# Electronic Supplementary Material (ESI) for Chemical Science
# This journal is © The Royal Society of Chemistry 2011


data_global
_journal_name_full               'Chemical Science'

_journal_coden_Cambridge         1475
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Dr Jin-Heng Li'
_publ_contact_author_email       jhli@hnu.edu.cn

_publ_section_title              
;
Ruthenium-Catalyzed Intramolecular Carbocyclization
of Alkynes with an sp3 Carbon involving an Oxidative Deprotonation Process

;
loop_
_publ_author_name
'Jin-Heng Li'
'Bo-Xiao Tang'
'Ren-Jie Song'
'Cui-Yan Wu'
;
Zhi-Qiang Wang
;
'Yu Liu'
'Xiao-Cheng Huang'
'Ye-Xiang Xie'

# Attachment '- cd29238.cif'

data_cd29238
_database_code_depnum_ccdc_archive 'CCDC 832462'
#TrackingRef '- cd29238.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C19 H16 N2 O3'
_chemical_formula_weight         320.34

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P2(1)/c

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   10.4908(14)
_cell_length_b                   17.614(2)
_cell_length_c                   9.1784(12)
_cell_angle_alpha                90.00
_cell_angle_beta                 106.541(2)
_cell_angle_gamma                90.00
_cell_volume                     1625.8(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2587
_cell_measurement_theta_min      4.625
_cell_measurement_theta_max      49.880

