Contorting the hetero phosphaquinoid: synthesis and electronic insights into a non-planar, ferrocenyl phosphaquinoid.
Deka, Rajesh; Chattopadhyay, Samir; Orthaber, Andreas; Dalton transactions (Cambridge, England : 2003) 54 (2025) 3113–3117; doi:10.1039/d4dt03542a

data_7717855
_publ_section_title
;
 Contorting the hetero phosphaquinoid: synthesis and electronic insights
 into a non-planar, ferrocenyl phosphaquinoid.
;
_journal_issue                   8
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3113
_journal_page_last               3117
_journal_paper_doi               10.1039/d4dt03542a
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C49 H51 Fe P, C6 H6'
_chemical_formula_sum            'C55 H57 Fe P'
_chemical_formula_weight         804.82
_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             2024-12-10
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-23 deposited with the CCDC.	2025-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.3570(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.43921(10)
_cell_length_b                   15.8638(2)
_cell_length_c                   28.9421(4)
_cell_measurement_reflns_used    18728
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      78.8270
_cell_measurement_theta_min      2.7990
_cell_volume                     4332.62(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_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)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.963
_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    -73.00  -3.00   1.00    8.85    --  -50.67  86.00 145.00   70
  2  \w    -14.00  28.00   1.00    8.85    --   50.67 -86.00  27.00   42
  3  \w   -153.00-128.00   1.00   35.40    -- -106.00 -86.00  27.00   25
  4  \w     42.00  68.00   1.00   35.40    --  110.51 -86.00  27.00   26
  5  \w     87.00 159.00   1.00   35.40    --  110.51  86.00 145.00   72
  6  \w    107.00 134.00   1.00   35.40    --  110.51 -86.00  27.00   27
  7  \w    -25.00  22.00   1.00    8.85    --  -50.67  19.00 150.00   47
  8  \w    -23.00   9.00   1.00    8.85    --  -50.67  19.00 -60.00   32
  9  \w    -18.00  25.00   1.00    8.85    --   50.67 -19.00 -90.00   43
 10  \w    -11.00  25.00   1.00    8.85    --   50.67 -19.00 -30.00   36
 11  \w    -21.00  25.00   1.00    8.85    --   50.67 -19.00 120.00   46
 12  \w    -63.00 -35.00   1.00   35.40    -- -106.00  57.00   0.00   28
 13  \w    -63.00 -36.00   1.00   35.40    -- -106.00  57.00 -60.00   27
 14  \w    -66.00 -41.00   1.00   35.40    -- -106.00  57.00  30.00   25
 15  \w   -110.00 -73.00   1.00   35.40    -- -106.00 125.00-150.00   37
 16  \w    -66.00 -34.00   1.00   35.40    -- -106.00  57.00-150.00   32
 17  \w   -167.00 -98.00   1.00   35.40    -- -106.00 -38.00  90.00   69
 18  \w   -107.00 -82.00   1.00   35.40    -- -106.00  86.00 145.00   25
 19  \w    -62.00 -36.00   1.00   35.40    -- -106.00  57.00 -90.00   26
 20  \w     41.00  66.00   1.00   35.40    --  110.51 -57.00 -60.00   25
 21  \w     42.00 102.00   1.00   35.40    --  110.51-125.00-180.00   60
 22  \w     79.00 104.00   1.00   35.40    --  110.51 -99.00  60.00   25
 23  \w     45.00  73.00   1.00   35.40    --  110.51 -99.00  60.00   28
 24  \w     39.00  64.00   1.00   35.40    --  110.51 -57.00  30.00   25
 25  \w    109.00 175.00   1.00   35.40    --  110.51  38.00-150.00   66
 26  \w     56.00  96.00   1.00   35.40    --  110.51 -99.00-180.00   40
 27  \w     73.00  98.00   1.00   35.40    --  110.51 -99.00 -90.00   25
 28  \w    153.00 178.00   1.00   35.40    --  110.51  19.00  60.00   25
 29  \w    103.00 135.00   1.00   35.40    --  110.51  19.00  60.00   32
 30  \w     39.00  64.00   1.00   35.40    --  110.51 -57.00 150.00   25
 31  \w     42.00  67.00   1.00   35.40    --  110.51 -99.00 -90.00   25
 32  \w     41.00  66.00   1.00   35.40    --  110.51 -57.00-180.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0347434000
_diffrn_orient_matrix_UB_12      0.0946470000
_diffrn_orient_matrix_UB_13      0.0030495000
_diffrn_orient_matrix_UB_21      0.0780826000
_diffrn_orient_matrix_UB_22      0.0046921000
_diffrn_orient_matrix_UB_23      0.0472945000
_diffrn_orient_matrix_UB_31      0.1391269000
_diffrn_orient_matrix_UB_32      0.0210363000
_diffrn_orient_matrix_UB_33      -0.0243000000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0278
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            35457
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.597
_diffrn_reflns_theta_min         3.055
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.403
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70059
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.142a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.234
_exptl_crystal_description       block
_exptl_crystal_F_000             1712
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.09
_refine_diff_density_max         2.015
_refine_diff_density_min         -0.763
_refine_diff_density_rms         0.065
_refine_ls_extinction_coef       0.00047(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     524
_refine_ls_number_reflns         9064
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0580
_refine_ls_R_factor_gt           0.0547
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0836P)^2^+3.9387P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1517
_refine_ls_wR_factor_ref         0.1543
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8384
_reflns_number_total             9064
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03542a2.cif
_cod_data_source_block           ao_rdferrocenepc_cis_1_auto
_cod_depositor_comments
'Adding full bibliography for 7717855--7717856.cif.'
_cod_original_cell_volume        4332.63(9)
_cod_database_code               7717855
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C55 H58 P1 Fe1 '
_shelx_estimated_absorpt_t_max   0.749
_shelx_estimated_absorpt_t_min   0.579
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C7(H7), C32(H32), C4(H4), C30(H30), C6(H6), C1(H1), C3(H3), C13(H13),
 C5(H5), C2(H2), C19(H19), C15(H15), C17(H17), C22(H22), C16(H16), C14(H14),
 C21(H21), C20(H20), C27(H27), C23(H23), C24(H24), C26(H26), C25(H25), C5S(H5S),
  C2S(H2S), C4S(H4S), C3S(H3S), C6S(H6S), C1S(H1S)
2.b Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C36(H36A,H36B,H36C), C44(H44A,H44B,H44C), C43(H43A,H43B,
 H43C), C35(H35A,H35B,H35C), C45(H45A,H45B,H45C), C41(H41A,H41B,H41C), C39(H39A,
 H39B,H39C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              16886
_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 1.750
_oxdiff_exptl_absorpt_empirical_full_min 0.592