Functionalised organometallic photoswitches containing dihydropyrene units
Gillespie, Angus A.; Roemer, Max; Jago, David; Sobolev, Alexandre N.; Nealon, Gareth L.; Spackman, Peter R.; Moggach, Stephen A.; Koutsantonis, George; Dalton Transactions  (2023) –; doi:10.1039/D3DT02505E

data_7714055
_publ_section_title
;
 Functionalised organometallic photoswitches containing dihydropyrene
 units
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02505E
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C75 H90 P2 Ru Si, C H2 Cl2'
_chemical_formula_sum            'C76 H92 Cl2 P2 Ru Si'
_chemical_formula_weight         1267.49
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-09
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-30 deposited with the CCDC.	2023-09-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.0052(2)
_cell_length_b                   27.3628(2)
_cell_length_c                   8.73920(10)
_cell_measurement_reflns_used    39443
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.8940
_cell_measurement_theta_min      3.1390
_cell_volume                     6696.85(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(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 0.988
_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     33.00 121.00   0.50    3.50    --   45.98  19.00 -37.00  176
  2  \w   -106.00 -30.00   0.50   15.00    -- -102.37 106.00 117.00  152
  3  \w     30.00 114.00   0.50   15.00    --  102.37-129.00 -58.00  168
  4  \w    -44.00  27.00   0.50    3.50    --  -45.98  37.00 120.00  142
  5  \w     74.00 119.00   0.50    3.50    --   45.98 125.00 150.00   90
  6  \w    -27.00  40.00   0.50    3.50    --   45.98 -37.00  30.00  134
  7  \w    -73.00 -30.00   0.50   15.00    -- -102.37  61.00  30.00   86
  8  \w    -73.00 -30.00   0.50   15.00    -- -102.37  61.00  60.00   86
  9  \w   -177.00 -89.00   0.50   15.00    -- -102.37 -15.00 -60.00  176
 10  \w    -73.00 -30.00   0.50   15.00    -- -102.37  61.00-120.00   86
 11  \w    -73.00 -30.00   0.50   15.00    -- -102.37  61.00 -30.00   86
 12  \w    -73.00 -30.00   0.50   15.00    -- -102.37  61.00 -90.00   86
 13  \w     30.00  69.00   0.50   15.00    --  102.37 -61.00  60.00   78
 14  \w     30.00  69.00   0.50   15.00    --  102.37 -61.00-150.00   78
 15  \w     30.00  69.00   0.50   15.00    --  102.37 -61.00  90.00   78
 16  \w     30.00 103.00   0.50   15.00    --  102.37 -77.00   0.00  146
 17  \w     30.00 105.00   0.50   15.00    --  102.37 -94.00   0.00  150
 18  \w     90.00 178.00   0.50   15.00    --  102.37  19.00 -37.00  176
 19  \w     31.00 118.00   0.50    3.50    --   45.98  57.00-180.00  174
 20  \w     74.00 119.00   0.50    3.50    --   45.98 125.00  90.00   90
 21  \w     23.00 119.00   0.50    3.50    --   45.98  77.00  60.00  192
 22  \w     34.00 119.00   0.50    3.50    --   45.98  37.00  30.00  170
 23  \w   -175.00 -80.00   0.50   15.00    -- -102.37 -77.00 150.00  190
 24  \w   -177.00 -89.00   0.50   15.00    -- -102.37 -15.00  30.00  176
 25  \w   -177.00 -89.00   0.50   15.00    -- -102.37 -15.00-150.00  176
 26  \w   -174.00 -90.00   0.50   15.00    -- -102.37 -45.00  90.00  168
 27  \w   -177.00 -89.00   0.50   15.00    -- -102.37 -15.00 120.00  176
 28  \w   -175.00 -80.00   0.50   15.00    -- -102.37 -77.00  30.00  190
 29  \w   -174.00 -90.00   0.50   15.00    -- -102.37 -45.00 -90.00  168
 30  \w   -174.00 -90.00   0.50   15.00    -- -102.37 -45.00-180.00  168
;
_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      0.0197336000
_diffrn_orient_matrix_UB_12      0.0520581000
_diffrn_orient_matrix_UB_13      -0.0229414000
