Novel synthetic route for (parent) phosphetanes, phospholanes, phosphinanes and phosphepanes.
Reichl, Stephan; Balázs, Gábor; Scheer, Manfred; Chemical science 14 (2023) 3834–3838; doi:10.1039/d3sc00580a

data_1568640
_publ_section_title
;
 Novel synthetic route for (parent) phosphetanes, phospholanes,
 phosphinanes and phosphepanes.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              3834
_journal_page_last               3838
_journal_paper_doi               10.1039/d3sc00580a
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C12 H17 P S'
_chemical_formula_sum            'C12 H17 P S'
_chemical_formula_weight         224.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-16
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-12-23 deposited with the CCDC.	2023-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.346(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.0300(5)
_cell_length_b                   6.1666(2)
_cell_length_c                   10.2233(2)
_cell_measurement_reflns_used    9236
_cell_measurement_temperature    122.97(11)
_cell_measurement_theta_max      72.8940
_cell_measurement_theta_min      4.6260
_cell_volume                     1189.86(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.83a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.83a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.83a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      122.97(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     37.00  62.00   0.50    0.50    --   34.00  78.00-121.68   50
  2  \w     37.00  62.00   0.50    0.50    --   34.00  78.00-167.60   50
  3  \w     76.00 101.00   0.50    0.50    --   70.00  73.00-176.40   50
  4  \w     80.00 105.00   0.50    0.50    --   78.00  79.00  -0.35   50
  5  \w     65.00  90.00   0.50    0.50    --   58.00  71.00 -84.55   50
  6  \w     69.00  94.00   0.50    0.50    --   62.00  71.00  36.82   50
  7  \w     65.00  90.00   0.50    0.50    --   58.00  71.00  86.01   50
  8  \w     68.00  93.00   0.50    0.50    --   62.00  72.00 109.44   50
  9  \w     76.00 101.00   0.50    0.50    --   70.00  73.00 165.95   50
 10  \w     76.00 102.00   0.50    0.50    --   70.00  73.00 148.41   52
 11  \w     69.00  94.00   0.50    0.50    --   62.00  71.00 105.29   50
 12  \w     69.00  94.00   0.50    0.50    --   62.00  71.00  70.12   50
 13  \w     57.00 118.00   0.50    0.50    --   79.50  19.00  26.19  122
 14  \w     48.00  73.00   0.50    0.50    --   79.50  18.00 -72.87   50
 15  \w     38.00  63.00   0.50    0.50    --   62.33  -0.00-122.00   50
 16  \w     98.00 123.00   0.50    0.50    --   79.50  18.00 -72.87   50
 17  \w     65.00  90.00   0.50    0.50    --   58.00  70.00-163.37   50
 18  \w     65.00  90.00   0.50    0.50    --   58.00  71.00 -89.74   50
 19  \w     51.00  76.00   0.50    0.50    --   75.20  -0.00-122.00   50
 20  \w     62.00  90.00   0.50    0.50    --   62.33   0.00  54.00   56
 21  \w     73.00 112.00   0.50    0.50    --   75.56   0.00  54.00   78
 22  \w     78.00 113.00   0.50    0.50    --   75.56   0.00 120.00   70
 23  \w     44.00  71.00   0.50    0.50    --   75.56   0.00 120.00   54
 24  \w     51.00  76.00   0.50    0.50    --   75.56  -0.00-122.00   50
 25  \w    -88.00 -62.00   0.50    0.50    --  -64.06  -0.00-122.00   52
 26  \w   -105.00 -64.00   0.50    0.50    --  -70.25  -0.00-122.00   82
 27  \w    -59.00 -34.00   0.50    0.50    --  -75.50  60.00 -86.55   50
 28  \w    -97.00 -72.00   0.50    0.50    --  -64.06   0.00  54.00   50
