The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study
Heift, Dominikus; Benkő, Zoltán; Suter, Riccardo; Verel, René; Grützmacher, Hansjörg; Chem. Sci. 7 (2016) 6125–; doi:10.1039/C6SC01269H

data_1543490
_publ_section_title
;
 The reactivity of acyl chlorides towards sodium phosphaethynolate,
 Na(OCP): a mechanistic case study
;
_journal_issue                   9
_journal_name_full               'Chem. Sci.'
_journal_page_first              6125
_journal_paper_doi               10.1039/C6SC01269H
_journal_volume                  7
_journal_year                    2016
_chemical_formula_moiety         'C38 H62 Na2 O10 P4 S2'
_chemical_formula_sum            'C38 H62 Na2 O10 P4 S2'
_chemical_formula_weight         912.86
_chemical_name_common            124-thiodiphospholide
_chemical_name_systematic
sodium(1-thio-2,4-diphosphol-5-mesitoyl-3-olate)
_chemical_properties_physical    'Air-sensitive, Oxygen-sensitive'
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-03-14
_audit_creation_method
;
Olex2 1.2
(compiled 2014.02.28 svn.r2899 for OlexSys, GUI svn.r4781)
;
_audit_update_record
;
2016-02-19 deposited with the CCDC.
2016-05-31 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 100.2517(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   9.4422(4)
_cell_length_b                   10.6570(4)
_cell_length_c                   24.5794(10)
_cell_measurement_reflns_used    6600
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.141
_cell_measurement_theta_min      2.204
_cell_volume                     2433.83(17)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    OLEX2
_computing_publication_material  OLEX2
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'fixed chi three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker equipped with an APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0265
_diffrn_reflns_av_unetI/netI     0.0255
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            18542
_diffrn_reflns_theta_full        26.37
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         1.68
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.307
_exptl_absorpt_correction_T_max  0.8880
_exptl_absorpt_correction_T_min  0.8123
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0465 before and 0.0347 after correction.
The Ratio of minimum to maximum transmission is 0.9148.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.246
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             968
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dme/MTBE'
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.756
_refine_diff_density_min         -0.628
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         4974
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0612
_refine_ls_R_factor_gt           0.0501
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0537P)^2^+2.8604P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1225
_refine_ls_wR_factor_ref         0.1310
_reflns_number_gt                4123
_reflns_number_total             4974
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c6sc01269h2.cif
_cod_data_source_block           publishable_micha9_test9
_cod_depositor_comments
'Adding full bibliography for 1543489--1543491.cif.'
_cod_database_code               1543490
_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. Same fragment restrains
{C12A, O2A, C13A, C14A, O3A, C15A}
as
