Desolvation and aggregation of sterically demanding alkali metal diarylphosphides
Izod, Keith; Evans, Peter; Waddell, Paul G.; Dalton Trans.  (2017) –; doi:10.1039/C7DT02238G

data_7044380
_publ_section_title
;
 Desolvation and aggregation of sterically demanding alkali metal
 diarylphosphides
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT02238G
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H57 N3 Na P'
_chemical_formula_sum            'C33 H57 N3 Na P'
_chemical_formula_weight         549.77
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_symmetry_space_group_name_Hall  'P 4nw 2abw'
_symmetry_space_group_name_H-M   'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-11-10
_audit_creation_method
;
Olex2 1.2
(compiled Sep  9 2016 16:03:45 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-06-20 deposited with the CCDC.
2017-07-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.67110(10)
_cell_length_b                   12.67110(10)
_cell_length_c                   42.8676(5)
_cell_measurement_reflns_used    14842
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      66.6280
_cell_measurement_theta_min      3.5970
_cell_volume                     6882.68(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.42b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.42b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.42b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      150.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3968
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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     19.00  84.00   1.00   20.00    --   41.59 -99.00   0.00   65
  2  \w     21.00  53.00   1.00   20.00    --   41.59  38.00-180.00   32
  3  \w     15.00 116.00   1.00   20.00    --   41.59  57.00-150.00  101
  4  \w     75.00 110.00   1.00   80.00    --   93.50 -93.00-139.00   35
  5  \w     66.00 114.00   1.00   80.00    --   93.50  45.00-150.00   48
  6  \w     15.00 100.00   1.00   80.00    --   93.50 -77.00 -60.00   85
  7  \w     24.00 121.00   1.00   80.00    --   93.50 -45.00  30.00   97
  8  \w     55.00 124.00   1.00   80.00    --   93.50 -61.00 -60.00   69
  9  \w     63.00 157.00   1.00   80.00    --   93.50  30.00 150.00   94
 10  \w      8.00 129.00   1.00   80.00    --   93.50 -91.00 -63.99  121
 11  \w     32.00  94.00   1.00   80.00    --   93.50 -45.00 -60.00   62
 12  \w     17.00  91.00   1.00   80.00    --   93.50-115.00 -73.00   74
 13  \w     94.00 170.00   1.00   80.00    --   93.50  30.00-150.00   76
 14  \w     20.00  51.00   1.00   80.00    --   93.50 -61.00 -60.00   31
 15  \w     37.00  63.00   1.00   80.00    --   93.50 -93.00-139.00   26
 16  \w     66.00 104.00   1.00   80.00    --   93.50 -92.00 -24.17   38
 17  \w    122.00 150.00   1.00   80.00    --   93.50 125.00   0.00   28
 18  \w     11.00  37.00   1.00   80.00    --   93.50 -94.00  30.00   26
 19  \w     98.00 124.00   1.00   80.00    --   93.50 -93.00-102.10   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0572504000
_diffrn_orient_matrix_UB_12      -0.1054559000
_diffrn_orient_matrix_UB_13      0.0057567000
_diffrn_orient_matrix_UB_21      0.1072751000
_diffrn_orient_matrix_UB_22      0.0568153000
_diffrn_orient_matrix_UB_23      -0.0021129000
_diffrn_orient_matrix_UB_31      -0.0029468000
_diffrn_orient_matrix_UB_32      0.0205720000
_diffrn_orient_matrix_UB_33      0.0354075000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0594
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            52251
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.500
_diffrn_reflns_theta_max         66.892
_diffrn_reflns_theta_min         3.637
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.993
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71608