 29  \w   -108.00 -82.00   0.50    0.50    --  -70.25   0.00  54.00   52
 30  \w     54.00  79.00   0.50    0.50    --   54.00  83.00 176.12   50
 31  \w     54.00  79.00   0.50    0.50    --   54.00  83.00 142.15   50
 32  \w      6.00  31.00   0.50    0.50    --   14.00  94.00 164.23   50
 33  \w     34.00  59.00   0.50    0.50    --   34.00  83.00 114.74   50
 34  \w      5.00  30.00   0.50    0.50    --   14.00  96.00  83.64   50
 35  \w     46.00  71.00   0.50    0.50    --   46.00  83.00 141.19   50
 36  \w     42.00  68.00   0.50    0.50    --   42.00  83.00  69.97   52
 37  \w     46.00  71.00   0.50    0.50    --   46.00  82.00 104.36   50
 38  \w     54.00  79.00   0.50    0.50    --   54.00  82.00 -24.31   50
 39  \w     50.00  75.00   0.50    0.50    --   50.00  83.00-145.48   50
 40  \w     38.00  63.00   0.50    0.50    --   38.00  83.00-152.78   50
 41  \w     43.00  68.00   0.50    0.50    --   42.00  81.00-164.53   50
 42  \w      0.00  25.00   0.50    0.50    --   10.00  98.00 -61.29   50
 43  \w     39.00  64.00   0.50    0.50    --   38.00  81.00 -11.43   50
 44  \w     43.00  68.00   0.50    0.50    --   42.00  81.00  98.68   50
 45  \w     39.00  64.00   0.50    0.50    --   38.00  81.00 129.36   50
 46  \w     43.00  68.00   0.50    0.50    --   42.00  81.00 137.12   50
 47  \w     28.00  54.00   0.50    0.50    --   62.33 -95.00   0.00   52
 48  \w     76.00 116.00   0.50    0.50    --   79.50-139.00 -68.95   80
 49  \w     39.00  65.00   0.50    0.50    --   75.20-125.00 -90.00   52
 50  \w     44.00  69.00   0.50    0.50    --   75.20-125.00-120.00   50
 51  \w     79.00 104.00   0.50    0.50    --   75.56-125.00-150.00   50
 52  \w     36.00  86.00   0.50    0.50    --   75.56-125.00-180.00  100
 53  \w     36.00  61.00   0.50    0.50    --   75.56-125.00-150.00   50
 54  \w     38.00  63.00   0.50    0.50    --   75.56 -95.00-180.00   50
 55  \w     48.00  73.00   0.50    0.50    --   75.56 -95.00-150.00   50
 56  \w     30.00  59.00   0.50    0.50    --   62.33 -95.00-150.00   58
 57  \w     37.00  62.00   0.50    0.50    --   75.20 -95.00 -90.00   50
 58  \w     62.00 104.00   0.50    0.50    --   75.20-125.00 -30.00   84
 59  \w     28.00  58.00   0.50    0.50    --   62.33 -95.00 -60.00   60
 60  \w    -87.00 -61.00   0.50    0.50    --  -58.00 -79.00 125.00   52
 61  \w   -110.00 -79.00   0.50    0.50    --  -75.50 -76.00 156.94   62
 62  \w   -108.00 -79.00   0.50    0.50    --  -75.50 -76.00 140.15   58
 63  \w   -106.00 -78.00   0.50    0.50    --  -74.00 -75.00 113.74   56
 64  \w   -104.00 -78.00   0.50    0.50    --  -74.00 -76.00   9.69   52
 65  \w   -101.00 -75.00   0.50    0.50    --  -70.00 -75.00 136.36   52
 66  \w   -103.00 -78.00   0.50    0.50    --  -74.00 -76.00  -6.77   50
 67  \w   -103.00 -77.00   0.50    0.50    --  -70.00 -74.00 -71.46   52
 68  \w   -104.00 -79.00   0.50    0.50    --  -75.50 -79.00-118.70   50
 69  \w   -103.00 -76.00   0.50    0.50    --  -70.00 -74.00-124.72   54
 70  \w   -107.00 -78.00   0.50    0.50    --  -74.00 -77.00-153.20   58
 71  \w   -122.00 -97.00   0.50    0.50    --  -75.50 -40.00-167.95   50
 72  \w   -103.00 -77.00   0.50    0.50    --  -70.00 -74.00-151.37   52
 73  \w   -100.00 -75.00   0.50    0.50    --  -70.00 -73.00-120.74   50
 74  \w   -117.00 -92.00   0.50    0.50    --  -75.50 -59.00  32.66   50
 75  \w    -95.00 -69.00   0.50    0.50    --  -62.00 -70.00  63.53   52
 76  \w   -111.00 -79.00   0.50    0.50    --  -75.50 -89.00 131.14   64
