A 2,2′-diphosphinotolane as a versatile precursor for the synthesis of P-ylidic mesoionic carbenes via reversible C‒P bond formation
Wagner, Hannah K.; Wadepohl, Hubert; Ballmann, Joachim; Chemical Science 12 (2021) 3693–3701; doi:10.1039/D0SC06128J

data_1560233
_publ_section_title
;
 A 2,2&#x2032;-diphosphinotolane as a versatile precursor for the
 synthesis of P-ylidic mesoionic carbenes via reversible C--P bond
 formation
;
_journal_issue                   10
_journal_name_full               'Chemical Science'
_journal_page_first              3693
_journal_page_last               3701
_journal_paper_doi               10.1039/D0SC06128J
_journal_volume                  12
_journal_year                    2021
_chemical_formula_sum            'C56 H82 O3 P2 S2 Zn'
_chemical_formula_weight         994.64
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_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     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_hw14
_audit_creation_date             2020-10-08
_audit_creation_method
;
encif (version 1.121)

encifer (version_id = 274361.64)

Olex2 1.3
(compiled 2020.07.31 svn.rc2a7746 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2020-10-08 deposited with the CCDC.	2021-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.990(10)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   20.688(11)
_cell_length_b                   26.218(15)
_cell_length_c                   40.07(2)
_cell_measurement_reflns_used    23320
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.34
_cell_measurement_theta_min      2.27
_cell_volume                     21615(2)
_computing_cell_refinement
;
SAINT (see _computing_data_reduction).
Standard uncertainties of the cell constants include systematic error
contributions from Monte Carlo simulations.
;
_computing_data_collection       'SMART-5.631 (Bruker AXS, 2003)'
_computing_data_reduction
'SAINT (Bruker AXS, 1997-2013),SADABS-2016_2 (Sheldrick and Bruker AXS, 1997-2014)'
_computing_publication_material
'encif (Wadepohl, 2009-19); encifer (Allen et al., 2004)'
_computing_structure_refinement  'SHELXL-20xx (Sheldrick, 2015)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      100(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.19
_diffrn_detector_type            CCD-PXL-KAF2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker AXS Smart 1000'
_diffrn_measurement_method       '\f- and \w-scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_radiation_collimation    'monocapillary collimator'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.1665
_diffrn_reflns_av_unetI/netI     0.0975
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            403063
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.407
_diffrn_reflns_theta_min         1.258
_diffrn_source                   'sealed X-Ray tube (Mo)'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              'fine focus tube'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.632
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6509
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
multi-scan from symmetry-related measurements (Blessing 1995)
SADABS (see _computing_data_reduction)
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.223
_exptl_crystal_description       plate
_exptl_crystal_F_000             8544
_exptl_crystal_size_max          0.260
_exptl_crystal_size_mid          0.210
_exptl_crystal_size_min          0.090
_refine_diff_density_max         1.161
_refine_diff_density_min         -1.011
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2166
_refine_ls_number_reflns         44237
_refine_ls_number_restraints     662
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1325
_refine_ls_R_factor_gt           0.0627
_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^)+(0.0622P)^2^+32.5081P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1318
_refine_ls_wR_factor_ref         0.1603
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24856
_reflns_number_total             44237
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc06128j2.cif
_cod_data_source_block           ba_hw14_sq
_cod_depositor_comments
'Adding full bibliography for 1560218--1560233.cif.'
_cod_original_cell_volume        21614(20)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               1560233
_audit_block_refno               3336
_audit_block_usercomment         HW149
_shelxl_version_number           2018/3
_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
 P51-C68A \\sim P51-C68B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C101 \\sim C102 \\sim C103 \\sim C104 \\sim
C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109 \\sim C110 \\sim C111 \\sim
C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116 \\sim C117 \\sim C118 \\sim
C119 \\sim C120 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim C125 \\sim
C126 \\sim C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132 \\sim
C133 \\sim C134 \\sim C135 \\sim C136 \\sim C137 \\sim C138 \\sim C139 \\sim
C140 \\sim C141 \\sim C142 \\sim C143 \\sim C144 \\sim C151 \\sim C152 \\sim
C153 \\sim C154 \\sim C155 \\sim C156 \\sim C157 \\sim C158 \\sim C159 \\sim