_diffrn_orient_matrix_UB_21      0.0495003000
_diffrn_orient_matrix_UB_22      -0.0213644000
_diffrn_orient_matrix_UB_23      -0.0380181000
_diffrn_orient_matrix_UB_31      -0.0136680000
_diffrn_orient_matrix_UB_32      -0.0022266000
_diffrn_orient_matrix_UB_33      -0.1705378000
_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  0.0906
_diffrn_reflns_av_unetI/netI     0.0463
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            100784
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.517
_diffrn_reflns_theta_min         3.156
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.560
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58141
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.103a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark purple'
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       block
_exptl_crystal_F_000             2680
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.002
_refine_diff_density_min         -0.855
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 5231 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     761
_refine_ls_number_reflns         13538
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0438
_refine_ls_R_factor_gt           0.0410
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0266P)^2^+9.1966P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0890
_refine_ls_wR_factor_ref         0.0901
_reflns_Friedel_coverage         0.782
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.962
_reflns_number_gt                12993
_reflns_number_total             13538
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02505e2.cif
_cod_data_source_block           gk604_auto
_cod_database_code               7714055
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C75 H90 P2 Ru1 Si1'
_chemical_oxdiff_usercomment     'Angus for George'
_shelx_estimated_absorpt_t_max   0.842
_shelx_estimated_absorpt_t_min   0.740
_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
 C029-C028 \\sim C2-C0 \\sim C024-C022 \\sim C3-C1
 with sigma of 0.02
 C028-C024 \\sim C3-C2
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C029) = Uanis(C0) = Uanis(C1) = Uanis(C022)
Uanis(C3) = Uanis(C028) = Uanis(C2) = Uanis(C024)
4. Others
 Sof(C022)=Sof(H02A)=Sof(H02B)=Sof(H02C)=Sof(C024)=Sof(C028)=Sof(C029)=
 Sof(H02P)=Sof(H02Q)=Sof(H02R)=1-FVAR(1)
 Sof(C0)=Sof(H0A)=Sof(H0B)=Sof(H0C)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=
 Sof(C3)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C011(H011), C01M(H01T), C01Z(H8)
5.b Secondary CH2 refined with riding coordinates:
 C00T(H00H,H00J), C019(H01A,H01B), C02A(H02S,H02T)
5.c Aromatic/amide H refined with riding coordinates:
 C007(H007), C00A(H00A), C00D(H00D), C00E(H00E), C00F(H00F), C00I(H00I),
 C00K(H00K), C00N(H00N), C00Q(H00Q), C00U(H00U), C00Y(H00Y), C013(H013),
 C016(H016), C017(H017), C018(H018), C01A(H01C), C01C(H01G), C01I(H01Q),
 C01J(H01R), C01K(H01S), C01R(H01), C01U(H3), C01V(H4), C01W(H5), C020(H020),
 C021(H021)
5.d Idealised Me refined as rotating group:
 C00M(H00B,H00C,H00G), C00V(H00L,H00M,H00O), C01B(H01D,H01E,H01F), C01E(H01H,
 H01I,H01J), C01F(H01K,H01L,H01M), C01G(H01N,H01O,H01P), C01O(H01U,H01V,H01W),
 C01P(H01X,H01Y,H), C01Q(H01Z,HA,HB), C01S(H1,HC,HD), C01T(H2,HE,HF), C01X(H6,
 HG,HH), C01Y(H7,HI,HJ), C022(H02A,H02B,H02C), C023(H02D,H02E,H02F), C025(H02G,
 H02H,H02I), C026(H02J,H02K,H02L), C027(H02M,H02N,H02O), C029(H02P,H02Q,H02R),
 C0(H0A,H0B,H0C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              33806
_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 1.982
_oxdiff_exptl_absorpt_empirical_full_min 0.632