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.42b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.061
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2416
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.371
_refine_diff_density_min         -0.186
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 2136 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.001(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     387
_refine_ls_number_reflns         6116
_refine_ls_number_restraints     32
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0452
_refine_ls_R_factor_gt           0.0394
_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^)+(0.0536P)^2^+1.7582P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0990
_refine_ls_wR_factor_ref         0.1035
_reflns_Friedel_coverage         0.698
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                5571
_reflns_number_total             6116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt02238g2.cif
_cod_data_source_block           3c
_cod_original_cell_volume        6882.68(14)
_cod_database_code               7044380
_chemical_oxdiff_formula         'C32 H54 N3 Na1 P1'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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
 N1A-C25A \\sim N1-C25
 with sigma of 0.02
 C27A-C25A \\sim C27-C25
 with sigma of 0.02
 Na1-N1 \\sim Na1-N1A
 with sigma of 0.02
 Na1-N2 \\sim Na1-N2A
 with sigma of 0.02
 Na1-N3 \\sim Na1-N3A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C26) = Uanis(C26A)
Uanis(C25) = Uanis(C25A)
Uanis(N1) = Uanis(N1A)
Uanis(C27) = Uanis(C27A)
Uanis(C28) = Uanis(C28A)
Uanis(C29) = Uanis(C29A)
Uanis(C30) = Uanis(C30A)
Uanis(C31) = Uanis(C31A)
Uanis(N3) = Uanis(N3A)
Uanis(N2) = Uanis(N2A)
Uanis(C32) = Uanis(C32A)
Uanis(C33) = Uanis(C33A)
4. Same fragment restrains
{N1A, C27A, C28A, N2A, C30A, C31A, N3A, C25A, C26A, C29A, C33A, C32A} sigma for
1-2: 0.02, 1-3: 0.02
as
{N1, C27, C28, N2, C30, C31, N3, C25, C26, C29, C33, C32}
5. Others
 Fixed Sof: N1(0.61026) C27(0.61026) H27A(0.61026) H27B(0.61026) C28(0.61026)
 H28A(0.61026) H28B(0.61026) N2(0.61026) C30(0.61026) H30A(0.61026)
 H30B(0.61026) C31(0.61026) H31A(0.61026) H31B(0.61026) N3(0.61026)
 C25(0.61026) H25A(0.61026) H25B(0.61026) H25C(0.61026) C26(0.61026)
 H26A(0.61026) H26B(0.61026) H26C(0.61026) C29(0.61026) H29A(0.61026)
 H29B(0.61026) H29C(0.61026) C33(0.61026) H33A(0.61026) H33B(0.61026)
 H33C(0.61026) C32(0.61026) H32A(0.61026) H32B(0.61026) H32C(0.61026)
 N1A(0.38974) C27A(0.38974) H27C(0.38974) H27D(0.38974) C28A(0.38974)
 H28C(0.38974) H28D(0.38974) N2A(0.38974) C30A(0.38974) H30C(0.38974)
 H30D(0.38974) C31A(0.38974) H31C(0.38974) H31D(0.38974) N3A(0.38974)
 C25A(0.38974) H25D(0.38974) H25E(0.38974) H25F(0.38974) C26A(0.38974)
 H26D(0.38974) H26E(0.38974) H26F(0.38974) C29A(0.38974) H29D(0.38974)
 H29E(0.38974) H29F(0.38974) C33A(0.38974) H33D(0.38974) H33E(0.38974)
 H33F(0.38974) C32A(0.38974) H32D(0.38974) H32E(0.38974) H32F(0.38974)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C10(H10), C19(H19), C22(H22)
6.b Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C28(H28A,H28B), C30(H30A,H30B), C31(H31A,H31B), C27A(H27C,
 H27D), C28A(H28C,H28D), C30A(H30C,H30D), C31A(H31C,H31D)
6.c Me refined with riding coordinates:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C29(H29A,H29B,H29C), C33(H33A,H33B,
 H33C), C32(H32A,H32B,H32C), C25A(H25D,H25E,H25F), C26A(H26D,H26E,H26F),
 C29A(H29D,H29E,H29F), C33A(H33D,H33E,H33F), C32A(H32D,H32E,H32F)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C15(H15), C16(H16), C17(H17)
6.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C)
;
_shelx_res_checksum              79205
_shelx_shelxl_version_number     2014/7
_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 1.353
_oxdiff_exptl_absorpt_empirical_full_min 0.737