Planar-chiral arene ruthenium complexes: synthesis, separation of enantiomers, and application for catalytic C-H activation.
Boym, Mikhail A.; Pototskiy, Roman A.; Podyacheva, Evgeniya S.; Chusov, Denis A.; Nelyubina, Yulia V.; Perekalin, Dmitry S.; Chemical communications (Cambridge, England) 60 (2024) 4491–4494; doi:10.1039/d4cc00181h

data_7132894
_publ_section_title
;
 Planar-chiral arene ruthenium complexes: synthesis, separation of
 enantiomers, and application for catalytic C-H activation.
;
_journal_issue                   33
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              4491
_journal_page_last               4494
_journal_paper_doi               10.1039/d4cc00181h
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H19 Br N2 O2'
_chemical_formula_sum            'C15 H19 Br N2 O2'
_chemical_formula_weight         339.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-08
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2024-01-08 deposited with the CCDC.	2024-03-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.623(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.049(3)
_cell_length_b                   11.480(5)
_cell_length_c                   19.450(8)
_cell_measurement_reflns_used    4390
_cell_measurement_temperature    220
_cell_measurement_theta_max      21.24
_cell_measurement_theta_min      2.76
_cell_volume                     1556.2(11)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      220.00
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEXII Quazar'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0931
_diffrn_reflns_av_unetI/netI     0.1114
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            24861
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.999
_diffrn_reflns_theta_min         2.118
_exptl_absorpt_coefficient_mu    2.645
_exptl_absorpt_correction_T_max  0.3359
_exptl_absorpt_correction_T_min  0.2161
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1281 before and 0.0743 after correction.
The Ratio of minimum to maximum transmission is 0.6433.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.448
_exptl_crystal_description       needle
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.538
_refine_diff_density_min         -0.655
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Flack x determined using 1159 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.049(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     394
_refine_ls_number_reflns         6497
_refine_ls_number_restraints     43
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.1548
_refine_ls_R_factor_gt           0.0679
_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^)+(0.0161P)^2^+3.5013P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1185
_refine_ls_wR_factor_ref         0.1504
_reflns_Friedel_coverage         0.837
_reflns_Friedel_fraction_full    0.949
_reflns_Friedel_fraction_max     0.922
_reflns_number_gt                3457
_reflns_number_total             6497
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc00181h3.cif
_cod_data_source_block           8hMe
_cod_depositor_comments
'Adding full bibliography for 7132893--7132895.cif.'
_cod_original_cell_volume        1556.1(11)
_cod_database_code               7132894
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.879
_shelx_estimated_absorpt_t_min   0.778
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C15-C12 \\sim C15'-C12
 with sigma of 0.02
 C15"-C12A \\sim C15A-C12A
 with sigma of 0.02
 C14"-C12A \\sim C14A-C12A
 with sigma of 0.02
 C13A-C12A \\sim C13"-C12A
 with sigma of 0.02
 C13-C12 \\sim C13'-C12
 with sigma of 0.02
 C14'-C12 \\sim C14-C12
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C13A) \\sim Ueq, Uanis(C15") \\sim Ueq, Uanis(C14") \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
Uanis(C15) \\sim Ueq, Uanis(C13') \\sim Ueq, Uanis(C14') \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
Uanis(C15) = Uanis(C15')
Uanis(C13A) = Uanis(C13")
Uanis(C14") = Uanis(C14A)
Uanis(C15") = Uanis(C15A)
Uanis(C14) = Uanis(C14')
Uanis(C13') = Uanis(C13)
4. Others
 Sof(C13")=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14")=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(C15")=Sof(H15A)=Sof(H15B)=Sof(H15C)=1-FVAR(1)
 Sof(C13A)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14A)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=FVAR(1)
 Sof(C13')=Sof(H13J)=Sof(H13K)=Sof(H13L)=Sof(C15')=Sof(H15J)=Sof(H15K)=
 Sof(H15L)=Sof(C14')=Sof(H14J)=Sof(H14K)=Sof(H14L)=1-FVAR(2)
 Sof(C15)=Sof(H15G)=Sof(H15H)=Sof(H15I)=Sof(C14)=Sof(H14G)=Sof(H14H)=Sof(H14I)=
 Sof(C13)=Sof(H13G)=Sof(H13H)=Sof(H13I)=FVAR(2)
5.a Riding coordinates:
 N4A(H4AA), N2(H2)
5.b Ternary CH refined with riding coordinates:
 C1A(H1A), C1(H1)
5.c Secondary CH2 refined with riding coordinates:
 C9A(H9AA,H9AB), C9(H9A,H9B)
5.d Me refined with riding coordinates:
 C15'(H15J,H15K,H15L)
5.e Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C5A(H5A), C7A(H7A), C4(H4), C5(H5), C7(H7)
5.f Idealised Me refined as rotating group:
 C10A(H10A,H10B,H10C), C13A(H13A,H13B,H13C), C13"(H13D,H13E,H13F), C14"(H14A,
 H14B,H14C), C14A(H14D,H14E,H14F), C15"(H15A,H15B,H15C), C15A(H15D,H15E,H15F),
 C15(H15G,H15H,H15I), C10(H10D,H10E,H10F), C14(H14G,H14H,H14I), C13(H13G,H13H,
 H13I), C13'(H13J,H13K,H13L), C14'(H14J,H14K,H14L)
;
_shelx_res_checksum              46371
_shelx_hkl_checksum              50326
_olex2_submission_special_instructions 'No special instructions were received'