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_7714059
_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         '2(C18 H24 Si)'
_chemical_formula_sum            'C36 H48 Si2'
_chemical_formula_weight         536.92
_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     dual
_audit_creation_date             2023-06-06
_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                 112.687(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.9812(4)
_cell_length_b                   21.0158(5)
_cell_length_c                   15.1892(4)
_cell_measurement_reflns_used    14752
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      70.2840
_cell_measurement_theta_min      3.7650
_cell_volume                     3528.6(2)
_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    'XT  (Sheldrick, 2015)'
_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 0.925
_diffrn_measured_fraction_theta_max 0.833
_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    -14.00  12.00   0.50    8.00    --   46.23 -87.00  90.00   52
  2  \w     14.00  42.00   0.50    8.00    --   46.23 -87.00  90.00   56
  3  \w   -151.00-126.00   0.50    8.00    -- -102.37 -87.00  90.00   50
  4  \w    -65.00 -32.00   0.50    8.00    -- -102.37  87.00-152.00   66
  5  \w    150.00 175.00   0.50    8.00    --  102.37  87.00-152.00   50
  6  \w     86.00 130.00   0.50    8.00    --  102.37  87.00-152.00   88
  7  \w    -42.00 -16.00   0.50    8.00    --    6.00 128.00 -13.97   52
  8  \w    -17.00  11.00   0.50    8.00    --   14.00  99.00-135.76   56
  9  \w    -12.00  26.00   0.50    8.00    --   18.00  97.00 -52.07   76
 10  \w    -14.00  17.00   0.50    8.00    --   18.00  98.00  49.04   62
 11  \w      0.00  26.00   0.50    8.00    --   30.00  96.00 -12.65   52
 12  \w      9.00  34.00   0.50    8.00    --   38.00  91.00-152.79   50
 13  \w     12.00  37.00   0.50    8.00    --   42.00  92.00 -64.74   50
 14  \w     12.00  37.00   0.50    8.00    --   42.00  92.00  85.37   50
 15  \w     17.00  42.00   0.50    8.00    --   46.00  90.00  47.27   50
 16  \w    -73.00  12.00   0.50    8.00    --  -46.23  87.00-152.00  170
 17  \w     24.00  52.00   0.50    8.00    --   46.23  77.00-120.00   56
 18  \w    -17.00  37.00   0.50    8.00    --   46.23 -37.00 120.00  108
 19  \w     46.00  73.00   0.50    8.00    --   46.23 -87.00  90.00   54
 20  \w     39.00  91.00   0.50    8.00    --   46.23  19.00-150.00  104
 21  \w    -23.00  15.00   0.50    8.00    --   46.23 -19.00-180.00   76
 22  \w     24.00  57.00   0.50    8.00    --   46.23  77.00 -60.00   66
 23  \w     73.00  99.00   0.50    8.00    --   50.00  77.00  -8.64   52
 24  \w     27.00  53.00   0.50    8.00    --   50.00  77.00  -8.64   52
 25  \w     85.00 111.00   0.50    8.00    --   54.00  77.00 138.50   52
 26  \w     34.00  59.00   0.50    8.00    --   54.00  77.00 138.50   50
 27  \w     36.00  79.00   0.50    8.00    --   58.00  76.00 177.86   86
 28  \w     37.00  63.00   0.50    8.00    --   58.00  76.00 -16.91   52
 29  \w     81.00 128.00   0.50    8.00    --   58.00  75.00  26.93   94
 30  \w     37.00  63.00   0.50    8.00    --   58.00  75.00  26.93   52
 31  \w     37.00  63.00   0.50    8.00    --   58.00  77.00 108.09   52
 32  \w     40.00  66.00   0.50    8.00    --   62.00  75.00 -99.02   52
 33  \w     87.00 135.00   0.50    8.00    --   62.00  77.00-133.34   96
 34  \w     39.00  73.00   0.50    8.00    --   62.00  77.00-133.34   68