_exptl_crystal_description       prismatic
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.397
_exptl_crystal_size_mid          0.361
_exptl_crystal_size_min          0.201
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.309
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             672
_exptl_absorpt_coefficient_mu    0.090
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.77427
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8791
_diffrn_reflns_av_R_equivalents  0.0779
_diffrn_reflns_av_sigmaI/netI    0.0613
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.03
_diffrn_reflns_theta_max         25.99
_reflns_number_total             3203
_reflns_number_gt                2286
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0795P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.069(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_number_reflns         3203
_refine_ls_number_parameters     224
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0706
_refine_ls_R_factor_gt           0.0524
_refine_ls_wR_factor_ref         0.1441
_refine_ls_wR_factor_gt          0.1339
_refine_ls_goodness_of_fit_ref   0.984
_refine_ls_restrained_S_all      0.985
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
N1 N 0.97889(14) 0.02729(8) 0.74111(17) 0.0444(4) Uani 1 1 d . . .
N2 N 0.77196(14) 0.19308(8) 0.74524(16) 0.0394(4) Uani 1 1 d D . .
O1 O 0.97570(14) 0.14657(8) 0.64486(17) 0.0610(4) Uani 1 1 d . . .
O2 O 0.75456(14) 0.21497(7) 0.98055(13) 0.0527(4) Uani 1 1 d . . .
O3 O 0.62475(13) 0.06886(7) 1.00526(14) 0.0501(4) Uani 1 1 d . . .
C1 C 0.92876(18) 0.09957(11) 0.71387(19) 0.0428(4) Uani 1 1 d . . .
C2 C 0.81436(16) 0.11723(10) 0.76805(18) 0.0374(4) Uani 1 1 d . . .
C3 C 0.75424(16) 0.06413(10) 0.83167(18) 0.0368(4) Uani 1 1 d . . .
C4 C 0.80916(17) -0.01127(10) 0.85753(18) 0.0392(4) Uani 1 1 d . . .
C5 C 0.75248(19) -0.06926(10) 0.9223(2) 0.0481(5) Uani 1 1 d . . .
H5 H 0.6759 -0.0593 0.9508 0.058 Uiso 1 1 calc R . .
C6 C 0.8070(2) -0.14026(11) 0.9447(2) 0.0573(6) Uani 1 1 d . . .
H6 H 0.7678 -0.1781 0.9880 0.069 Uiso 1 1 calc R . .
C7 C 0.9205(2) -0.15542(11) 0.9029(2) 0.0594(6) Uani 1 1 d . . .
H7 H 0.9581 -0.2036 0.9189 0.071 Uiso 1 1 calc R . .
C8 C 0.9784(2) -0.10067(11) 0.8383(2) 0.0532(5) Uani 1 1 d . . .
H8 H 1.0554 -0.1116 0.8114 0.064 Uiso 1 1 calc R . .
C9 C 0.92295(17) -0.02842(10) 0.81227(19) 0.0415(5) Uani 1 1 d . . .
C10 C 0.74547(17) 0.23802(10) 0.85320(19) 0.0395(4) Uani 1 1 d . . .
C11 C 0.7018(2) 0.31682(11) 0.8048(2) 0.0635(6) Uani 1 1 d . . .
H11A H 0.6121 0.3240 0.8085 0.095 Uiso 1 1 calc R . .
H11B H 0.7061 0.3249 0.7029 0.095 Uiso 1 1 calc R . .
H11C H 0.7592 0.3524 0.8718 0.095 Uiso 1 1 calc R . .
