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_7714056
_publ_section_title
;
 Functionalised organometallic photoswitches containing dihydropyrene
 units
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02505E
_journal_year                    2023
_chemical_formula_moiety         'C64 H70 P2 Ru'
_chemical_formula_sum            'C64 H70 P2 Ru'
_chemical_formula_weight         1002.21
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-07
_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                 99.4930(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   28.3238(2)
_cell_length_b                   8.83780(10)
_cell_length_c                   44.5941(3)
_cell_measurement_reflns_used    122647
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.5180
_cell_measurement_theta_min      3.1360
_cell_volume                     11009.93(17)
_computing_cell_refinement       'CrysAlisPro 1.171.43.70a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 41.104a 64-bit (release 16-03-2021))'
_computing_data_reduction        'CrysAlisPro 1.171.43.70a (Rigaku OD, 2023)'
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.967
_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   -110.00 -27.00   0.50    0.30    --  -46.23 152.00  66.00  166
  2  \w    -92.00 -10.00   0.50    0.30    --  -46.23 121.00 -93.00  164
  3  \w   -118.00 -55.00   0.50    0.30    --  -46.23-152.00  24.00  126
  4  \w     10.00  92.00   0.50    0.30    --   46.23-121.00-176.00  164
  5  \w     27.00 111.00   0.50    0.30    --   46.23-152.00  24.00  168
  6  \w     55.00 118.00   0.50    0.30    --   46.23 152.00  66.00  126
  7  \w   -110.00 -30.00   0.50    0.80    -- -102.37 121.00 -93.00  160
  8  \w   -160.00-125.00   0.50    0.80    -- -102.37-121.00-176.00   70
  9  \w   -134.00-109.00   0.50    0.80    -- -102.37-152.00  24.00   50
 10  \w     85.00 110.00   0.50    0.80    --  102.37 152.00  66.00   50
 11  \w     31.00 131.00   0.50    0.80    --  102.37-152.00  24.00  200
 12  \w     79.00 129.00   0.50    0.80    --  102.37 121.00 -93.00  100
 13  \w     47.00 110.00   0.50    0.80    --  102.37-121.00-176.00  126
 14  \w    -48.00 -17.00   0.50    0.30    --    2.00 130.00  54.01   62
 15  \w    -13.00  14.00   0.50    0.30    --   18.00 102.00  66.79   54
 16  \w    -15.00  10.00   0.50    0.30    --   18.00  98.00 -44.14   50
 17  \w     -8.00  21.00   0.50    0.30    --   22.00 100.00 117.71   58
 18  \w      9.00  39.00   0.50    0.30    --   38.00  90.00  80.84   60
 19  \w     14.00  41.00   0.50    0.30    --   42.00  92.00 -43.25   54
 20  \w     14.00  40.00   0.50    0.30    --   42.00  88.00 -76.71   52
 21  \w     15.00  40.00   0.50    0.30    --   42.00  86.00-177.11   50
 22  \w     17.00  42.00   0.50    0.30    --   46.00  90.00  49.39   50
 23  \w     17.00  42.00   0.50    0.30    --   46.00  90.00-164.50   50
 24  \w    -98.00 -33.00   0.50    0.30    --  -46.23 -19.00-120.00  130
 25  \w     28.00  60.00   0.50    0.30    --   50.00  76.00  87.32   64
 26  \w     82.00 122.00   0.50    0.30    --   50.00  76.00  87.32   80
 27  \w     27.00  53.00   0.50    0.30    --   50.00  77.00 150.59   52
 28  \w     77.00 122.00   0.50    0.30    --   50.00  77.00 150.59   90
 29  \w     31.00  62.00   0.50    0.30    --   54.00  77.00 -52.53   62
 30  \w     84.00 126.00   0.50    0.30    --   54.00  77.00  -4.60   84
 31  \w     31.00  78.00   0.50    0.30    --   54.00  77.00  -4.60   94
 32  \w     33.00  64.00   0.50    0.30    --   54.00  76.00 161.42   62
 33  \w     69.00  96.00   0.50    0.30    --   54.00  77.00 -52.53   54
