A missing member of conjugated N-heterocycles: realizing pyrido[1,2-α]azepine by reacting ruthenium alkenylcarbene complex with alkyne.
Zhou, Xiaoxi; Huang, Fanping; Tang, Chun; Zhuo, Qingde; Chen, Zhixin; Zhang, Hong; Xia, Haiping; Chemical communications (Cambridge, England) 54 (2018) 4009–4012; doi:10.1039/c8cc00758f

data_7121416
_publ_section_title
;
 A missing member of conjugated N-heterocycles: realizing
 pyrido[1,2-\a]azepine by reacting ruthenium alkenylcarbene complex with
 alkyne.
;
_journal_issue                   32
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              4009
_journal_page_last               4012
_journal_paper_doi               10.1039/c8cc00758f
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety
'C62 H54 Cl3 N2 P2 Ru2, 3(B F4), C2 H4 Cl2, 0.5(C H4 O), 1.5(O)'
_chemical_formula_sum            'C64.5 H60 B3 Cl5 F12 N2 O2 P2 Ru2'
_chemical_formula_weight         1596.90
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_audit_creation_date             2017-05-07
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_audit_update_record
;
2017-05-07 deposited with the CCDC.
2018-03-20 downloaded from the CCDC.
;
_cell_angle_alpha                84.684(2)
_cell_angle_beta                 67.829(2)
_cell_angle_gamma                74.648(2)
_cell_formula_units_Z            2
_cell_length_a                   13.9016(3)
_cell_length_b                   15.3374(4)
_cell_length_c                   17.6017(5)
_cell_measurement_reflns_used    13983
_cell_measurement_temperature    100.01
_cell_measurement_theta_max      29.2970
_cell_measurement_theta_min      3.8340
_cell_volume                     3351.33(16)
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      100.01
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'multiwire proportional'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0340
_diffrn_reflns_av_unetI/netI     0.0450
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            26045
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         3.305
_exptl_absorpt_coefficient_mu    0.776
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66261
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.582
_exptl_crystal_description       block
_exptl_crystal_F_000             1606
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.908
_refine_diff_density_min         -1.247
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     849
_refine_ls_number_reflns         11764
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0576
_refine_ls_R_factor_gt           0.0469
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0729P)^2^+6.3494P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1280
_refine_ls_wR_factor_ref         0.1363
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9943
_reflns_number_total             11764
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc00758f2.cif
_cod_data_source_block           1_CCDC2
_cod_depositor_comments
'Adding full bibliography for 7121414--7121417.cif.'
_cod_original_formula_sum        'C64.50 H60 B3 Cl5 F12 N2 O2 P2 Ru2'
_cod_database_code               7121416
_shelx_shelxl_version_number     2014/7
_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, All O(H) groups
2. Restrained distances
 O3-C0AA
 1.35 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: O3(0.5) H3B(0.5) C0AA(0.5) H0AA(0.5) H0AB(0.5) H0AC(0.5) O1(0.5)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C5A(H5A), C11A(H11A), C3A(H3A), C2A(H2A), C11(H11), C5(H5), C3(H3)
5.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C12(H12A,H12B), C12A(H12C,H12D), C13A(H13C,H13D), C2S(H2SA,
 H2SB), C1S(H1SA,H1SB)
5.c Aromatic/amide H refined with riding coordinates:
 C222(H222), C216(H216), C215(H215), C112(H112), C236(H236), C135(H135),
 C122(H122), C8A(H8A), C232(H232), C126(H126), C226(H226), C7A(H7A), C10(H10),
 C214(H214), C136(H136), C9(H9), C225(H225), C125(H125), C123(H123), C212(H212),
  C8(H8), C10A(H10A), C213(H213), C7(H7), C235(H235), C9A(H9A), C224(H224),
 C223(H223), C132(H132), C234(H234), C233(H233), C133(H133), C134(H134),
 C124(H124), C113(H113), C116(H116), C114(H114), C115(H115)
5.d Idealised Me refined as rotating group:
 C0AA(H0AA,H0AB,H0AC)
5.e Idealised tetrahedral OH refined as rotating group:
 O3(H3B)
;
_olex2_submission_special_instructions 'No special instructions were received'