Iron vs. ruthenium: syntheses, structures and IR spectroelectrochemical characterisation of half-sandwich Group 8 acetylide complexes
Harrison, Daniel P.; Kumar, Varshini J.; Noppers, Johanna N.; Gluyas, Josef B. G.; Sobolev, Alexandre N.; Moggach, Stephen A.; Low, Paul J.; New Journal of Chemistry 45 (2021) 14932–14943; doi:10.1039/D0NJ03093G

data_7059882
_publ_section_title
;
 Iron vs. ruthenium: syntheses, structures and IR spectroelectrochemical
 characterisation of half-sandwich Group 8 acetylide complexes
;
_journal_issue                   33
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              14932
_journal_page_last               14943
_journal_paper_doi               10.1039/D0NJ03093G
_journal_volume                  45
_journal_year                    2021
_chemical_formula_moiety         'C37 H38 P2 Ru'
_chemical_formula_sum            'C37 H38 P2 Ru'
_chemical_formula_weight         645.68
_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
_audit_creation_date             2020-06-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-06-15 deposited with the CCDC.	2020-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.0410(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.66800(10)
_cell_length_b                   18.5220(2)
_cell_length_c                   20.3518(2)
_cell_measurement_reflns_used    55076
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      78.1480
_cell_measurement_theta_min      3.1940
_cell_volume                     3235.33(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_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    -60.00  28.00   0.50    0.05    --  -45.37  52.00-145.00  176
  2  \w   -117.00 -30.00   0.50    0.05    --  -45.37 -52.00  69.00  174
  3  \w     30.00 118.00   0.50    0.05    --   45.37  52.00-145.00  176
  4  \w    -26.00  61.00   0.50    0.05    --   45.37 -52.00  69.00  174
  5  \w   -177.00 -91.00   0.50    0.05    -- -106.00 -52.00  69.00  172
  6  \w   -121.00 -33.00   0.50    0.05    -- -106.00  52.00-145.00  176
  7  \w     95.00 178.00   0.50    0.05    --  110.00  52.00-145.00  166
  8  \w     38.00 125.00   0.50    0.05    --  110.00 -52.00  69.00  174
  9  \w     29.00 118.00   0.50    0.05    --   45.37  57.00 -30.00  178
 10  \w     71.00 118.00   0.50    0.05    --   45.37 125.00  60.00   94
 11  \w     31.00 119.00   0.50    0.05    --   45.37  37.00  30.00  176
 12  \w     71.00 118.00   0.50    0.05    --   45.37 125.00-120.00   94
 13  \w     29.00 118.00   0.50    0.05    --   45.37  57.00 -60.00  178
 14  \w     71.00 118.00   0.50    0.05    --   45.37 125.00-150.00   94
 15  \w    -26.00  62.00   0.50    0.05    --   45.37 -57.00-180.00  176
 16  \w     10.00  94.00   0.50    0.05    --   45.37-125.00 -60.00  168
 17  \w   -177.00 -83.00   0.50    0.05    -- -106.00 -74.00 -47.11  188
 18  \w   -177.00 -83.00   0.50    0.05    -- -106.00 -74.00  21.21  188
 19  \w   -177.00 -91.00   0.50    0.05    -- -106.00 -45.00 -42.78  172
 20  \w   -177.00 -81.00   0.50    0.05    -- -106.00 -79.00  -9.78  192
 21  \w   -177.00 -87.00   0.50    0.05    -- -106.00 -64.00  -3.93  180
 22  \w   -177.00 -91.00   0.50    0.05    -- -106.00 -45.00  30.00  172
 23  \w   -177.00 -82.00   0.50    0.05    -- -106.00 -77.00   0.00  190
 24  \w   -117.00 -33.00   0.50    0.05    -- -106.00 125.00-120.00  168
 25  \w   -177.00 -88.00   0.50    0.05    -- -106.00 -62.00 -52.98  178
 26  \w   -177.00 -79.00   0.50    0.05    -- -106.00 -83.00  11.40  196
 27  \w   -177.00 -91.00   0.50    0.05    -- -106.00 -44.00 -10.52  172
 28  \w   -177.00 -91.00   0.50    0.05    -- -106.00 -44.00 -16.93  172