 34  \w     76.00 102.00   0.50    0.30    --   58.00  77.00-115.49   52
 35  \w     68.00  94.00   0.50    0.30    --   58.00  76.00-139.25   52
 36  \w     97.00 130.00   0.50    0.30    --   58.00  77.00  14.47   66
 37  \w     35.00  61.00   0.50    0.30    --   58.00  77.00-115.49   52
 38  \w     37.00  63.00   0.50    0.30    --   58.00  76.00 135.17   52
 39  \w     36.00  69.00   0.50    0.30    --   58.00  77.00  14.47   66
 40  \w     38.00  64.00   0.50    0.30    --   58.00  74.00 100.03   52
 41  \w     36.00  64.00   0.50    0.30    --   58.00  76.00-139.25   56
 42  \w     39.00  75.00   0.50    0.30    --   62.00  77.00-174.41   72
 43  \w     43.00  68.00   0.50    0.30    --   66.00  77.00 -48.00   50
 44  \w     43.00  73.00   0.50    0.30    --   66.00  77.00-108.20   60
 45  \w     43.00  74.00   0.50    0.30    --   66.00  77.00 -25.30   62
 46  \w     43.00  71.00   0.50    0.30    --   66.00  77.00  28.88   56
 47  \w     43.00  68.00   0.50    0.30    --   66.00  77.00 -79.60   50
 48  \w     43.00  68.00   0.50    0.30    --   66.00  77.00-156.18   50
 49  \w     45.00  73.00   0.50    0.30    --   66.00  76.00 147.49   56
 50  \w    -73.00 -47.00   0.50    0.30    --  -70.00 -77.00  24.75   52
 51  \w    -77.00 -47.00   0.50    0.30    --  -70.00 -76.00  68.39   60
 52  \w    -73.00 -47.00   0.50    0.30    --  -70.00 -76.00  98.95   52
 53  \w     47.00  73.00   0.50    0.30    --   70.00  77.00-141.01   52
 54  \w    -77.00 -51.00   0.50    0.30    --  -74.00 -76.00  55.29   52
 55  \w    -78.00 -52.00   0.50    0.30    --  -74.00 -75.00  96.15   52
 56  \w    -77.00 -51.00   0.50    0.30    --  -74.00 -76.00 -14.07   52
 57  \w    -77.00 -51.00   0.50    0.30    --  -74.00 -76.00 -65.24   52
 58  \w    -89.00 -55.00   0.50    0.30    --  -74.00 -73.00  10.37   68
 59  \w     52.00  78.00   0.50    0.30    --   74.00  75.00  56.46   52
 60  \w   -106.00 -57.00   0.50    0.80    --  -78.00 -72.00-174.18   98
 61  \w    -83.00 -57.00   0.50    0.80    --  -78.00 -73.00 -85.12   52
 62  \w    -88.00 -62.00   0.50    0.80    --  -82.00 -72.00 142.44   52
 63  \w    -86.00 -60.00   0.50    0.80    --  -82.00 -74.00 128.97   52
 64  \w    -87.00 -61.00   0.50    0.80    --  -82.00 -73.00-159.51   52
 65  \w    -85.00 -60.00   0.50    0.80    --  -82.00 -75.00 166.78   50
 66  \w    -87.00 -61.00   0.50    0.80    --  -82.00 -72.00 -95.59   52
 67  \w   -101.00 -61.00   0.50    0.80    --  -82.00 -74.00-133.85   80
 68  \w    -87.00 -60.00   0.50    0.80    --  -82.00 -77.00 160.38   54
 69  \w    -86.00 -60.00   0.50    0.80    --  -82.00 -76.00  87.46   52
 70  \w    -91.00 -65.00   0.50    0.80    --  -86.00 -72.00 -67.56   52
 71  \w    -95.00 -64.00   0.50    0.80    --  -86.00 -74.00 -14.47   62
 72  \w   -101.00 -65.00   0.50    0.80    --  -86.00 -73.00 132.51   72
 73  \w    -90.00 -64.00   0.50    0.80    --  -86.00 -74.00  70.54   52
 74  \w   -147.00-121.00   0.50    0.80    --  -86.00 -74.00  70.54   52
 75  \w    -95.00 -64.00   0.50    0.80    --  -86.00 -74.00 -25.98   62
 76  \w   -159.00-115.00   0.50    0.80    --  -86.00 -74.00 -25.98   88
 77  \w    -90.00 -64.00   0.50    0.80    --  -86.00 -74.00-109.87   52
 78  \w   -157.00 -70.00   0.50    0.80    --  -90.00 -69.00  -5.17  174
 79  \w   -162.00 -72.00   0.50    0.80    --  -90.00 -66.00  97.85  180
 80  \w   -104.00 -68.00   0.50    0.80    --  -90.00 -75.00 -36.05   72
 81  \w   -161.00-122.00   0.50    0.80    --  -90.00 -75.00 -36.05   78
 82  \w   -120.00 -72.00   0.50    0.80    --  -90.00 -65.00 -62.37   96