 35  \w     44.00  70.00   0.50    8.00    --   66.00  76.00  47.85   52
 36  \w     47.00  73.00   0.50    8.00    --   66.00  75.00 -70.93   52
 37  \w     45.00  71.00   0.50    8.00    --   66.00  77.00 -49.04   52
 38  \w     45.00  75.00   0.50    8.00    --   66.00  74.00 -11.63   60
 39  \w     50.00  91.00   0.50    8.00    --   70.00  77.00  66.68   82
 40  \w    -87.00 -54.00   0.50    8.00    --  -74.00 -73.00  85.93   66
 41  \w    -90.00 -53.00   0.50    8.00    --  -74.00 -72.00 104.47   74
 42  \w    -90.00 -54.00   0.50    8.00    --  -74.00 -73.00-175.45   72
 43  \w    -85.00 -57.00   0.50    8.00    --  -78.00 -73.00-149.77   56
 44  \w    -83.00 -57.00   0.50    8.00    --  -78.00 -72.00 159.99   52
 45  \w    -84.00 -58.00   0.50    8.00    --  -78.00 -73.00 -36.97   52
 46  \w   -100.00 -62.00   0.50    8.00    --  -82.00 -71.00  67.92   76
 47  \w    -87.00 -61.00   0.50    8.00    --  -82.00 -73.00  14.67   52
 48  \w    -91.00 -61.00   0.50    8.00    --  -82.00 -72.00 137.25   60
 49  \w    -86.00 -60.00   0.50    8.00    --  -82.00 -74.00  -7.54   52
 50  \w   -155.00-128.00   0.50    8.00    --  -86.00 -72.00   3.96   54
 51  \w    -95.00 -64.00   0.50    8.00    --  -86.00 -75.00  39.92   62
 52  \w    -90.00 -64.00   0.50    8.00    --  -86.00 -74.00 -80.82   52
 53  \w    -96.00 -65.00   0.50    8.00    --  -86.00 -73.00-165.68   62
 54  \w    -94.00 -64.00   0.50    8.00    --  -86.00 -74.00 -94.97   60
 55  \w   -157.00-131.00   0.50    8.00    --  -86.00 -74.00 -94.97   52
 56  \w    -89.00 -64.00   0.50    8.00    --  -86.00 -75.00-141.09   50
 57  \w    -92.00 -67.00   0.50    8.00    --  -86.00 -72.00   3.96   50
 58  \w   -123.00 -95.00   0.50    8.00    --  -86.00 -72.00   3.96   56
 59  \w   -161.00 -69.00   0.50    8.00    --  -90.00 -72.00 -37.94  184
 60  \w    -99.00 -69.00   0.50    8.00    --  -90.00 -73.00  92.26   60
 61  \w   -101.00 -74.00   0.50    8.00    --  -90.00 -62.00  56.24   54
 62  \w    -98.00 -70.00   0.50    8.00    --  -90.00 -72.00-114.94   56
 63  \w   -111.00 -69.00   0.50    8.00    --  -90.00 -73.00  36.81   84
 64  \w   -145.00-115.00   0.50    8.00    --  -90.00 -73.00  36.81   60
 65  \w    -97.00 -70.00   0.50    8.00    --  -90.00 -72.00-172.35   54
 66  \w   -139.00-113.00   0.50    8.00    --  -90.00 -72.00-114.94   52
 67  \w    -99.00 -73.00   0.50    8.00    --  -90.00 -63.00 -61.51   52
 68  \w   -151.00 -68.00   0.50    8.00    --  -90.00 -74.00 155.63  166
 69  \w   -167.00 -71.00   0.50    8.00    --  -94.00 -76.00 -93.72  192
 70  \w   -140.00 -71.00   0.50    8.00    --  -94.00 -77.00-173.08  138
 71  \w   -141.00-111.00   0.50    8.00    --  -94.00 -67.00  56.40   60
 72  \w   -157.00 -76.00   0.50    8.00    --  -94.00 -66.00 -11.55  162
 73  \w    -98.00 -71.00   0.50    8.00    --  -94.00 -76.00 122.32   54
 74  \w   -164.00-114.00   0.50    8.00    --  -94.00 -76.00 122.32  100
 75  \w   -108.00 -75.00   0.50    8.00    --  -94.00 -67.00  56.40   66
 76  \w    -97.00 -72.00   0.50    8.00    --  -94.00 -75.00-138.86   50
 77  \w   -166.00-111.00   0.50    8.00    --  -94.00 -75.00-138.86  110
 78  \w   -101.00 -75.00   0.50    8.00    --  -94.00 -67.00  99.83   52
 79  \w   -167.00-123.00   0.50    8.00    --  -94.00 -67.00  99.83   88
 80  \w   -105.00 -77.00   0.50    8.00    --  -94.00 -65.00  22.48   56
 81  \w   -162.00-110.00   0.50    8.00    --  -94.00 -65.00  22.48  104
