Wavelength-dependent rearrangements of an α-dione chromophore: a chemical pearl in a bis(hypersilyl) oyster.
Glotz, Gabriel; Drusgala, Manfred; Hamm, Florian; Fischer, Roland C.; Došlić, Nađa; Kelterer, Anne-Marie; Gescheidt, Georg; Haas, Michael; Chemical science 15 (2024) 4427–4433; doi:10.1039/d4sc00064a

data_1571016
_publ_section_title
;
 Wavelength-dependent rearrangements of an &#x3b1;-dione chromophore: a
 chemical pearl in a bis(hypersilyl) oyster.
;
_journal_issue                   12
_journal_name_full               'Chemical science'
_journal_page_first              4427
_journal_page_last               4433
_journal_paper_doi               10.1039/d4sc00064a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C20 H54 O2 Si8'
_chemical_formula_sum            'C20 H54 O2 Si8'
_chemical_formula_weight         551.35
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-01-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2023-02-15 deposited with the CCDC.	2024-02-14 downloaded from the CCDC.
;
_cell_angle_alpha                93.065(3)
_cell_angle_beta                 108.756(3)
_cell_angle_gamma                118.620(3)
_cell_formula_units_Z            1
_cell_length_a                   9.2895(6)
_cell_length_b                   9.5681(6)
_cell_length_c                   12.3723(7)
_cell_measurement_reflns_used    9879
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.463
_cell_measurement_theta_min      2.504
_cell_volume                     885.12(10)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.8
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0640
_diffrn_reflns_av_unetI/netI     0.0482
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            34665
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        25.999
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         2.504
_diffrn_source_current           0.86
_diffrn_source_power             0.043
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.317
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5270
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1437 before and 0.0756 after correction.
The Ratio of minimum to maximum transmission is 0.7068.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.034
_exptl_crystal_description       plate
_exptl_crystal_F_000             302
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.541
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.5(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     474
_refine_ls_number_reflns         6621
_refine_ls_number_restraints     312
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0803
_refine_ls_R_factor_gt           0.0592
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0771P)^2^+1.1424P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1456
_refine_ls_wR_factor_ref         0.1631
_reflns_Friedel_coverage         0.909
_reflns_Friedel_fraction_full    0.907
_reflns_Friedel_fraction_max     0.907
_reflns_number_gt                5226
_reflns_number_total             6621
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00064a3.cif
_cod_data_source_block           rf1671c_0m
_cod_depositor_comments
'Adding full bibliography for 1571016--1571017.cif.'
_cod_database_code               1571016
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.951
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5(4)
 0.5(4)
2. Fixed Uiso
 At 1.2 times of:
  {H14A,H14B,H14C} of C14, {H5A,H5B,H5C} of C5, {H10A,H10B,H10C} of C10
 At 1.5 times of:
  {H11A,H11B,H11C} of C11, {H18A,H18B,H18C} of C18, {H4A,H4B,H4C} of C4, {H8A,
  H8B,H8C} of C8, {H9A,H9B,H9C} of C9, {H19A,H19B,H19C} of C19, {H6A,H6B,H6C}
  of C6, {H20A,H20B,H20C} of C20, {H7A,H7B,H7C} of C7, {H13A,H13B,H13C} of C13,
  {H12A,H12B,H12C} of C12, {H13D,H13E,H13F} of C13A, {H18D,H18E,H18F} of C18A,
  {H20D,H20E,H20F} of C20A, {H12D,H12E,H12F} of C12A, {H19D,H19E,H19F} of C19A,
  {H15D,H15E,H15F} of C15A, {H17D,H17E,H17F} of C17A, {H6AA,H6AB,H6AC} of C6A,
  {H7AA,H7AB,H7AC} of C7A, {H9AA,H9AB,H9AC} of C9A, {H10D,H10E,H10F} of C10A,
  {H11D,H11E,H11F} of C11A, {H8AA,H8AB,H8AC} of C8A, {H16D,H16E,H16F} of C16A,
  {H14D,H14E,H14F} of C14A, {H3A,H3B,H3C} of C3, {H17A,H17B,H17C} of C17, {H16A,
  H16B,H16C} of C16, {H15A,H15B,H15C} of C15
3. Restrained distances
 Si6-C9A = Si6-C10A = Si6-C11A = Si6-C12 = Si6-C13 = Si6-C14
 1.86 with sigma of 0.01
 O1-C1 \\sim O1A-C1A
 with sigma of 0.01
 C1-C2 \\sim C1A-C2A
 with sigma of 0.01
 O2A-C2A \\sim C2-O2
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Si2 \\sim C17A \\sim C3 \\sim C15A \\sim C5 \\sim C16A \\sim C4: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
Si1 \\sim O1 \\sim O1A \\sim Si5: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C15) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C3)
\\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C4) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C10)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C7) \\sim Ueq,
Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C1A) \\sim Ueq,
Uanis(C2A) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C17A)
\\sim Ueq, Uanis(C20A) \\sim Ueq, Uanis(C19A) \\sim Ueq, Uanis(C18A) \\sim Ueq,
Uanis(C12A) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C6A)
\\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C9A) \\sim Ueq,
Uanis(C10A) \\sim Ueq, Uanis(C11A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C7) \\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C12A) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C20A) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(Si3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Si6) = Uanis(C11A) = Uanis(C14) = Uanis(Si6) = Uanis(C9A)
Uanis(Si3) = Uanis(C13A)
5. Others
 Sof(Si8A)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C19A)=Sof(H19D)=
 Sof(H19E)=Sof(H19F)=Sof(Si3A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=
 Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13A)=Sof(H13D)=Sof(H13E)=
 Sof(H13F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=
 Sof(H6AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=
 Sof(H7AC)=1-FVAR(1)
 Sof(Si4)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C11)=Sof(H11A)=Sof(H11B)=
 Sof(H11C)=Sof(Si8)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C6)=Sof(H6A)=
 Sof(H6B)=Sof(H6C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(H7C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(1)
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=
 Sof(H15F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(2)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(2)
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=Sof(C11A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=1-FVAR(3)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(3)
 Sof(C1A)=Sof(O2A)=Sof(C2A)=Sof(O1A)=1-FVAR(4)
 Sof(O1)=Sof(C1)=Sof(O2)=Sof(C2)=FVAR(4)
6.a Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C3(H3A,H3B,
 H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C),
 C10(H10A,H10B,H10C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C7(H7A,H7B,H7C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C18(H18A,H18B,H18C), C13(H13A,H13B,
 H13C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C16A(H16D,H16E,H16F),
 C15A(H15D,H15E,H15F), C17A(H17D,H17E,H17F), C20A(H20D,H20E,H20F), C19A(H19D,
 H19E,H19F), C18A(H18D,H18E,H18F), C12A(H12D,H12E,H12F), C13A(H13D,H13E,H13F),
 C14A(H14D,H14E,H14F), C6A(H6AA,H6AB,H6AC), C8A(H8AA,H8AB,H8AC), C7A(H7AA,H7AB,
 H7AC), C9A(H9AA,H9AB,H9AC), C10A(H10D,H10E,H10F), C11A(H11D,H11E,H11F)
;
_shelx_res_checksum              3628
_olex2_submission_special_instructions 'No special instructions were received'