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_7714060
_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         'C64 H69 Br P2 Ru'
_chemical_formula_sum            'C64 H69 Br P2 Ru'
_chemical_formula_weight         1081.11
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_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                   31.4242(14)
_cell_length_b                   19.2612(9)
_cell_length_c                   8.9346(7)
_cell_measurement_reflns_used    6837
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.6690
_cell_measurement_theta_min      2.7770
_cell_volume                     5407.8(5)
_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 0.999
_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   -117.00 -43.00   0.50   10.00    --  -45.98-174.00 -63.00  148
  2  \w   -119.00 -37.00   0.50   10.00    --  -45.98 174.00 -53.00  164
  3  \w    -87.00  -5.00   0.50   10.00    --  -45.98 114.00 166.00  164
  4  \w      5.00  88.00   0.50   10.00    --   45.98-114.00  76.00  166
  5  \w     37.00 119.00   0.50   10.00    --   45.98-174.00 -63.00  164
  6  \w     43.00 118.00   0.50   10.00    --   45.98 174.00 -53.00  150
  7  \w   -144.00 -94.00   0.50   80.00    -- -102.37-174.00 -63.00  100
  8  \w   -107.00 -62.00   0.50   80.00    -- -102.37 114.00 166.00   90
  9  \w   -147.00 -81.00   0.50   80.00    -- -102.37-114.00  76.00  132
 10  \w   -116.00 -91.00   0.50   80.00    -- -102.37 174.00 -53.00   50
 11  \w    114.00 140.00   0.50   80.00    --  102.37 114.00 166.00   52
 12  \w     52.00 109.00   0.50   80.00    --  102.37-114.00  76.00  114
 13  \w   -118.00 -75.00   0.50   10.00    --  -45.98-125.00-180.00   86
 14  \w    -25.00  30.00   0.50   10.00    --  -45.98  19.00  30.00  110
 15  \w   -118.00 -81.00   0.50   10.00    --  -45.98-125.00 150.00   74
 16  \w     75.00 103.00   0.50   10.00    --   45.98 125.00  30.00   56
 17  \w    -27.00  22.00   0.50   10.00    --   45.98 -19.00 150.00   98
 18  \w   -100.00 -32.00   0.50   80.00    -- -102.37  77.00-180.00  136
 19  \w    -73.00 -31.00   0.50   80.00    -- -102.37  61.00 120.00   84
 20  \w    -73.00 -45.00   0.50   80.00    -- -102.37  61.00   0.00   56
 21  \w   -106.00 -33.00   0.50   80.00    -- -102.37  77.00 150.00  146
 22  \w   -176.00 -91.00   0.50   80.00    -- -102.37 -30.00 -90.00  170
 23  \w    -63.00 -37.00   0.50   80.00    -- -102.37  61.00 150.00   52
 24  \w   -171.00 -97.00   0.50   80.00    -- -102.37 -15.00 -30.00  148
 25  \w    -73.00 -48.00   0.50   80.00    -- -102.37  61.00 -60.00   50
 26  \w     35.00  64.00   0.50   80.00    --  102.37 -61.00-150.00   58
 27  \w     31.00  68.00   0.50   80.00    --  102.37 -61.00   0.00   74
;
_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      -0.0203175000
_diffrn_orient_matrix_UB_12      0.0603079000
_diffrn_orient_matrix_UB_13      0.0877698000
_diffrn_orient_matrix_UB_21      -0.0203235000
_diffrn_orient_matrix_UB_22      0.0272647000
_diffrn_orient_matrix_UB_23      -0.1457067000
_diffrn_orient_matrix_UB_31      -0.0397300000
_diffrn_orient_matrix_UB_32      -0.0447222000
_diffrn_orient_matrix_UB_33      0.0294212000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1562
_diffrn_reflns_av_unetI/netI     0.1098
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            46934
_diffrn_reflns_point_group_measured_fraction_full 0.930
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        66.588
_diffrn_reflns_theta_max         66.587
_diffrn_reflns_theta_min         2.691
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.058
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75191
_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 black'
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_description       block
_exptl_crystal_F_000             2248
_exptl_crystal_size_max          0.066
_exptl_crystal_size_mid          0.045
_exptl_crystal_size_min          0.024
_refine_diff_density_max         1.706
_refine_diff_density_min         -1.672
_refine_diff_density_rms         0.117
_refine_ls_abs_structure_details
;
 Flack x determined using 1652 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.012(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     557