 82  \w   -117.00 -71.00   0.50    8.00    --  -94.00 -76.00 -11.79   92
 83  \w   -169.00 -75.00   0.50    8.00    --  -98.00 -77.00 140.81  188
 84  \w   -173.00 -80.00   0.50    8.00    -- -102.37 -75.00 -51.37  186
 85  \w   -173.00 -83.00   0.50    8.00    -- -102.37 -69.00  63.99  180
 86  \w   -163.00 -85.00   0.50    8.00    -- -102.37 -67.00-153.40  156
 87  \w    -73.00 -34.00   0.50    8.00    -- -102.37  77.00-120.00   78
 88  \w   -108.00 -46.00   0.50    8.00    -- -102.37 108.00 -93.23  124
 89  \w   -106.00 -43.00   0.50    8.00    -- -102.37 125.00 -90.00  126
 90  \w     40.00  68.00   0.50    8.00    --  102.37 -61.00  30.00   56
 91  \w     30.00 104.00   0.50    8.00    --  102.37 -94.00  60.00  148
 92  \w     59.00  87.00   0.50    8.00    --  102.37 -87.00  90.00   56
 93  \w     76.00 103.00   0.50    8.00    --  102.37 -94.00-180.00   54
 94  \w     31.00  71.00   0.50    8.00    --  102.37 -94.00-180.00   80
 95  \w     30.00  80.00   0.50    8.00    --  102.37 -77.00  30.00  100
 96  \w     30.00 102.00   0.50    8.00    --  102.37 -94.00 150.00  144
 97  \w     31.00 106.00   0.50    8.00    --  102.37-125.00  30.00  150
 98  \w     91.00 117.00   0.50    8.00    --  102.37-132.00 166.32   52
 99  \w     49.00  80.00   0.50    8.00    --  102.37-132.00 166.32   62
100  \w     81.00 106.00   0.50    8.00    --  102.37 -95.00 -50.95   50
101  \w     38.00  63.00   0.50    8.00    --  102.37 -95.00 -50.95   50
;
_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      0.0146619000
_diffrn_orient_matrix_UB_12      -0.0447672000
_diffrn_orient_matrix_UB_13      0.0840086000
_diffrn_orient_matrix_UB_21      0.0363317000
_diffrn_orient_matrix_UB_22      -0.0545440000
_diffrn_orient_matrix_UB_23      -0.0513649000
_diffrn_orient_matrix_UB_31      0.1337103000
_diffrn_orient_matrix_UB_32      0.0198672000
_diffrn_orient_matrix_UB_33      0.0488972000
_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  0.1206
_diffrn_reflns_av_unetI/netI     0.0463
_diffrn_reflns_Laue_measured_fraction_full 0.925
_diffrn_reflns_Laue_measured_fraction_max 0.833
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            6014
_diffrn_reflns_point_group_measured_fraction_full 0.925
_diffrn_reflns_point_group_measured_fraction_max 0.833
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.643
_diffrn_reflns_theta_min         3.791
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.044
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30971
_exptl_absorpt_correction_type   gaussian
_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 light yellow'
_exptl_crystal_density_diffrn    1.011
_exptl_crystal_description       block
_exptl_crystal_F_000             1168
_exptl_crystal_size_max          0.092
_exptl_crystal_size_mid          0.078
_exptl_crystal_size_min          0.069
_refine_diff_density_max         0.661
_refine_diff_density_min         -0.645
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.154
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     362
_refine_ls_number_reflns         6014
_refine_ls_number_restraints     70
_refine_ls_restrained_S_all      1.254
_refine_ls_R_factor_all          0.1466
_refine_ls_R_factor_gt           0.1242
_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^)+(0.0884P)^2^+9.9808P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2671
_refine_ls_wR_factor_ref         0.2794
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4939
