Trimerisation of carbon suboxide at a di-titanium centre to form a pyrone ring system.
Tsoureas, Nikolaos; Green, Jennifer C.; Cloke, F Geoffrey N; Puschmann, Horst; Roe, S. Mark; Tizzard, Graham; Chemical science 9 (2018) 5008–5014; doi:10.1039/c8sc01127c

data_1549388
_publ_section_title
;
 Trimerisation of carbon suboxide at a di-titanium centre to form a pyrone
 ring system.
;
_journal_issue                   22
_journal_name_full               'Chemical science'
_journal_page_first              5008
_journal_page_last               5014
_journal_paper_doi               10.1039/c8sc01127c
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         'C113 H184 O6 Si8 Ti4'
_chemical_formula_sum            'C113 H184 O6 Si8 Ti4'
_chemical_formula_weight         2054.91
_chemical_name_common            2
_chemical_name_systematic        2
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-12-20
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2017.12.08 svn.r3473 for OlexSys, GUI svn.r5356)
;
_audit_update_record
;
2018-01-15 deposited with the CCDC.
2018-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.2490(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.5653(2)
_cell_length_b                   25.3532(5)
_cell_length_c                   31.1528(4)
_cell_measurement_reflns_used    17449
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      65.6910
_cell_measurement_theta_min      3.3030
_cell_volume                     11501.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'DIRDIFF 2008'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 22.2
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0544
_diffrn_reflns_av_unetI/netI     0.0486
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            67640
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.627
_diffrn_reflns_theta_max         67.627
_diffrn_reflns_theta_min         2.838
_exptl_absorpt_coefficient_mu    3.459
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.35952
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'Light Brown'
_exptl_crystal_density_diffrn    1.187
_exptl_crystal_density_meas      ?
_exptl_crystal_description       Plate
_exptl_crystal_F_000             4440
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-pentane'
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.784
_refine_diff_density_min         -1.472
_refine_diff_density_rms         0.126
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.942
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1362
_refine_ls_number_reflns         20424
_refine_ls_number_restraints     997
_refine_ls_restrained_S_all      0.953
_refine_ls_R_factor_all          0.1441
_refine_ls_R_factor_gt           0.1285
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w={1-exp[-3.0000(sin\q/\l)^2^)]}/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3566
_refine_ls_wR_factor_ref         0.3833
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16144
_reflns_number_total             20424
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01127c2.cif
_cod_data_source_block           2
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_crystal_density_meas' value 'not measured' was changed to '?'
- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 

 Adding full bibliography for 1549388--1549389.cif.
;
_cod_database_code               1549388
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.769
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C14_34) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C21_34) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C9_1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 Si1_43, Si2_43, C1_43, C2_43, C3_43, C4_43, C5_43, C6_43, C7_43, C8_43,
 C11_43, C12_43, C13_43, C14_43, C15_43, C16_43, C17_43, C18_43, C19_43, C21_43,
  C22_43, C23_43, C24_43, C25_43, C26_43, C27_43, C28_43, C29_43
 with sigma for 1-2 distances of -1 and sigma for 1-3 distances of -1
 Si1_34, C14_34, C15_34, C16_34
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O1_2, O2_2, O3_2, O4_2, O5_2, O6_2, C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2,
 C8_2, C9_2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O1_1, O2_1, O3_1, O4_1, O5_1, O6_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1,
 C8_1, C9_1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Si2_34, C21_34, C22_34, C23_34, C24_34, C25_34, C26_34
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Same fragment restrains
{O2_2, O6_2, O5_2, O1_2, O4_2, O3_2, C1_2, C9_2, C5_2, C8_2, C3_2, C7_2, C6_2,
C4_2, C2_2} sigma for 1-2: 0.02, 1-3: 0.02
as
{O1_1, O2_1, O3_1, O4_1, O5_1, O6_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1,
C8_1, C9_1}
{Si1_34, Si2_34, C1_34, C2_34, C3_34, C4_34, C5_34, C6_34, C7_34, C8_34,
C11_34, C12_34, C13_34, C14_34, C15_34, C16_34, C17_34, C18_34, C19_34, C21_34,
C22_34, C23_34, C24_34, C25_34, C26_34, C27_34, C28_34, C29_34} sigma for 1-2:
0.02, 1-3: 0.02
{Si1_21, Si2_21, C1_21, C2_21, C3_21, C4_21, C5_21, C6_21, C7_21, C8_21,
C11_21, C12_21, C13_21, C14_21, C15_21, C16_21, C17_21, C18_21, C19_21, C21_21,
C22_21, C23_21, C24_21, C25_21, C26_21, C27_21, C28_21, C29_21} sigma for 1-2:
0.02, 1-3: 0.02
{Si1_12, Si2_12, C1_12, C2_12, C3_12, C4_12, C5_12, C6_12, C7_12, C8_12,
C11_12, C12_12, C13_12, C14_12, C15_12, C16_12, C17_12, C18_12, C19_12, C21_12,
C22_12, C23_12, C24_12, C25_12, C26_12, C27_12, C28_12, C29_12} sigma for 1-2:
0.02, 1-3: 0.02
as
{Si1_43, Si2_43, C1_43, C2_43, C3_43, C4_43, C5_43, C6_43, C7_43, C8_43,
C11_43, C12_43, C13_43, C14_43, C15_43, C16_43, C17_43, C18_43, C19_43, C21_43,
C22_43, C23_43, C24_43, C25_43, C26_43, C27_43, C28_43, C29_43}
5. Others
 Fixed Sof: O1(0.5) O2(0.5) O3(0.5) O4(0.5) O5(0.5) O6(0.5) C1(0.5) C2(0.5)
 C3(0.5) C4(0.5) C5(0.5) C6(0.5) C7(0.5) C8(0.5) C9(0.5) O1(0.5) O2(0.5)
 O3(0.5) O4(0.5) O5(0.5) O6(0.5) C1(0.5) C2(0.5) C3(0.5) C4(0.5) C5(0.5)
 C6(0.5) C7(0.5) C8(0.5) C9(0.5)
6.a Riding coordinates:
 C22(H22A,H22B,H22C)
6.b Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C17(H17), C21(H21), C24(H24), C27(H27), C11(H11),
 C14(H14), C17(H17), C21(H21), C24(H24), C27(H27), C11(H11), C14(H14), C17(H17),
  C21(H21), C24(H24), C27(H27), C11(H11), C14(H14), C17(H17), C21(H21),
 C24(H24), C27(H27)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C2(H2), C3(H3), C6(H6), C7(H7), C2(H2),
 C3(H3), C6(H6), C7(H7), C2(H2), C3(H3), C6(H6), C7(H7)
6.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C),
 C29(H29A,H29B,H29C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C23(H23A,
 H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C),
 C29(H29A,H29B,H29C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C22(H22A,
 H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C),
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,
 H19B,H19C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C),
 C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              98979
_olex2_submission_original_sample_id suboxide
_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
;