 83  \w    -95.00 -70.00   0.50    0.80    --  -90.00 -71.00  19.79   50
 84  \w   -159.00 -68.00   0.50    0.80    --  -90.00 -74.00   7.19  182
 85  \w   -148.00-118.00   0.50    0.80    --  -90.00 -71.00  19.79   60
 86  \w    -93.00 -68.00   0.50    0.80    --  -90.00 -74.00-111.84   50
 87  \w   -160.00-107.00   0.50    0.80    --  -90.00 -74.00-111.84  106
 88  \w    -94.00 -69.00   0.50    0.80    --  -90.00 -72.00  53.03   50
 89  \w   -160.00 -67.00   0.50    0.80    --  -90.00 -76.00 -70.62  186
 90  \w    -98.00 -71.00   0.50    0.80    --  -94.00 -77.00  75.58   54
 91  \w   -134.00-108.00   0.50    0.80    --  -94.00 -77.00  75.58   52
 92  \w   -167.00 -73.00   0.50    0.80    --  -94.00 -75.00-175.64  188
 93  \w    -99.00 -72.00   0.50    0.80    --  -94.00 -75.00 102.51   54
 94  \w   -167.00-141.00   0.50    0.80    --  -94.00 -75.00 102.51   52
 95  \w   -165.00 -73.00   0.50    0.80    --  -94.00 -75.00-126.91  184
 96  \w    -99.00 -74.00   0.50    0.80    --  -94.00 -70.00 161.21   50
 97  \w   -142.00-104.00   0.50    0.80    --  -94.00 -70.00 161.21   76
 98  \w   -100.00 -73.00   0.50    0.80    --  -94.00 -74.00-146.10   54
 99  \w   -149.00-123.00   0.50    0.80    --  -94.00 -74.00-146.10   52
100  \w   -166.00 -71.00   0.50    0.80    --  -94.00 -77.00-163.30  190
101  \w    -97.00 -71.00   0.50    0.80    --  -94.00 -77.00 122.08   52
102  \w   -153.00-108.00   0.50    0.80    --  -94.00 -77.00 122.08   90
103  \w   -166.00 -71.00   0.50    0.80    --  -94.00 -76.00 127.18  190
104  \w   -166.00 -71.00   0.50    0.80    --  -94.00 -76.00 -79.18  190
105  \w   -169.00 -75.00   0.50    0.80    --  -98.00 -77.00  60.58  188
106  \w   -170.00 -75.00   0.50    0.80    --  -98.00 -76.00  47.51  190
107  \w    -82.00 -57.00   0.50    0.80    -- -102.37 137.00 116.07   50
108  \w   -121.00 -94.00   0.50    0.80    -- -102.37 137.00 116.07   54
109  \w    -62.00 -37.00   0.50    0.80    -- -102.37 105.00  29.16   50
110  \w   -106.00 -65.00   0.50    0.80    -- -102.37 105.00  29.16   82
111  \w   -107.00 -31.00   0.50    0.80    -- -102.37 125.00  60.00  152
112  \w   -108.00 -55.00   0.50    0.80    -- -102.37 108.00 -31.62  106
113  \w   -105.00 -31.00   0.50    0.80    -- -102.37  77.00  90.00  148
114  \w   -119.00 -64.00   0.50    0.80    -- -102.37 152.00  66.00  110
115  \w     42.00  68.00   0.50    0.80    --  102.37 -61.00-120.00   52
116  \w     33.00  65.00   0.50    0.80    --  102.37 -61.00 -30.00   64
117  \w     42.00 103.00   0.50    0.80    --  102.37 -77.00-150.00  122
118  \w     33.00 103.00   0.50    0.80    --  102.37 -94.00-150.00  140
119  \w     30.00  61.00   0.50    0.80    --  102.37 -61.00   0.00   62
;
_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      0.0106647000
_diffrn_orient_matrix_UB_12      0.0461390000
_diffrn_orient_matrix_UB_13      -0.0315390000
_diffrn_orient_matrix_UB_21      0.0539999000
_diffrn_orient_matrix_UB_22      -0.0206660000
_diffrn_orient_matrix_UB_23      0.0114593000
_diffrn_orient_matrix_UB_31      -0.0035776000
_diffrn_orient_matrix_UB_32      -0.1667630000
_diffrn_orient_matrix_UB_33      -0.0100490000
_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  0.0423
_diffrn_reflns_av_unetI/netI     0.0132
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -55
_diffrn_reflns_number            192618
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.363
_diffrn_reflns_theta_min         3.164
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.129
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.621
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.70a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark green'
