# Supplementary Material (ESI) for Chemical Communications
# This journal is (c) The Royal Society of Chemistry 2009

data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Yuguo Ma'
_publ_contact_author_email       YGMA@PKU.EDU.CN

_publ_section_title              
;
Copper-Free Cycloaddition of Azide
and Alkyne in Crystalline State Facilitated
by Arene-Perfluoroarene Interaction
;
loop_
_publ_author_name
'Yuguo Ma.'
'Ben-Bo Ni.'
'Jian Pei.'
'Chong Wang.'
'Huxian Wu.'

# Attachment 'imine_11.cif'

data_r90115f
_database_code_depnum_ccdc_archive 'CCDC 731680'
#TrackingRef 'imine_11.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C15 H6 F4 N4'
_chemical_formula_weight         318.24

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'
F F 0.0171 0.0103 '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                   6.1856(12)
_cell_length_b                   7.2446(14)
_cell_length_c                   29.281(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 92.57(3)
_cell_angle_gamma                90.00
_cell_volume                     1310.8(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    113(2)
_cell_measurement_reflns_used    2358
_cell_measurement_theta_min      2.897
_cell_measurement_theta_max      27.113

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.613
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             640
_exptl_absorpt_coefficient_mu    0.141
_exptl_absorpt_correction_type   MULTI-SCAN
_exptl_absorpt_correction_T_min  0.9751
_exptl_absorpt_correction_T_max  0.9861
_exptl_absorpt_process_details   crystalclear

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      113(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_monochromator  confocal
_diffrn_measurement_device_type  'rigaku saturn'
_diffrn_measurement_method       '\w scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_decay_%        0
_diffrn_reflns_number            9472
_diffrn_reflns_av_R_equivalents  0.0430
_diffrn_reflns_av_sigmaI/netI    0.0314
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_theta_min         1.39
_diffrn_reflns_theta_max         25.02
_reflns_number_total             2317
_reflns_number_gt                1968
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       crystalclear
_computing_cell_refinement       crystalclear
_computing_data_reduction        crystalclear
_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^)+(0.0709P)^2^+0.1539P] 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    CONSTR
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2317
_refine_ls_number_parameters     208
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0545
_refine_ls_R_factor_gt           0.0450
_refine_ls_wR_factor_ref         0.1244
_refine_ls_wR_factor_gt          0.1170
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_restrained_S_all      1.076
_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
F1 F 0.98231(17) 0.54116(16) 0.30217(4) 0.0290(3) Uani 1 1 d . . .
F2 F 1.10399(17) 0.54625(16) 0.39079(4) 0.0294(3) Uani 1 1 d . . .
F3 F 0.44329(18) 0.26584(16) 0.42653(3) 0.0293(3) Uani 1 1 d . . .
F4 F 0.31940(17) 0.26381(15) 0.33829(3) 0.0260(3) Uani 1 1 d . . .
N1 N 0.8680(3) 0.4072(3) 0.45636(5) 0.0300(4) Uani 1 1 d . . .
N2 N 0.7488(3) 0.3713(3) 0.48857(6) 0.0340(5) Uani 1 1 d . . .
N3 N 0.6691(3) 0.3429(3) 0.52161(6) 0.0533(6) Uani 1 1 d . . .
N4 N 0.6068(3) 0.3880(2) 0.26939(5) 0.0235(4) Uani 1 1 d . . .
C1 C 0.6473(3) 0.4026(3) 0.31691(6) 0.0221(4) Uani 1 1 d . . .
C2 C 0.8469(3) 0.4710(3) 0.33265(6) 0.0225(4) Uani 1 1 d . . .
C3 C 0.9102(3) 0.4738(3) 0.37803(6) 0.0233(5) Uani 1 1 d . . .
C4 C 0.7785(3) 0.4048(3) 0.41129(6) 0.0237(5) Uani 1 1 d . . .
C5 C 0.5781(3) 0.3372(3) 0.39620(6) 0.0235(5) Uani 1 1 d . . .
C6 C 0.5138(3) 0.3378(3) 0.35041(6) 0.0221(4) Uani 1 1 d . . .
C7 C 0.4214(3) 0.4316(3) 0.25199(6) 0.0232(5) Uani 1 1 d . . .
H7 H 0.3154 0.4745 0.2709 0.028 Uiso 1 1 calc R . .
C8 C 0.3721(3) 0.4155(3) 0.20273(6) 0.0227(4) Uani 1 1 d . . .
C9 C 0.1676(3) 0.4666(3) 0.18518(7) 0.0256(5) Uani 1 1 d . . .
H9 H 0.0632 0.5064 0.2049 0.031 Uiso 1 1 calc R . .
C10 C 0.1189(3) 0.4582(3) 0.13856(6) 0.0265(5) Uani 1 1 d . . .
H10 H -0.0177 0.4929 0.1270 0.032 Uiso 1 1 calc R . .
C11 C 0.2740(3) 0.3980(3) 0.10903(6) 0.0242(5) Uani 1 1 d . . .
C12 C 0.4786(3) 0.3443(3) 0.12652(6) 0.0252(5) Uani 1 1 d . . .
H12 H 0.5824 0.3029 0.1069 0.030 Uiso 1 1 calc R . .
C13 C 0.5258(3) 0.3530(3) 0.17302(6) 0.0236(4) Uani 1 1 d . . .
H13 H 0.6617 0.3168 0.1846 0.028 Uiso 1 1 calc R . .
C14 C 0.2293(3) 0.3900(3) 0.06010(7) 0.0299(5) Uani 1 1 d . . .
C15 C 0.2031(4) 0.3809(3) 0.02020(7) 0.0404(6) Uani 1 1 d . . .
H15 H 0.1824 0.3736 -0.0114 0.048 Uiso 1 1 calc R . .

