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_1574152
_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         'C43 H61 K N O6 P S2, 2.001(C7 H8)'
_chemical_formula_sum            'C57.01 H77.01 K N O6 P S2'
_chemical_formula_weight         1006.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-01-21
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-02-27 deposited with the CCDC.	2025-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.183(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.4061(7)
_cell_length_b                   40.667(2)
_cell_length_c                   22.5868(13)
_cell_measurement_reflns_used    9724
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      66.77
_cell_measurement_theta_min      3.80
_cell_volume                     11393.0(11)
_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)'
_diffrn_ambient_temperature      150.00
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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  0.0433
_diffrn_reflns_av_unetI/netI     0.0274
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       48
_diffrn_reflns_limit_k_min       -48
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            118615
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.840
_diffrn_reflns_theta_max         66.840
_diffrn_reflns_theta_min         2.173
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.134
_exptl_absorpt_correction_T_max  0.848
_exptl_absorpt_correction_T_min  0.577
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2014/5'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.174
_exptl_crystal_description       block
_exptl_crystal_F_000             4320
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.396
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1422
_refine_ls_number_reflns         20120
_refine_ls_number_restraints     387
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0371
_refine_ls_R_factor_gt           0.0328
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0504P)^2^+2.9652P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0876
_refine_ls_wR_factor_ref         0.0912
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18092
_reflns_number_total             20120
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07636b3.cif
_cod_data_source_block           ax2813_cmpd_2S2
_cod_depositor_comments
'Adding full bibliography for 1574150--1574157.cif.'
_cod_database_code               1574152
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.848
_shelx_estimated_absorpt_t_min   0.577
_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. Restrained distances
 C1P-C1R
 1.55 with sigma of 0.01
 C102-C107 \\sim C1B-C1C
 with sigma of 0.02
 C102-C103 \\sim C1B-C1G
 with sigma of 0.02
 C102-C101 \\sim C1B-C1A
 with sigma of 0.02
 C109-C110 \\sim C1K-C1L
 with sigma of 0.02
 C109-C108 \\sim C1K-C1I
 with sigma of 0.02
 C105-C103 \\sim C1E-C1G
 with sigma of 0.04
 C107-C106 \\sim C1C-C1D
 with sigma of 0.02
 C110-C112 \\sim C1L-C1N
 with sigma of 0.04
 C103-C101 \\sim C1G-C1A
 with sigma of 0.04
 C110-C111 \\sim C1L-C1M
 with sigma of 0.02
 C106-C105 \\sim C1D-C1E
 with sigma of 0.02
 C111-C112 \\sim C1M-C1N
 with sigma of 0.02
 C105-C104 \\sim C1E-C1F
 with sigma of 0.02
 C111-C113 \\sim C1M-C1O
 with sigma of 0.04
 C104-C103 \\sim C1F-C1G
 with sigma of 0.02
 C112-C113 \\sim C1N-C1O
 with sigma of 0.02
