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_7121415
_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
'C31 H28 N P, 2(B F4), 0.5(C H2 Cl2), 0.25(O)'
_chemical_formula_sum            'C31.5 H28 B2 Cl F8 N O0.25 P'
_chemical_formula_weight         664.59
_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             2015-01-28
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2017-05-07 deposited with the CCDC.
2018-03-20 downloaded from the CCDC.
;
_cell_angle_alpha                107.395(2)
_cell_angle_beta                 100.184(2)
_cell_angle_gamma                106.684(2)
_cell_formula_units_Z            2
_cell_length_a                   9.2290(7)
_cell_length_b                   12.4861(7)
_cell_length_c                   15.3456(7)
_cell_measurement_reflns_used    7012
_cell_measurement_temperature    173
_cell_measurement_theta_max      54.89
_cell_measurement_theta_min      6.29
_cell_volume                     1548.27(17)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      173
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.992
_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  0.0500
_diffrn_reflns_av_unetI/netI     0.0718
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            15215
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.483
_diffrn_reflns_theta_min         3.147
_exptl_absorpt_coefficient_mu    0.248
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.2629
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.426
_exptl_crystal_description       block
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.477
_refine_diff_density_min         -0.806
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.146
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     511
_refine_ls_number_reflns         7031
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.1568
_refine_ls_R_factor_gt           0.0838
_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^)+(0.1409P)^2^+0.9087P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2123
_refine_ls_wR_factor_ref         0.3042
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3543
_reflns_number_total             7031
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc00758f2.cif
_cod_data_source_block           1_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7121414--7121417.cif.'
_cod_original_cell_volume        1548.27(16)
_cod_original_formula_sum        'C31.50 H28 B2 Cl F8 N O0.25 P'
_cod_database_code               7121415
_shelxl_version_number           2013-2
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(F13B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F2B) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(F3C) = Uanis(F3A)
Uanis(F3B) = Uanis(F3A)
Uanis(F4A) = Uanis(F4B)
3. Others
 Fixed Sof: F3A(0.85) F4A(0.85) F2A(0.75) F1A(0.85) Cl1(0.5) F11A(0.4)
 F12A(0.4) F13A(0.4) F11B(0.3) F13B(0.3) F12C(0.3) F12B(0.3) F13C(0.3)
 F11C(0.3) F1B(0.15) F4B(0.15) F3B(0.1) F3C(0.05) F2C(0.1) F2B(0.15) C1s(0.5)
 H1sa(0.5) H1sb(0.5) O2(0.25)
4.a Ternary CH refined with riding coordinates:
 C11(H11)
4.b Secondary CH2 refined with riding coordinates:
 C5(H5a,H5b), C12(H12a,H12b), C13(H13a,H13b), C1s(H1sa,H1sb)
4.c Aromatic/amide H refined with riding coordinates:
 C122(H122), C7(H7), C126(H126), C132(H132), C133(H133), C136(H136),
 C112(H112), C8(H8), C3(H3), C125(H125), C116(H116), C10(H10), C135(H135),
 C9(H9), C2(H2), C123(H123), C113(H113), C124(H124), C134(H134), C115(H115),
 C114(H114)
;
_olex2_submission_special_instructions 'No special instructions were received'