{C16, O4, C17, C18, O5, C19}
{C16A, O4A, C17A, C18A, O5A, C19A}
as
{C12, O2, C13, C14, O3, C15}
{C20, O6, C21, C22, O7, C23}
as
{C12A, O2A, C13A, C14A, O3A, C15A}
{C24, O8, C25, C26, O9, C27}
as
{C16A, O4A, C17A, C18A, O5A, C19A}
3. Others
 1*[Sof(C16)+Sof(H16A)+Sof(H16B)+Sof(H16C)+Sof(O4)+Sof(C17)+Sof(H17A)+
 Sof(H17B)+Sof(C18)+Sof(H18A)+Sof(H18B)+Sof(O5)+Sof(C19)+Sof(H19A)+Sof(H19B)+
 Sof(H19C)+Sof(C12)+Sof(H12A)+Sof(H12B)+Sof(H12C)+Sof(O2)+Sof(C13)+Sof(H13A)+
 Sof(H13B)+Sof(C14)+Sof(H14B)+Sof(H14A)+Sof(O3)+Sof(C15)+Sof(H15A)+Sof(H15B)+
 Sof(H15C)]+1*[Sof(C12A)+Sof(H12D)+Sof(H12E)+Sof(H12F)+Sof(O2A)+Sof(C13A)+
 Sof(H13C)+Sof(H13D)+Sof(C14A)+Sof(H14C)+Sof(H14D)+Sof(O3A)+Sof(C15A)+Sof(H15D)+
 Sof(H15E)+Sof(H15F)+Sof(C16A)+Sof(H16D)+Sof(H16E)+Sof(H16F)+Sof(O4A)+Sof(C17A)+
 Sof(H17C)+Sof(H17D)+Sof(C18A)+Sof(H18C)+Sof(H18D)+Sof(O5A)+Sof(C19A)+Sof(H19D)+
 Sof(H19E)+Sof(H19F)]+1*[Sof(C20)+Sof(H20A)+Sof(H20B)+Sof(H20C)+Sof(O6)+
 Sof(C21)+Sof(H21A)+Sof(H21B)+Sof(C22)+Sof(H22A)+Sof(H22B)+Sof(O7)+Sof(C23)+
 Sof(H23A)+Sof(H23B)+Sof(H23C)+Sof(C24)+Sof(H24A)+Sof(H24B)+Sof(H24C)+Sof(O8)+
 Sof(C25)+Sof(H25A)+Sof(H25B)+Sof(C26)+Sof(H26A)+Sof(H26B)+Sof(O9)+Sof(C27)+
 Sof(H27A)+Sof(H27B)+Sof(H27C)]=1 with esd of 0.0001
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(O4)=Sof(C17)=Sof(H17A)=Sof(H17B)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(O5)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(O2)=Sof(C13)=Sof(H13A)=Sof(H13B)=
 Sof(C14)=Sof(H14B)=Sof(H14A)=Sof(O3)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=
 FVAR(1)
 Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(O2A)=Sof(C13A)=Sof(H13C)=
 Sof(H13D)=Sof(C14A)=Sof(H14C)=Sof(H14D)=Sof(O3A)=Sof(C15A)=Sof(H15D)=Sof(H15E)=
 Sof(H15F)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(O4A)=Sof(C17A)=Sof(H17C)=
 Sof(H17D)=Sof(C18A)=Sof(H18C)=Sof(H18D)=Sof(O5A)=Sof(C19A)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=FVAR(2)
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(O6)=Sof(C21)=Sof(H21A)=Sof(H21B)=
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(O7)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(O8)=Sof(C25)=Sof(H25A)=Sof(H25B)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(O9)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=
 FVAR(3)
 Uiso(O4)=Uiso(O5)=Uiso(O2)=Uiso(O3)=Uiso(O2A)=Uiso(O3A)=Uiso(O4A)=Uiso(O5A)=
 Uiso(O6)=Uiso(O7)=Uiso(O8)=Uiso(O9)=FVAR(4)
 Uiso(C16)=Uiso(C19)=Uiso(C12)=Uiso(C15)=Uiso(C12A)=Uiso(C15A)=Uiso(C16A)=
 Uiso(C19A)=Uiso(C20)=Uiso(C23)=Uiso(C24)=Uiso(C27)=FVAR(5)
 Uiso(C17)=Uiso(C18)=Uiso(C13)=Uiso(C14)=Uiso(C13A)=Uiso(C14A)=Uiso(C17A)=
 Uiso(C18A)=Uiso(C21)=Uiso(C22)=Uiso(C25)=Uiso(C26)=FVAR(6)
4.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B), C13(H13A,H13B), C14(H14B,H14A), C13A(H13C,
 H13D), C14A(H14C,H14D), C17A(H17C,H17D), C18A(H18C,H18D), C21(H21A,H21B),
 C22(H22A,H22B), C25(H25A,H25B), C26(H26A,H26B)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7)
4.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C16(H16A,H16B,
 H16C), C19(H19A,H19B,H19C), C12(H12A,H12B,H12C), C15(H15A,H15B,H15C),
 C12A(H12D,H12E,H12F), C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F), C19A(H19D,
 H19E,H19F), C20(H20A,H20B,H20C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C),
 C27(H27A,H27B,H27C)
;
_olex2_computing_structure_refinement_long 'SHELXL-97 (Sheldrick, 2008)'
_olex2_computing_structure_solution_long 'SHELXS-97 (Sheldrick, 2008)'