sof(H86D)=Sof(C84A)=Sof(H84C)=
 Sof(H84D)=Sof(C83A)=Sof(H83C)=Sof(H83D)=1-FVAR(1)
 Sof(O9)=Sof(O8)=Sof(O7)=Sof(O11)=Sof(O12)=Sof(C83)=Sof(H83A)=Sof(H83B)=
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(C81)=Sof(H81A)=
 Sof(H81B)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(C76)=
 Sof(H76A)=Sof(H76B)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C86)=Sof(H86A)=Sof(H86B)=
 Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(O10)=Sof(C80)=
 Sof(H80A)=Sof(H80B)=FVAR(1)
 Sof(H38C)=Sof(H38D)=Sof(C42A)=Sof(H42A)=Sof(H42B)=Sof(H43C)=Sof(H43D)=
 Sof(O5A)=Sof(O6A)=Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=
 Sof(C39A)=Sof(H39C)=Sof(H39D)=1-FVAR(2)
 Sof(H38A)=Sof(H38B)=Sof(H43A)=Sof(H43B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C40)=
 Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(O5)=Sof(O6)=Sof(C42)=
 Sof(H42C)=Sof(H42D)=FVAR(2)
 Sof(C61)=Sof(H61D)=Sof(H61E)=Sof(H61F)=Sof(C62)=Sof(H62D)=Sof(H62E)=Sof(H62F)=
 Sof(C60)=Sof(H60)=1-FVAR(3)
 Sof(C61A)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C62A)=Sof(H62A)=Sof(H62B)=
 Sof(H62C)=Sof(C60A)=Sof(H60A)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C26(H26), C29(H29), C57(H57), C14(H14), C69(H69), C17(H17), C72(H72),
 C60A(H60A), C60(H60)
5.b Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B), C35(H35A,H35B), C34(H34A,H34B), C37(H37A,H37B), C38(H38C,
 H38D), C38(H38A,H38B), C42A(H42A,H42B), C33(H33A,H33B), C43(H43C,H43D),
 C43(H43A,H43B), C32(H32A,H32B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B),
  C41A(H41C,H41D), C40A(H40C,H40D), C83(H83A,H83B), C78(H78A,H78B), C79(H79A,
 H79B), C81(H81A,H81B), C77(H77A,H77B), C85(H85A,H85B), C76(H76A,H76B),
 C75(H75A,H75B), C86(H86A,H86B), C84(H84A,H84B), C82(H82A,H82B), C80(H80A,H80B),
  C77A(H77C,H77D), C79A(H79C,H79D), C82A(H82C,H82D), C81A(H81C,H81D), C80A(H80C,
 H80D), C78A(H78C,H78D), C76A(H76C,H76D), C85A(H85C,H85D), C75A(H75C,H75D),
 C86A(H86C,H86D), C84A(H84C,H84D), C83A(H83C,H83D), C39A(H39C,H39D), C42(H42C,
 H42D)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C49(H49), C5(H5), C6(H6), C47(H47), C48(H48), C55(H55), C53(H53),
 C54(H54), C24(H24), C10(H10), C11(H11), C22(H22), C12(H12), C23(H23), C66(H66),
  C65(H65), C67(H67)
5.d Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C59(H59A,H59B,H59C), C19(H19A,H19B,H19C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C74(H74A,H74B,H74C), C28(H28A,
 H28B,H28C), C70(H70A,H70B,H70C), C73(H73A,H73B,H73C), C71(H71A,H71B,H71C),
 C31(H31A,H31B,H31C), C30(H30A,H30B,H30C), C58(H58A,H58B,H58C), C61A(H61A,H61B,
 H61C), C62A(H62A,H62B,H62C), C61(H61D,H61E,H61F), C62(H62D,H62E,H62F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              48858
_shelx_fab_checksum              41343
_olex2_submission_special_instructions 'No special instructions were received'