C160 \\sim C161 \\sim C162 \\sim C163 \\sim C164 \\sim C165 \\sim C166 \\sim
C167 \\sim C168 \\sim C169 \\sim C170 \\sim C171 \\sim C172 \\sim C173 \\sim
C174 \\sim C175 \\sim C176 \\sim C177 \\sim C178 \\sim C179 \\sim C180 \\sim
C181 \\sim C182 \\sim C183 \\sim C184 \\sim C185 \\sim C186 \\sim C187 \\sim
C188 \\sim C189 \\sim C190 \\sim C191 \\sim C192 \\sim C193 \\sim C194 \\sim
C5CA \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76
\\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84
\\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92
\\sim C93 \\sim C68A \\sim C69A \\sim C70A \\sim C68B \\sim C69B \\sim C70B
\\sim C201 \\sim C202 \\sim C203 \\sim C204 \\sim C301 \\sim C302 \\sim C303
\\sim C304 \\sim C401 \\sim C402 \\sim C403 \\sim C404 \\sim C501 \\sim C502
\\sim C503 \\sim C504 \\sim C601 \\sim C602 \\sim C603 \\sim C604 \\sim C701
\\sim C702 \\sim C703 \\sim C704 \\sim C801 \\sim C802 \\sim C803 \\sim C804:
within 1A with sigma of 0.01 and sigma for terminal atoms of 0.01 within 1A
4. Rigid body (RIGU) restrains
 C68A, C69A, C70A, C68B, C69B, C70B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O201, C201, C202, C203, C204, O301, C301, C302, C303, C304, O401, C401, C402,
 C403, C404, O501, C501, C502, C503, C504, O601, C601, C602, C603, C604, O701,
 C701, C702, C703, C704, O801, C801, C802, C803, C804
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C65, C66, C67} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C68A, C69A, C70A}
{C65, C66, C67} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C68B, C69B, C70B}
{O201, C204, C203, C202, C201} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O201, C201, C202, C203, C204}
{O201, C201, C202, C203, C204} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O301, C301, C302, C303, C304}
{O201, C201, C202, C203, C204} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O401, C401, C402, C403, C404}
{O201, C201, C202, C203, C204} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O501, C501, C502, C503, C504}
{O201, C201, C202, C203, C204} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O601, C601, C602, C603, C604}
{O201, C201, C202, C203, C204} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O701, C701, C702, C703, C704}
{O201, C201, C202, C203, C204} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O801, C801, C802, C803, C804}
6. Others
 Sof(C68B)=Sof(H68B)=Sof(C69B)=Sof(H69D)=Sof(H69E)=Sof(H69F)=Sof(C70B)=
 Sof(H70D)=Sof(H70E)=Sof(H70F)=1-FVAR(1)
 Sof(C68A)=Sof(H68A)=Sof(C69A)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70A)=
 Sof(H70A)=Sof(H70B)=Sof(H70C)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C21(H21), C24(H24), C115(H115), C118(H118), C121(H121),
 C124(H124), C165(H165), C168(H168), C171(H171), C174(H174), C65(H65), C71(H71),
  C74(H74), C68A(H68A), C68B(H68B)
7.b Secondary CH2 refined with riding coordinates:
 C201(H20D,H20E), C202(H20F,H20G), C203(H20H,H20I), C204(H20J,H20K), C301(H30A,
 H30B), C302(H30C,H30D), C303(H30E,H30F), C304(H30G,H30H), C401(H40A,H40B),
 C402(H40C,H40D), C403(H40E,H40F), C404(H40G,H40H), C501(H50A,H50B), C502(H50C,
 H50D), C503(H50E,H50F), C504(H50G,H50H), C601(H60A,H60B), C602(H60C,H60D),
 C603(H60E,H60F), C604(H60G,H60H), C701(H70G,H70H), C702(H70I,H70J), C703(H70K,
 H70L), C704(H70M,H70N), C801(H80A,H80B), C802(H80C,H80D), C803(H80E,H80F),
 C804(H80G,H80H)
7.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13), C14(H14),
 C29(H29), C31(H31), C38(H38), C40(H40), C104(H104), C105(H105), C106(H106),
 C107(H107), C111(H111), C112(H112), C113(H113), C114(H114), C129(H129),
 C131(H131), C138(H138), C140(H140), C154(H154), C155(H155), C156(H156),
 C157(H157), C161(H161), C162(H162), C163(H163), C164(H164), C179(H179),
 C181(H181), C188(H188), C190(H190), C54(H54), C55(H55), C56(H56), C57(H57),
 C61(H61), C62(H62), C63(H63), C64(H64), C79(H79), C81(H81), C88(H88), C90(H90)
7.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C),
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C116(H11A,H11B,
 H11C), C117(H11D,H11E,H11F), C119(H11G,H11H,H11I), C120(H12A,H12B,H12C),
 C122(H12D,H12E,H12F), C123(H12G,H12H,H12I), C125(H12J,H12K,H12L), C126(H12M,
 H12N,H12O), C133(H13A,H13B,H13C), C134(H13D,H13E,H13F), C135(H13G,H13H,H13I),
 C142(H14A,H14B,H14C), C143(H14D,H14E,H14F), C144(H14G,H14H,H14I), C166(H16D,
 H16E,H16F), C167(H16G,H16H,H16I), C169(H16J,H16K,H16L), C170(H17D,H17E,H17F),
 C172(H17G,H17H,H17I), C173(H17J,H17K,H17L), C175(H17M,H17N,H17O), C176(H17P,
 H17Q,H17R), C183(H18A,H18B,H18C), C184(H18D,H18E,H18F), C185(H18G,H18H,H18I),
 C192(H19D,H19E,H19F), C193(H19G,H19H,H19I), C194(H19J,H19K,H19L), C66(H66A,
 H66B,H66C), C67(H67A,H67B,H67C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C),
 C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C83(H83A,H83B,H83C), C84(H84A,H84B,
 H84C), C85(H85A,H85B,H85C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C93(H93A,
 H93B,H93C), C69A(H69A,H69B,H69C), C70A(H70A,H70B,H70C), C69B(H69D,H69E,H69F),
 C70B(H70D,H70E,H70F)
;
_shelx_hkl_checksum              63626
_shelx_fab_checksum              17824
_platon_squeeze_void_probe_radius 1.20
_shelx_res_checksum              67142