 77  \w   -110.00 -67.00   0.50    0.50    --  -75.50-140.00 -25.67   86
 78  \w   -102.00 -77.00   0.50    0.50    --  -75.50 -89.00  68.55   50
 79  \w    -61.00 -36.00   0.50    0.50    --  -75.50 121.00  66.56   50
 80  \w    -55.00 -17.00   0.50    0.50    --  -42.00 134.00 178.68   76
 81  \w    -19.00   6.00   0.50    0.50    --   -6.00 102.00 123.96   50
 82  \w    -94.00 -68.00   0.50    0.50    --  -70.25 125.00 -60.00   52
 83  \w    -54.00 -28.00   0.50    0.50    --  -70.25 125.00 -60.00   52
 84  \w    -72.00 -47.00   0.50    0.50    --  -75.50 130.00-151.45   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0800815000
_diffrn_orient_matrix_UB_12      0.0008947000
_diffrn_orient_matrix_UB_13      -0.0479171000
_diffrn_orient_matrix_UB_21      0.0158007000
_diffrn_orient_matrix_UB_22      -0.0000539000
_diffrn_orient_matrix_UB_23      -0.1441891000
_diffrn_orient_matrix_UB_31      -0.0003580000
_diffrn_orient_matrix_UB_32      -0.2496965000
_diffrn_orient_matrix_UB_33      -0.0001120000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            6716
_diffrn_reflns_point_group_measured_fraction_full 0.941
_diffrn_reflns_point_group_measured_fraction_max 0.900
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.906
_diffrn_reflns_theta_min         2.341
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.342
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80429
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.83a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.252
_exptl_crystal_description       needle
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.206
_exptl_crystal_size_mid          0.047
_exptl_crystal_size_min          0.027
_refine_diff_density_max         1.014
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.084
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     254
_refine_ls_number_reflns         6716
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0654
_refine_ls_R_factor_gt           0.0599
_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^)+(0.1185P)^2^+0.3336P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1648
_refine_ls_wR_factor_ref         0.1704
_reflns_Friedel_coverage         0.847
_reflns_Friedel_fraction_full    0.888
_reflns_Friedel_fraction_max     0.827
_reflns_number_gt                6045
_reflns_number_total             6716
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9243\% 
around [-0.23 0.00 0.97] (reciprocal) or [-0.00 -0.00 1.00] (direct)
;
_cod_data_source_file            d3sc00580a2.cif
_cod_data_source_block           twin_nochmal_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 1568634--1568643.cif.'
_cod_database_code               1568640
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C12H17PS
_shelx_estimated_absorpt_t_max   0.915
_shelx_estimated_absorpt_t_min   0.546
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.556(3)
 0.444(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C1(H1A,H1B), C16(H16A,H16B), C14(H14A,H14B), C15(H15A,H15B),
 C4(H4A,H4B), C2(H2A,H2B), C17(H17A,H17B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,
 H6B), C13(H13A,H13B)
3.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C22(H22), C11(H11), C9(H9), C21(H21), C24(H24), C23(H23), C20(H20),
 C12(H12), C8(H8)
;
_shelx_res_checksum              87833
_shelx_hkl_checksum              33876
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.480
_oxdiff_exptl_absorpt_empirical_full_min 0.718
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2