_reflns_number_total             6014
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02505e2.cif
_cod_data_source_block           GK605
_cod_database_code               7714059
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C36 H48 Si2'
_chemical_oxdiff_usercomment     'Angus for George'
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.910
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9771(19)
 0.0229(19)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C00Y-C00L \\sim C00Z-C00L \\sim C010-C00L \\sim C00X-C00L \\sim C00T-C00L
\\sim C011-C00L
 with sigma of 0.02
 C9-C10 \\sim C10-C11
 with sigma of 0.02
 C00S-C00Q \\sim C10-C00Q \\sim C00W-C00Q \\sim C11-C00Q \\sim C00R-C00Q \\sim
C9-C00Q
 with sigma of 0.02
 C00S-C00W \\sim C00W-C00R
 with sigma of 0.02
 C00R-C00S \\sim C00S-C00W
 with sigma of 0.02
 C5-C00V \\sim C00V-C4
 with sigma of 0.02
 C5A-C2 \\sim C2-C4A
 with sigma of 0.02
 Si01-C4A \\sim Si01-C4 \\sim Si01-C00V \\sim Si01-C2 \\sim Si01-C5A \\sim
Si01-C5
 with sigma of 0.02
 C1A-C3 \\sim C3-C6A
 with sigma of 0.02
 C6-C00U \\sim C00U-C1
 with sigma of 0.02
 Si02-C1A \\sim Si02-C1 \\sim Si02-C6 \\sim Si02-C6A \\sim Si02-C00U \\sim
Si02-C3
 with sigma of 0.02
 C6-C1 \\sim C1-C00U
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C00Z) = Uanis(C010) = Uanis(C00X) = Uanis(C00T) = Uanis(C011) =
Uanis(C00Y)
Uanis(C10) = Uanis(C00W) = Uanis(C11) = Uanis(C00R) = Uanis(C9) = Uanis(C00S)
Uanis(C5) = Uanis(C4A) = Uanis(C4) = Uanis(C2) = Uanis(C00V) = Uanis(C5A)
Uanis(C1A) = Uanis(C1) = Uanis(C3) = Uanis(C00U) = Uanis(C6A) = Uanis(C6)
5. Others
 Sof(C00T)=Sof(H00d)=Sof(H00e)=Sof(H00f)=Sof(C00Y)=Sof(H00m)=Sof(H00n)=
 Sof(H00o)=Sof(C010)=Sof(H01a)=Sof(H01b)=Sof(H01c)=1-FVAR(1)
 Sof(C00X)=Sof(H00j)=Sof(H00k)=Sof(H00l)=Sof(C00Z)=Sof(H00p)=Sof(H00q)=
 Sof(H00r)=Sof(C011)=Sof(H01d)=Sof(H01e)=Sof(H01f)=FVAR(1)
 Sof(C9)=Sof(H9a)=Sof(H9b)=Sof(H9c)=Sof(C10)=Sof(H10a)=Sof(H10b)=Sof(H10c)=
 Sof(C11)=Sof(H11a)=Sof(H11b)=Sof(H11c)=1-FVAR(2)
 Sof(C00R)=Sof(H00y)=Sof(H)=Sof(Ha)=Sof(C00S)=Sof(H00z)=Sof(Hb)=Sof(Hc)=
 Sof(C00W)=Sof(H1)=Sof(Hf)=Sof(Hg)=FVAR(2)
 Sof(C2)=Sof(H2a)=Sof(H2b)=Sof(H2c)=Sof(C5A)=Sof(H5Aa)=Sof(H5Ab)=Sof(H5Ac)=
 Sof(C4A)=Sof(H4Aa)=Sof(H4Ab)=Sof(H4Ac)=1-FVAR(3)
 Sof(C00V)=Sof(H00g)=Sof(H00h)=Sof(H00i)=Sof(C4)=Sof(H4a)=Sof(H4b)=Sof(H4c)=
 Sof(C5)=Sof(H5a)=Sof(H5b)=Sof(H5c)=FVAR(3)
 Sof(C1A)=Sof(H1Aa)=Sof(H1Ab)=Sof(H1Ac)=Sof(C6A)=Sof(H6Aa)=Sof(H6Ab)=Sof(H6Ac)=
 Sof(C3)=Sof(H3a)=Sof(H3b)=Sof(H3c)=1-FVAR(4)
 Sof(C00U)=Sof(H00)=Sof(Hd)=Sof(He)=Sof(C1)=Sof(H1a)=Sof(H1b)=Sof(H1c)=Sof(C6)=
 Sof(H6a)=Sof(H6b)=Sof(H6c)=FVAR(4)
6.a Aromatic/amide H refined with riding coordinates:
 C006(H006), C007(H007), C009(H009), C00G(H00s), C00H(H00t), C00I(H00u)
6.b Idealised Me refined as rotating group:
 C00D(H00a,H00b,H00c), C00K(H00v,H00w,H00x), C00R(H00y,H,Ha), C00S(H00z,Hb,Hc),
  C00T(H00d,H00e,H00f), C00U(H00,Hd,He), C00V(H00g,H00h,H00i), C00W(H1,Hf,Hg),
 C00X(H00j,H00k,H00l), C00Y(H00m,H00n,H00o), C00Z(H00p,H00q,H00r), C010(H01a,
 H01b,H01c), C011(H01d,H01e,H01f), C1(H1a,H1b,H1c), C6(H6a,H6b,H6c), C4(H4a,H4b,
 H4c), C5(H5a,H5b,H5c), C9(H9a,H9b,H9c), C10(H10a,H10b,H10c), C11(H11a,H11b,
 H11c), C2(H2a,H2b,H2c), C5A(H5Aa,H5Ab,H5Ac), C4A(H4Aa,H4Ab,H4Ac), C1A(H1Aa,
 H1Ab,H1Ac), C6A(H6Aa,H6Ab,H6Ac), C3(H3a,H3b,H3c)
;
_shelx_res_checksum              50690
_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 2.237
_oxdiff_exptl_absorpt_empirical_full_min 0.420