C12 C 0.63055(17) 0.08157(9) 0.8775(2) 0.0395(4) Uani 1 1 d . . .
C13 C 0.51401(17) 0.11080(10) 0.7579(2) 0.0425(4) Uani 1 1 d . . .
C14 C 0.4949(2) 0.09514(12) 0.6067(2) 0.0604(6) Uani 1 1 d . . .
H14 H 0.5588 0.0681 0.5757 0.072 Uiso 1 1 calc R . .
C15 C 0.3798(2) 0.11980(14) 0.4998(3) 0.0756(7) Uani 1 1 d . . .
H15 H 0.3662 0.1091 0.3973 0.091 Uiso 1 1 calc R . .
C16 C 0.2864(2) 0.15996(13) 0.5462(3) 0.0749(7) Uani 1 1 d . . .
H16 H 0.2087 0.1757 0.4751 0.090 Uiso 1 1 calc R . .
C17 C 0.3067(2) 0.17683(14) 0.6951(3) 0.0739(7) Uani 1 1 d . . .
H17 H 0.2441 0.2055 0.7251 0.089 Uiso 1 1 calc R . .
C18 C 0.4184(2) 0.15201(11) 0.8015(3) 0.0570(6) Uani 1 1 d . . .
H18 H 0.4304 0.1628 0.9037 0.068 Uiso 1 1 calc R . .
C19 C 1.09749(19) 0.00912(12) 0.6930(2) 0.0598(6) Uani 1 1 d . . .
H19A H 1.1213 0.0522 0.6422 0.090 Uiso 1 1 calc R . .
H19B H 1.0789 -0.0334 0.6248 0.090 Uiso 1 1 calc R . .
H19C H 1.1698 -0.0033 0.7805 0.090 Uiso 1 1 calc R . .
H2 H 0.7745(19) 0.2166(10) 0.6608(18) 0.051(6) Uiso 1 1 d D . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
N1 0.0369(8) 0.0517(10) 0.0430(9) -0.0037(7) 0.0089(7) 0.0051(7)
N2 0.0461(9) 0.0413(9) 0.0321(8) 0.0033(7) 0.0131(7) 0.0012(7)
O1 0.0554(9) 0.0653(9) 0.0705(10) 0.0166(8) 0.0312(8) 0.0069(7)
O2 0.0805(10) 0.0460(8) 0.0357(7) -0.0015(6) 0.0228(7) -0.0003(6)
O3 0.0544(8) 0.0572(8) 0.0412(8) 0.0032(6) 0.0177(6) -0.0001(6)
C1 0.0396(10) 0.0506(11) 0.0364(10) -0.0016(8) 0.0076(8) 0.0007(8)
C2 0.0376(9) 0.0422(10) 0.0292(9) -0.0014(7) 0.0045(7) 0.0016(8)
C3 0.0358(9) 0.0421(10) 0.0290(9) -0.0038(7) 0.0034(7) -0.0012(7)
C4 0.0401(10) 0.0406(10) 0.0310(9) -0.0050(7) 0.0008(7) 0.0004(8)
C5 0.0530(12) 0.0448(11) 0.0449(11) -0.0009(8) 0.0113(9) -0.0011(9)
C6 0.0669(14) 0.0430(12) 0.0590(13) 0.0023(9) 0.0131(11) -0.0005(10)
C7 0.0635(14) 0.0429(12) 0.0617(13) 0.0012(10) 0.0015(11) 0.0083(10)
C8 0.0452(11) 0.0524(12) 0.0552(12) -0.0056(10) 0.0034(9) 0.0076(9)
C9 0.0373(9) 0.0465(11) 0.0338(9) -0.0042(8) -0.0013(7) 0.0013(8)
C10 0.0425(10) 0.0409(10) 0.0368(10) -0.0008(8) 0.0143(8) -0.0043(8)
C11 0.0930(17) 0.0468(12) 0.0579(13) 0.0016(10) 0.0331(12) 0.0094(11)
C12 0.0409(10) 0.0359(10) 0.0401(10) -0.0027(8) 0.0087(8) -0.0037(7)
C13 0.0365(10) 0.0413(10) 0.0474(11) 0.0011(8) 0.0082(8) -0.0046(8)
C14 0.0543(13) 0.0642(14) 0.0525(13) -0.0104(10) -0.0012(10) 0.0027(10)
C15 0.0723(16) 0.0793(17) 0.0546(14) -0.0075(12) -0.0153(12) -0.0047(13)
C16 0.0462(13) 0.0715(16) 0.0882(19) 0.0154(14) -0.0111(12) 0.0035(11)
C17 0.0500(13) 0.0795(17) 0.0895(19) 0.0180(14) 0.0157(13) 0.0179(12)
C18 0.0489(12) 0.0620(13) 0.0616(13) 0.0098(10) 0.0181(10) 0.0078(10)
C19 0.0455(11) 0.0722(14) 0.0642(14) -0.0031(11) 0.0197(10) 0.0124(10)