 29  \w   -177.00 -88.00   0.50    0.05    -- -106.00 -61.00   0.00  178
 30  \w   -177.00 -88.00   0.50    0.05    -- -106.00 -63.00 -41.86  178
 31  \w   -177.00 -82.00   0.50    0.05    -- -106.00 -77.00 -60.00  190
 32  \w   -177.00 -88.00   0.50    0.05    -- -106.00 -63.00 -38.47  178
 33  \w   -177.00 -91.00   0.50    0.05    -- -106.00 -45.00 -31.18  172
 34  \w   -124.00 -30.00   0.50    0.05    -- -106.00  15.00  60.00  188
 35  \w   -177.00 -86.00   0.50    0.05    -- -106.00 -68.00 -14.09  182
 36  \w   -177.00 -78.00   0.50    0.05    -- -106.00 -85.00 -23.41  198
 37  \w   -177.00 -88.00   0.50    0.05    -- -106.00 -63.00  25.92  178
 38  \w   -177.00 -80.00   0.50    0.05    -- -106.00 -94.00   0.00  194
 39  \w   -177.00 -83.00   0.50    0.05    -- -106.00 -74.00 -49.35  188
 40  \w   -177.00 -90.00   0.50    0.05    -- -106.00 -51.00 -49.01  174
 41  \w     38.00 117.00   0.50    0.05    --  110.00-125.00  30.00  158
 42  \w     35.00 125.00   0.50    0.05    --  110.00 -30.00 150.00  180
 43  \w     38.00 109.00   0.50    0.05    --  110.00 -94.00 150.00  142
 44  \w     38.00 117.00   0.50    0.05    --  110.00-125.00  60.00  158
 45  \w     96.00 178.00   0.50    0.05    --  110.00  45.00-180.00  164
 46  \w     37.00 178.00   0.50    0.05    --  110.00   0.00 150.00  282
 47  \w     93.00 178.00   0.50    0.05    --  110.00  61.00 -60.00  170
 48  \w     96.00 178.00   0.50    0.05    --  110.00  30.00  60.00  164
 49  \w     38.00 109.00   0.50    0.05    --  110.00 -94.00  90.00  142
 50  \w     38.00 109.00   0.50    0.05    --  110.00 -94.00-150.00  142
 51  \w     38.00 134.00   0.50    0.05    --  110.00 -77.00-150.00  192
 52  \w     86.00 178.00   0.50    0.05    --  110.00  77.00 -90.00  184
 53  \w     86.00 178.00   0.50    0.05    --  110.00  77.00-120.00  184
 54  \w     38.00 117.00   0.50    0.05    --  110.00-125.00 -30.00  158
 55  \w    -61.00  30.00   0.50    0.05    --  -45.37  19.00  30.00  182
 56  \w     22.00 118.00   0.50    0.05    --   45.37  77.00-180.00  192
 57  \w     22.00 118.00   0.50    0.05    --   45.37  77.00 120.00  192
 58  \w     22.00 118.00   0.50    0.05    --   45.37  77.00  60.00  192
 59  \w     22.00 118.00   0.50    0.05    --   45.37  77.00-150.00  192
 60  \w     22.00 118.00   0.50    0.05    --   45.37  77.00 -90.00  192
 61  \w     22.00 118.00   0.50    0.05    --   45.37  77.00 -30.00  192
 62  \w     29.00 118.00   0.50    0.05    --   45.37  57.00 120.00  178
 63  \w     31.00 119.00   0.50    0.05    --   45.37  37.00 120.00  176
 64  \w     22.00 118.00   0.50    0.05    --   45.37  77.00  30.00  192
 65  \w   -177.00 -89.00   0.50    0.05    -- -106.00 -74.00  46.21  176
 66  \w   -177.00 -81.00   0.50    0.05    -- -106.00 -79.00 142.30  192
 67  \w   -177.00 -77.00   0.50    0.05    -- -106.00 -89.00-110.97  200
 68  \w   -177.00 -76.00   0.50    0.05    -- -106.00 -90.00 -85.36  202
 69  \w   -177.00 -77.00   0.50    0.05    -- -106.00 -88.00 179.74  200
 70  \w   -177.00 -80.00   0.50    0.05    -- -106.00 -81.00 122.07  194
 71  \w   -177.00 -85.00   0.50    0.05    -- -106.00 -69.00-175.22  184
 72  \w   -177.00 -79.00   0.50    0.05    -- -106.00 -83.00 110.96  196
 73  \w   -177.00 -76.00   0.50    0.05    -- -106.00 -90.00-122.75  202
 74  \w   -177.00 -76.00   0.50    0.05    -- -106.00 -91.00  87.95  202
 75  \w   -177.00 -77.00   0.50    0.05    -- -106.00 -87.00 -68.54  200
 76  \w   -177.00 -84.00   0.50    0.05    -- -106.00 -72.00 155.73  186
 77  \w   -177.00 -79.00   0.50    0.05    -- -106.00 -83.00-151.84  196
 78  \w     38.00 109.00   0.50    0.05    --  110.00 -94.00  30.00  142
;