_exptl_crystal_density_diffrn    1.209
_exptl_crystal_description       block
_exptl_crystal_F_000             4224
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.611
_refine_diff_density_min         -1.036
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     635
_refine_ls_number_reflns         11004
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0357
_refine_ls_R_factor_gt           0.0346
_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^)+(0.0421P)^2^+24.8448P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0927
_refine_ls_wR_factor_ref         0.0934
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10607
_reflns_number_total             11004
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02505e2.cif
_cod_data_source_block           gk597
_cod_database_code               7714056
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C64 H70 P2 Ru1'
_chemical_oxdiff_usercomment     'Angus for George'
_shelx_estimated_absorpt_t_max   0.834
_shelx_estimated_absorpt_t_min   0.533
_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
 C01T-C01U \\sim C01T-C7
 with sigma of 0.02
 C00R-C01S \\sim C00R-C2
 with sigma of 0.02
 C011-C01S \\sim C011-C2
 with sigma of 0.02
 C01S-C01T \\sim C2-C01T
 with sigma of 0.02
 C01S-C01V \\sim C2-C01V
 with sigma of 0.02
 C01S-C01V \\sim C01S-C01W
 with sigma of 0.02
 C01V-C2 \\sim C01W-C2
 with sigma of 0.02
 C00G-C01T \\sim C00G-C3
 with sigma of 0.02
 C016-C01T \\sim C016-C3
 with sigma of 0.02
 C01S-C01T \\sim C01S-C3
 with sigma of 0.02
 C01T-C01U \\sim C3-C01U
 with sigma of 0.02
 C01T-C2 \\sim C3-C2
 with sigma of 0.02
 C01T-C01W \\sim C3-C01W
 with sigma of 0.02
 C01U-C01T \\sim C7-C01S \\sim C2-C01V \\sim C3-C01W
 with sigma of 0.02
 C3-C01S \\sim C2-C01T
 with sigma of 0.02
 C01T-C016 \\sim C3-C016
 with sigma of 0.02
 C01T-C00G \\sim C3-C00G
 with sigma of 0.02
 C01S-C011 \\sim C2-C011
 with sigma of 0.02
 C01S-C00R \\sim C2-C00R
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C01U) = Uanis(C7)
Uanis(C01T) = Uanis(C3)
Uanis(C01S) = Uanis(C2)
Uanis(C01W) = Uanis(C01V)
4. Others
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=1-FVAR(1)
 Sof(C01U)=Sof(H4)=Sof(HJ)=Sof(HK)=FVAR(1)
 Sof(C2)=1-FVAR(2)
 Sof(C01S)=FVAR(2)
 Sof(C01W)=Sof(H6)=Sof(HN)=Sof(HO)=1-FVAR(3)
 Sof(C01V)=Sof(H5)=Sof(HL)=Sof(HM)=FVAR(3)
 Sof(C3)=1-FVAR(4)
 Sof(C01T)=FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C00F(H00B,H00C), C00H(H00D,H00E)
5.b Aromatic/amide H refined with riding coordinates:
 C008(H008), C009(H009), C00A(H00A), C00M(H00M), C00N(H00N), C00O(H00O),
 C00P(H00P), C00S(H00S), C00T(H00T), C00U(H00U), C00W(H00W), C00X(H00X),
 C00Y(H00Y), C012(H012), C013(H013), C014(H014), C015(H015), C017(H017),
 C018(H018), C019(H019), C01A(H01D), C01B(H01E), C01E(H01L), C01F(H01M),
 C01H(H01N), C01K(H01U), C01L(H01V)
5.c Idealised Me refined as rotating group:
 C010(H01A,H01B,H01C), C01C(H01F,H01G,H01H), C01D(H01I,H01J,H01K), C01I(H01O,
 H01P,H01Q), C01J(H01R,H01S,H01T), C01M(H01W,H01X,H01Y), C01N(H01Z,H,HA),
 C01O(H01,HB,HC), C01P(H1,HD,HE), C01Q(H2,HF,HG), C01R(H3,HH,HI), C01U(H4,HJ,
 HK), C01V(H5,HL,HM), C7(H7A,H7B,H7C), C01W(H6,HN,HO)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 192 electrons were 
found in a volume of 1416\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1.3[CH3OH] per Asymmetric Unit 
which account for 187 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              6620
_shelx_fab_checksum              67521
_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 1.430
_oxdiff_exptl_absorpt_empirical_full_min 0.689