_refine_ls_number_reflns         8865
_refine_ls_number_restraints     296
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.1506
_refine_ls_R_factor_gt           0.1109
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+56.8036P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1883
_refine_ls_wR_factor_ref         0.2048
_reflns_Friedel_coverage         0.739
_reflns_Friedel_fraction_full    0.850
_reflns_Friedel_fraction_max     0.850
_reflns_number_gt                6320
_reflns_number_total             8865
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02505e2.cif
_cod_data_source_block           gk602
_cod_database_code               7714060
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C64 H69 Br1 P2 Ru1'
_chemical_oxdiff_usercomment     'Angus 4th atttempt '
_shelx_estimated_absorpt_t_max   0.909
_shelx_estimated_absorpt_t_min   0.776
_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
 Br00-C01G \\sim Br01-C01K
 with sigma of 0.02
 C1-C01{ \\sim C01Z-C01O \\sim C3A-C2 \\sim C3-C01R
 with sigma of 0.02
 C1-C01C \\sim C01R-C01C \\sim C1-C00L \\sim C01R-C00L \\sim C2-C00G \\sim
C01O-C00G \\sim C01O-C00I ~
 C2-C00I
 with sigma of 0.02
 C4-C01Q \\sim C01Y-C01Q \\sim C01W-C01Q \\sim C01V-C01Q \\sim C5-C01Q \\sim
C01U-C01Q
 with sigma of 0.02
 C01W-C5 \\sim C5-C4
 with sigma of 0.02
 C4-C01W \\sim C01W-C5
 with sigma of 0.02
 C01Y-C01U \\sim C01U-C01V
 with sigma of 0.02
 C01U-C01V \\sim C01V-C01Y
 with sigma of 0.02
 C01V-C01Y \\sim C01Y-C01U
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Br01) = Uanis(Br00)
Uanis(C01O) = Uanis(C2) = Uanis(C1) = Uanis(C01R)
Uanis(C01{) = Uanis(C01Z) = Uanis(C3) = Uanis(C3A)
Uanis(C01D) = Uanis(C010) = Uanis(C00Z) = Uanis(C017) = Uanis(C019)
Uanis(C01B) = Uanis(C00V) = Uanis(C00S) = Uanis(C01X) = Uanis(C00T)
Uanis(P003) = Uanis(C00P) = Uanis(P002) = Uanis(C00Y)
Uanis(C01Q) = Uanis(C01H)
Uanis(C01W) = Uanis(C01V)
Uanis(C5) = Uanis(C01U)
Uanis(C01Y) = Uanis(C4)
Uanis(C01Y) = Uanis(C4) = Uanis(C01U) = Uanis(C5) = Uanis(C01V) = Uanis(C01W)
Uanis(C01Q) = Uanis(C01Y) = Uanis(C4) = Uanis(C01W) = Uanis(C01V) = Uanis(C01U)
= Uanis(C5)
4. Rigid body (RIGU) restrains
 C008, C014, C00W, C00Q, C01P, C00R
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C01L, C01E, C01F, C012, C00X, C00U
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C00M, C015, C01I, C01N, C018, C00J
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C00A, C005, C00N, C00K, C00C, C007
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P003, C00Y, C00P, P002
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C00G, C006, C00H, C00E, C00I, C00O, C009, C00L, C01C, C011, C01J, C00D, C01K,
 C01G
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Br01)=Sof(H01I)=1-FVAR(1)
 Sof(Br00)=Sof(H01K)=FVAR(1)
 Sof(C1)=Sof(C2)=1-FVAR(2)
 Sof(C01O)=Sof(C01R)=FVAR(2)
 Sof(C01{)=Sof(H2)=Sof(HG)=Sof(HH)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=1-
 FVAR(3)
 Sof(C01Z)=Sof(H1)=Sof(HE)=Sof(HF)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=FVAR(3)
 Sof(C01W)=Sof(H3)=Sof(HI)=Sof(HJ)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=1-FVAR(4)
 Sof(C01U)=Sof(H01U)=Sof(H01V)=Sof(H01W)=Sof(C01V)=Sof(H01X)=Sof(H01Y)=Sof(H)=
 Sof(C01Y)=Sof(H01)=Sof(HC)=Sof(HD)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C00P(H00A,H00B), C00Y(H00U,H00V)
6.b Aromatic/amide H refined with riding coordinates:
 C005(H005), C006(H006), C007(H007), C00C(H00C), C00D(H00D), C00E(H00E),
 C00K(H00K), C00M(H00M), C00N(H00N), C00O(H00O), C00Q(H00Q), C00R(H00R),
 C00W(H00W), C00X(H00X), C011(H011), C012(H012), C014(H014), C015(H015),
 C018(H018), C01E(H01G), C01F(H01H), C01G(H01I), C01I(H01J), C01K(H01K),
 C01L(H01L), C01N(H01P), C01P(H01Q)
6.c Idealised Me refined as rotating group:
 C00S(H00F,H00G,H00H), C00T(H00I,H00J,H00L), C00V(H00P,H00S,H00T), C016(H01A,
 H01B,H01C), C01B(H01D,H01E,H01F), C01M(H01M,H01N,H01O), C01S(H01R,H01S,H01T),
 C01U(H01U,H01V,H01W), C01V(H01X,H01Y,H), C01X(H01Z,HA,HB), C01Y(H01,HC,HD),
 C01Z(H1,HE,HF), C3(H3A,H3B,H3C), C01{(H2,HG,HH), C3A(H3AA,H3AB,H3AC), C01W(H3,
 HI,HJ), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C)
;
_shelx_res_checksum              34079
_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 1.956
_oxdiff_exptl_absorpt_empirical_full_min 0.534