Electronically and sterically varied tungsten carbonyls applied to the selective dearomatization of N-heteroarenes.
Bai, Pengtao; Liu, Yuzan; Fang, Li; Li, Ying; Wang, Jiahao; Cai, Yougen; Chen, Lei; Zhao, Jia-Jia; Song, Heng; Zong, Luyi; Xu, Chen; Dalton transactions (Cambridge, England : 2003) 55 (2026) 3454–3459; doi:10.1039/d6dt00164e

data_7720057
_publ_section_title
;
 Electronically and sterically varied tungsten carbonyls applied to the
 selective dearomatization of N-heteroarenes.
;
_journal_issue                   8
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3454
_journal_page_last               3459
_journal_paper_doi               10.1039/d6dt00164e
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C22 H22 N2 O4 W'
_chemical_formula_sum            'C22 H22 N2 O4 W'
_chemical_formula_weight         562.26
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-11
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-06-12 deposited with the CCDC.	2026-01-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.0109(8)
_cell_length_b                   15.0108(8)
_cell_length_c                   19.9307(10)
_cell_measurement_reflns_used    7216
_cell_measurement_temperature    300.00
_cell_measurement_theta_max      27.02
_cell_measurement_theta_min      3.20
_cell_volume                     4490.9(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker D8 Venture diffractrometer'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      300.00
_diffrn_detector                 'CCD area detector'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            23229
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.564
_diffrn_reflns_theta_min         2.804
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.172
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6200
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0541 before and 0.0265 after correction.
The Ratio of minimum to maximum transmission is 0.8315.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'blackish violet'
_exptl_crystal_colour_modifier   blackish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.663
_exptl_crystal_description       block
_exptl_crystal_F_000             2192
_exptl_crystal_recrystallization_method
'The crystals were growth by means of evaporation of a mixture of n-hexane and toluene at RT.'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.717
_refine_diff_density_min         -0.530
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         5087
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0433
_refine_ls_R_factor_gt           0.0233
_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/[\s^2^(Fo^2^)+(0.0232P)^2^+2.3425P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0483
_refine_ls_wR_factor_ref         0.0555
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3701
_reflns_number_total             5087
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00164e2.cif
_cod_data_source_block           el
_cod_depositor_comments
'Adding full bibliography for 7720057--7720059.cif.'
_cod_database_code               7720057
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.576
_shelx_estimated_absorpt_t_min   0.511
_exptl_crystal_mounting_method
'Crystals were removed from the crystallisation vial and immediately coated with polybutenes oil (CAS: 9003-29-6) on a glass slide. A suitable single crystal coated with polybutenes oil was sealed in capillary tube filled with argon. The capillary tube with single crystal was mounted on copper pin with solid paraffin.'
_olex2_refinement_description
;
1. Restrained distances
 C18A-C17 = C18-C17 = C19-C17 = C19A-C17 = C22-C20 = C22A-C20 = C21-C20 = C21A-
 C20
 1.54 with sigma of 0.01
 C22-C21 = C22A-C21A = C18-C19 = C19A-C18A
 2.515 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
C21 \\sim C22 \\sim C21A \\sim C22A \\sim C18 \\sim C19 \\sim C18A \\sim C19A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Rigid body (RIGU) restrains
 C20, C21, C22, C21A, C22A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C17, C18, C19, C18A, C19A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Others
 Sof(H17A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=
 Sof(H19E)=Sof(H19F)=1-FVAR(1)
 Sof(H17)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=
 Sof(H19C)=FVAR(1)
 Sof(H20A)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22A)=Sof(H22D)=
 Sof(H22E)=Sof(H22F)=1-FVAR(2)
 Sof(H20)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C17(H17), C17(H17A), C20(H20), C20(H20A)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C13(H13), C14(H14), C15(H15)
5.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C18A(H18D,H18E,H18F), C19A(H19D,H19E,H19F), C21A(H21D,H21E,H21F),
 C22A(H22D,H22E,H22F)
;
_shelx_res_checksum              94064
_olex2_submission_special_instructions 'No special instructions were received'