_geom_special_details            
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
N1 C1 1.373(2) . ?
N1 C9 1.397(2) . ?
N1 C19 1.469(2) . ?
N2 C10 1.357(2) . ?
N2 C2 1.405(2) . ?
N2 H2 0.886(14) . ?
O1 C1 1.228(2) . ?
O2 C10 1.2152(19) . ?
O3 C12 1.212(2) . ?
C1 C2 1.457(2) . ?
C2 C3 1.350(2) . ?
C3 C4 1.440(2) . ?
C3 C12 1.505(2) . ?
C4 C5 1.397(2) . ?
C4 C9 1.404(2) . ?
C5 C6 1.366(3) . ?
C5 H5 0.9300 . ?
C6 C7 1.377(3) . ?
C6 H6 0.9300 . ?
C7 C8 1.362(3) . ?
C7 H7 0.9300 . ?
C8 C9 1.391(3) . ?
C8 H8 0.9300 . ?
C10 C11 1.489(3) . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C12 C13 1.483(2) . ?
C13 C14 1.373(3) . ?
C13 C18 1.386(3) . ?
C14 C15 1.391(3) . ?
C14 H14 0.9300 . ?
C15 C16 1.370(4) . ?
C15 H15 0.9300 . ?
C16 C17 1.355(4) . ?
C16 H16 0.9300 . ?
C17 C18 1.366(3) . ?
C17 H17 0.9300 . ?
C18 H18 0.9300 . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C1 N1 C9 123.11(15) . . ?
C1 N1 C19 117.43(16) . . ?
C9 N1 C19 119.46(15) . . ?
C10 N2 C2 124.59(15) . . ?
C10 N2 H2 115.4(12) . . ?
C2 N2 H2 119.2(12) . . ?
O1 C1 N1 122.01(16) . . ?
O1 C1 C2 121.49(17) . . ?
N1 C1 C2 116.48(16) . . ?
C3 C2 N2 123.79(15) . . ?
C3 C2 C1 122.07(16) . . ?
N2 C2 C1 114.13(15) . . ?
C2 C3 C4 119.73(16) . . ?
C2 C3 C12 121.70(15) . . ?
C4 C3 C12 118.57(15) . . ?
C5 C4 C9 117.99(16) . . ?
C5 C4 C3 123.07(16) . . ?
C9 C4 C3 118.92(16) . . ?
C6 C5 C4 121.50(18) . . ?
C6 C5 H5 119.2 . . ?
C4 C5 H5 119.2 . . ?
C5 C6 C7 119.59(19) . . ?
C5 C6 H6 120.2 . . ?
C7 C6 H6 120.2 . . ?
C8 C7 C6 120.78(19) . . ?
C8 C7 H7 119.6 . . ?
C6 C7 H7 119.6 . . ?
C7 C8 C9 120.43(19) . . ?
C7 C8 H8 119.8 . . ?
C9 C8 H8 119.8 . . ?
C8 C9 N1 120.81(17) . . ?
C8 C9 C4 119.66(17) . . ?
N1 C9 C4 119.53(15) . . ?
O2 C10 N2 122.07(16) . . ?
O2 C10 C11 122.11(16) . . ?
N2 C10 C11 115.80(16) . . ?
C10 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
O3 C12 C13 121.47(16) . . ?
O3 C12 C3 121.16(16) . . ?
C13 C12 C3 117.28(15) . . ?
C14 C13 C18 119.17(19) . . ?
C14 C13 C12 122.05(17) . . ?
C18 C13 C12 118.70(17) . . ?
C13 C14 C15 119.8(2) . . ?
C13 C14 H14 120.1 . . ?
C15 C14 H14 120.1 . . ?
C16 C15 C14 119.8(2) . . ?
C16 C15 H15 120.1 . . ?
C14 C15 H15 120.1 . . ?
C17 C16 C15 120.4(2) . . ?
C17 C16 H16 119.8 . . ?
C15 C16 H16 119.8 . . ?
C16 C17 C18 120.4(2) . . ?
C16 C17 H17 119.8 . . ?
C18 C17 H17 119.8 . . ?
C17 C18 C13 120.4(2) . . ?
C17 C18 H18 119.8 . . ?
C13 C18 H18 119.8 . . ?
N1 C19 H19A 109.5 . . ?
N1 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
N1 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C9 N1 C1 O1 -176.53(17) . . . . ?
C19 N1 C1 O1 3.9(3) . . . . ?
C9 N1 C1 C2 2.0(2) . . . . ?
C19 N1 C1 C2 -177.59(15) . . . . ?
C10 N2 C2 C3 49.4(2) . . . . ?
C10 N2 C2 C1 -131.84(17) . . . . ?
O1 C1 C2 C3 173.81(17) . . . . ?
N1 C1 C2 C3 -4.7(2) . . . . ?
O1 C1 C2 N2 -5.0(2) . . . . ?
N1 C1 C2 N2 176.45(15) . . . . ?
N2 C2 C3 C4 -176.80(15) . . . . ?
C1 C2 C3 C4 4.5(2) . . . . ?
N2 C2 C3 C12 2.9(2) . . . . ?
C1 C2 C3 C12 -175.74(15) . . . . ?
C2 C3 C4 C5 -179.80(16) . . . . ?
C12 C3 C4 C5 0.5(2) . . . . ?
C2 C3 C4 C9 -1.5(2) . . . . ?
C12 C3 C4 C9 178.72(14) . . . . ?
C9 C4 C5 C6 1.5(3) . . . . ?
C3 C4 C5 C6 179.78(17) . . . . ?
C4 C5 C6 C7 0.0(3) . . . . ?
C5 C6 C7 C8 -0.5(3) . . . . ?
C6 C7 C8 C9 -0.5(3) . . . . ?
C7 C8 C9 N1 -177.68(17) . . . . ?
C7 C8 C9 C4 2.1(3) . . . . ?
C1 N1 C9 C8 -179.46(17) . . . . ?
C19 N1 C9 C8 0.1(3) . . . . ?
C1 N1 C9 C4 0.8(2) . . . . ?
C19 N1 C9 C4 -179.64(15) . . . . ?
C5 C4 C9 C8 -2.5(2) . . . . ?
C3 C4 C9 C8 179.11(16) . . . . ?
C5 C4 C9 N1 177.25(15) . . . . ?
C3 C4 C9 N1 -1.1(2) . . . . ?
C2 N2 C10 O2 -1.3(3) . . . . ?
C2 N2 C10 C11 179.95(17) . . . . ?
C2 C3 C12 O3 -126.47(18) . . . . ?
C4 C3 C12 O3 53.3(2) . . . . ?
C2 C3 C12 C13 56.9(2) . . . . ?
C4 C3 C12 C13 -123.38(17) . . . . ?
O3 C12 C13 C14 -150.77(19) . . . . ?
C3 C12 C13 C14 25.9(2) . . . . ?
O3 C12 C13 C18 26.0(3) . . . . ?
C3 C12 C13 C18 -157.36(16) . . . . ?
C18 C13 C14 C15 -0.9(3) . . . . ?
C12 C13 C14 C15 175.90(19) . . . . ?
C13 C14 C15 C16 0.4(4) . . . . ?
C14 C15 C16 C17 1.1(4) . . . . ?
C15 C16 C17 C18 -2.0(4) . . . . ?
C16 C17 C18 C13 1.5(4) . . . . ?
C14 C13 C18 C17 -0.1(3) . . . . ?
C12 C13 C18 C17 -176.94(19) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C11 H11B O3 0.96 2.58 3.317(3) 134.1 4_565
C11 H11B O2 0.96 2.35 3.227(2) 152.2 4_565
N2 H2 O2 0.886(14) 2.009(15) 2.8820(19) 168.3(17) 4_565

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        25.99
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.215
_refine_diff_density_min         -0.215
_refine_diff_density_rms         0.049