_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      0.0094533000
_diffrn_orient_matrix_UB_12      0.0406286000
_diffrn_orient_matrix_UB_13      -0.0653745000
_diffrn_orient_matrix_UB_21      -0.1574007000
_diffrn_orient_matrix_UB_22      -0.0327769000
_diffrn_orient_matrix_UB_23      -0.0301788000
_diffrn_orient_matrix_UB_31      -0.0856164000
_diffrn_orient_matrix_UB_32      0.0647645000
_diffrn_orient_matrix_UB_33      0.0257631000
_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  0.0921
_diffrn_reflns_av_unetI/netI     0.0242
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            160066
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.036
_diffrn_reflns_theta_min         3.241
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.021
_exptl_absorpt_correction_T_max  0.912
_exptl_absorpt_correction_T_min  0.822
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_density_diffrn    1.326
_exptl_crystal_description       block
_exptl_crystal_F_000             1336
_exptl_crystal_size_max          0.218
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.103
_refine_diff_density_max         0.559
_refine_diff_density_min         -0.899
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     339
_refine_ls_number_reflns         6916
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0411
_refine_ls_R_factor_gt           0.0376
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0620P)^2^+1.6103P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1029
_refine_ls_wR_factor_ref         0.1062
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6215
_reflns_number_total             6916
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0nj03093g2.cif
_cod_data_source_block           dph1-32
_cod_depositor_comments
'Adding full bibliography for 7059874--7059882.cif.'
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7059882
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ru1 P2 C20 H20'
_shelx_estimated_absorpt_t_max   0.626
_shelx_estimated_absorpt_t_min   0.407
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 C8-C10 \\sim C8-C10A \\sim C9-C8 \\sim C9A-C8 \\sim C8-C11 \\sim C8-C11A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C11) = Uanis(C11A) = Uanis(C10) = Uanis(C10A) = Uanis(C9) = Uanis(C9A)
Uanis(C11A) = Uanis(C11) = Uanis(C9A) = Uanis(C9) = Uanis(C10A) = Uanis(C10)
Uanis(C5) = Uanis(C1) = Uanis(C2) = Uanis(C3) = Uanis(C4)
Uanis(C1) = Uanis(C2) = Uanis(C3) = Uanis(C4) = Uanis(C5) = Uanis(C4A) =
Uanis(C5A) = Uanis(C1A) = Uanis(C3A) = Uanis(C2A)
4. Others
 Sof(C11A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C10A)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=1-FVAR(1)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(1)
 Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C1A)=Sof(H1A)=
 Sof(C2A)=Sof(H2A)=1-FVAR(2)
 Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=
 Sof(H3)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C24(H24A,H24B)
5.b Aromatic/amide H refined with riding coordinates:
 C31(H31), C30(H30), C29(H29), C23(H23), C27(H27), C33(H33), C22(H22),
 C17(H17), C4(H4), C5(H5), C1(H1), C2(H2), C3(H3), C19(H19), C15(H15), C28(H28),
  C34(H34), C21(H21), C13(H13), C16(H16), C35(H35), C37(H37), C14(H14),
 C20(H20), C36(H36), C3A(H3A), C4A(H4A), C5A(H5A), C1A(H1A), C2A(H2A)
5.c Fitted pentagon refined as free rotating group:
 C4(C5,C1,C2,C3), C3A(C4A,C5A,C1A,C2A)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C), C11A(H11D,H11E,
 H11F), C10A(H10D,H10E,H10F), C9A(H9AA,H9AB,H9AC)
;
_shelx_res_checksum              99651
_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 1.758
_oxdiff_exptl_absorpt_empirical_full_min 0.689