 C106-C104 \\sim C1D-C1F
 with sigma of 0.04
 C114-C113 \\sim C1J-C1O
 with sigma of 0.02
 C102-C106 \\sim C1B-C1D
 with sigma of 0.04
 C110-C108 \\sim C1L-C1I
 with sigma of 0.04
 C102-C104 \\sim C1B-C1F
 with sigma of 0.04
 C114-C109 \\sim C1J-C1K
 with sigma of 0.02
 C107-C105 \\sim C1C-C1E
 with sigma of 0.04
 C114-C110 \\sim C1J-C1L
 with sigma of 0.04
 C114-C112 \\sim C1J-C1N
 with sigma of 0.04
 C107-C103 \\sim C1C-C1G
 with sigma of 0.04
 C107-C101 \\sim C1C-C1A
 with sigma of 0.04
 C114-C108 \\sim C1J-C1I
 with sigma of 0.04
 C109-C111 \\sim C1K-C1M
 with sigma of 0.04
 C109-C113 \\sim C1K-C1O
 with sigma of 0.04
 C95-C96 \\sim C95A-C96A
 with sigma of 0.02
 C100-C99 \\sim C1H-C99A
 with sigma of 0.02
 C95-C94 \\sim C95A-C94A
 with sigma of 0.02
 C97-C99 \\sim C97A-C99A
 with sigma of 0.04
 C95-C99 \\sim C95A-C99A
 with sigma of 0.04
 C100-C95 \\sim C1H-C95A
 with sigma of 0.02
 C96-C94 \\sim C96A-C94A
 with sigma of 0.04
 C96-C97 \\sim C96A-C97A
 with sigma of 0.02
 C95-C97 \\sim C95A-C97A
 with sigma of 0.04
 C97-C98 \\sim C97A-C98A
 with sigma of 0.02
 C96-C98 \\sim C96A-C98A
 with sigma of 0.04
 C98-C99 \\sim C98A-C99A
 with sigma of 0.02
 C100-C96 \\sim C1H-C96A
 with sigma of 0.04
 C100-C98 \\sim C1H-C98A
 with sigma of 0.04
 C100-C94 \\sim C1H-C94A
 with sigma of 0.04
 C1P-C1Q \\sim C1P-C1S
 with sigma of 0.001
3. Rigid bond restraints
 C114, C109, C113, C110, C108, C112, C111
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C101, C102, C103, C104, C105, C106, C107
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1N, C1I, C1K, C1J, C1L, C1O, C1M
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1A, C1B, C1C, C1G, C1D, C1F, C1E
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C112, C114, C109, C113, C110, C108, C111
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C98A, C1H, C95A, C99A, C96A, C94A, C97A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1S, C1R, C1Q, C1V, C1U, C1T
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C114) \\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C113) \\sim Ueq,
Uanis(C110) \\sim Ueq, Uanis(C108) \\sim Ueq, Uanis(C112) \\sim Ueq,
Uanis(C111) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C102) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C103) \\sim Ueq,
Uanis(C104) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C106) \\sim Ueq,
Uanis(C107) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1A) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C1C) \\sim Ueq, Uanis(C1G)
\\sim Ueq, Uanis(C1D) \\sim Ueq, Uanis(C1F) \\sim Ueq, Uanis(C1E) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C113) \\sim Ueq, Uanis(C114) \\sim Ueq, Uanis(C109) \\sim Ueq,
Uanis(C110) \\sim Ueq, Uanis(C108) \\sim Ueq, Uanis(C112) \\sim Ueq,
Uanis(C111) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1N) \\sim Ueq, Uanis(C1I) \\sim Ueq, Uanis(C1K) \\sim Ueq, Uanis(C1J)
\\sim Ueq, Uanis(C1L) \\sim Ueq, Uanis(C1O) \\sim Ueq, Uanis(C1M) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C98A) \\sim Ueq, Uanis(C1H) \\sim Ueq, Uanis(C95A) \\sim Ueq, Uanis(C99A)
\\sim Ueq, Uanis(C96A) \\sim Ueq, Uanis(C94A) \\sim Ueq, Uanis(C97A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1S) \\sim Ueq, Uanis(C1P) \\sim Ueq, Uanis(C1R) \\sim Ueq, Uanis(C1Q)
\\sim Ueq, Uanis(C1V) \\sim Ueq, Uanis(C1T) \\sim Ueq, Uanis(C1U) \\sim Ueq, :
with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 1*[Sof(C114)+Sof(H114)+Sof(C109)+Sof(C110)+Sof(H110)+Sof(C111)+Sof(H111)+
 Sof(C112)+Sof(H112)+Sof(C113)+Sof(H113)+Sof(C108)+Sof(H10D)+Sof(H10E)+
 Sof(H10F)]+1*[Sof(C1I)+Sof(H1IA)+Sof(H1IB)+Sof(H1IC)+Sof(C1J)+Sof(H1J)+
 Sof(C1K)+Sof(C1L)+Sof(H1L)+Sof(C1M)+Sof(H1M)+Sof(C1N)+Sof(H1N)+Sof(C1O)+
 Sof(H1O)]+1*[Sof(C1P)+Sof(H1PA)+Sof(H1PB)+Sof(H1PC)+Sof(C1Q)+Sof(H1Q)+Sof(C1R)+
 Sof(C1S)+Sof(H1S)+Sof(C1T)+Sof(H1T)+Sof(C1U)+Sof(H1U)+Sof(C1V)+Sof(H1V)]=1
 with esd of 0.001
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=
 Sof(H1D)=Sof(C1E)=Sof(H1E)=Sof(C1F)=Sof(H1F)=Sof(C1G)=Sof(H1G)=1-FVAR(1)
 Sof(C102)=Sof(C107)=Sof(H107)=Sof(C106)=Sof(H106)=Sof(C105)=Sof(H105)=
 Sof(C104)=Sof(H104)=Sof(C103)=Sof(H103)=Sof(C101)=Sof(H10A)=Sof(H10B)=
 Sof(H10C)=FVAR(1)
 Sof(C1H)=Sof(H1H)=Sof(C95A)=Sof(C96A)=Sof(H96A)=Sof(C97A)=Sof(H97A)=Sof(C98A)=
 Sof(H98A)=Sof(C99A)=Sof(H99A)=Sof(C94A)=Sof(H94D)=Sof(H94E)=Sof(H94F)=1-FVAR(2)
 Sof(C100)=Sof(H100)=Sof(C95)=Sof(C96)=Sof(H96)=Sof(C97)=Sof(H97)=Sof(C98)=
 Sof(H98)=Sof(C99)=Sof(H99)=Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(H94C)=FVAR(2)
 Sof(C114)=Sof(H114)=Sof(C109)=Sof(C110)=Sof(H110)=Sof(C111)=Sof(H111)=
 Sof(C112)=Sof(H112)=Sof(C113)=Sof(H113)=Sof(C108)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=FVAR(3)
 Sof(C1I)=Sof(H1IA)=Sof(H1IB)=Sof(H1IC)=Sof(C1J)=Sof(H1J)=Sof(C1K)=Sof(C1L)=
 Sof(H1L)=Sof(C1M)=Sof(H1M)=Sof(C1N)=Sof(H1N)=Sof(C1O)=Sof(H1O)=FVAR(4)
 Sof(C1P)=Sof(H1PA)=Sof(H1PB)=Sof(H1PC)=Sof(C1Q)=Sof(H1Q)=Sof(C1R)=Sof(C1S)=
 Sof(H1S)=Sof(C1T)=Sof(H1T)=Sof(C1U)=Sof(H1U)=Sof(C1V)=Sof(H1V)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C25(H25), C28(H28), C56(H56), C59(H59), C68(H68), C71(H71)
6.b Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,
 H36B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B),
 C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C75(H75A,H75B), C76(H76A,H76B),
  C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,
 H81B), C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B), C85(H85A,H85B),
 C86(H86A,H86B)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C21(H21), C22(H22),
 C23(H23), C46(H46), C47(H47), C48(H48), C52(H52), C53(H53), C54(H54), C64(H64),
  C65(H65), C66(H66), C107(H107), C106(H106), C105(H105), C104(H104),
 C103(H103), C89(H89), C90(H90), C91(H91), C92(H92), C93(H93), C1C(H1C),
 C1D(H1D), C1E(H1E), C1F(H1F), C1G(H1G), C100(H100), C96(H96), C97(H97),
 C98(H98), C99(H99), C1H(H1H), C96A(H96A), C97A(H97A), C98A(H98A), C99A(H99A),
 C114(H114), C110(H110), C111(H111), C112(H112), C113(H113), C1J(H1J), C1L(H1L),
  C1M(H1M), C1N(H1N), C1O(H1O), C1Q(H1Q), C1S(H1S), C1T(H1T), C1U(H1U), C1V(H1V)
6.d Fitted hexagon refined as free rotating group:
 C88(C89,C90,C91,C92,C93), C1B(C1C,C1D,C1E,C1F,C1G), C100(C95,C96,C97,C98,C99),
  C1H(C95A,C96A,C97A,C98A,C99A), C114(C109,C110,C111,C112,C113), C1J(C1K,C1L,
 C1M,C1N,C1O), C1Q(C1R,C1S,C1T,C1U,C1V)
6.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C60(H60A,H60B,H60C),
 C61(H61A,H61B,H61C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C72(H72A,H72B,
 H72C), C73(H73A,H73B,H73C), C101(H10A,H10B,H10C), C87(H87A,H87B,H87C),
 C1A(H1AA,H1AB,H1AC), C94(H94A,H94B,H94C), C94A(H94D,H94E,H94F), C108(H10D,H10E,
 H10F), C1I(H1IA,H1IB,H1IC), C1P(H1PA,H1PB,H1PC)
;
_shelx_res_checksum              15814
_olex2_submission_special_instructions 'No special instructions were received'