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
F1 0.0233(6) 0.0369(7) 0.0275(6) 0.0017(5) 0.0078(5) -0.0006(5)
F2 0.0211(6) 0.0356(7) 0.0314(6) -0.0031(5) -0.0016(5) -0.0031(5)
F3 0.0295(7) 0.0353(7) 0.0236(6) 0.0044(5) 0.0053(5) -0.0041(5)
F4 0.0222(6) 0.0277(7) 0.0279(6) 0.0002(5) 0.0000(5) -0.0030(5)
N1 0.0285(10) 0.0385(11) 0.0228(8) 0.0020(7) -0.0010(7) -0.0026(8)
N2 0.0297(10) 0.0453(12) 0.0265(10) -0.0018(8) -0.0036(8) -0.0056(9)
N3 0.0422(13) 0.0918(19) 0.0258(10) -0.0022(11) 0.0012(9) -0.0234(12)
N4 0.0256(9) 0.0235(9) 0.0214(8) -0.0013(6) 0.0001(7) 0.0015(7)
C1 0.0248(11) 0.0194(10) 0.0223(10) -0.0014(8) 0.0027(8) 0.0049(8)
C2 0.0216(10) 0.0213(11) 0.0251(10) 0.0014(8) 0.0057(8) 0.0041(8)
C3 0.0177(10) 0.0214(11) 0.0305(11) -0.0029(8) -0.0012(8) 0.0030(8)
C4 0.0280(11) 0.0208(11) 0.0222(9) -0.0009(8) -0.0011(8) 0.0038(8)
C5 0.0234(11) 0.0237(11) 0.0238(10) 0.0021(8) 0.0039(8) 0.0025(8)
C6 0.0186(10) 0.0196(10) 0.0277(10) -0.0011(8) -0.0021(8) 0.0021(8)
C7 0.0245(11) 0.0206(10) 0.0248(10) 0.0007(8) 0.0052(8) 0.0007(8)
C8 0.0235(11) 0.0207(10) 0.0240(10) 0.0007(8) 0.0011(8) -0.0033(8)
C9 0.0225(11) 0.0244(11) 0.0300(10) 0.0002(8) 0.0034(8) -0.0006(8)
C10 0.0213(11) 0.0254(11) 0.0322(11) 0.0016(9) -0.0048(9) -0.0031(9)
C11 0.0268(11) 0.0202(11) 0.0254(10) 0.0006(8) -0.0013(8) -0.0023(8)
C12 0.0266(11) 0.0223(11) 0.0269(10) -0.0013(8) 0.0031(8) -0.0011(9)
C13 0.0216(10) 0.0219(11) 0.0270(10) 0.0025(8) -0.0016(8) 0.0000(8)
C14 0.0293(12) 0.0271(12) 0.0329(12) -0.0007(9) -0.0036(9) 0.0020(9)
C15 0.0407(14) 0.0501(15) 0.0296(12) -0.0033(10) -0.0074(10) 0.0100(11)

_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
F1 C2 1.350(2) . ?
F2 C3 1.346(2) . ?
F3 C5 1.348(2) . ?
F4 C6 1.349(2) . ?
N1 N2 1.250(2) . ?
N1 C4 1.408(2) . ?
N2 N3 1.124(2) . ?
N4 C7 1.274(3) . ?
N4 C1 1.407(2) . ?
C1 C2 1.390(3) . ?
C1 C6 1.392(3) . ?
C2 C3 1.369(3) . ?
C3 C4 1.391(3) . ?
C4 C5 1.386(3) . ?
C5 C6 1.382(3) . ?
C7 C8 1.466(3) . ?
C7 H7 0.9300 . ?
C8 C13 1.393(3) . ?
C8 C9 1.394(3) . ?
C9 C10 1.386(3) . ?
C9 H9 0.9300 . ?
C10 C11 1.390(3) . ?
C10 H10 0.9300 . ?
C11 C12 1.399(3) . ?
C11 C14 1.448(3) . ?
C12 C13 1.381(3) . ?
C12 H12 0.9300 . ?
C13 H13 0.9300 . ?
C14 C15 1.174(3) . ?
C15 H15 0.9300 . ?

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
N2 N1 C4 118.96(17) . . ?
N3 N2 N1 169.5(2) . . ?
C7 N4 C1 119.60(17) . . ?
C2 C1 C6 115.66(17) . . ?
C2 C1 N4 118.09(17) . . ?
C6 C1 N4 125.93(18) . . ?
F1 C2 C3 118.48(17) . . ?
F1 C2 C1 118.91(16) . . ?
C3 C2 C1 122.59(18) . . ?
F2 C3 C2 119.20(17) . . ?
F2 C3 C4 119.23(16) . . ?
C2 C3 C4 121.57(18) . . ?
C5 C4 C3 116.57(17) . . ?
C5 C4 N1 127.68(18) . . ?
C3 C4 N1 115.72(18) . . ?
F3 C5 C6 118.73(17) . . ?
F3 C5 C4 119.74(16) . . ?
C6 C5 C4 121.52(17) . . ?
F4 C6 C5 117.94(17) . . ?
F4 C6 C1 119.90(16) . . ?
C5 C6 C1 122.07(18) . . ?
N4 C7 C8 121.18(17) . . ?
N4 C7 H7 119.4 . . ?
C8 C7 H7 119.4 . . ?
C13 C8 C9 119.33(17) . . ?
C13 C8 C7 121.51(17) . . ?
C9 C8 C7 119.15(17) . . ?
C10 C9 C8 120.33(18) . . ?
C10 C9 H9 119.8 . . ?
C8 C9 H9 119.8 . . ?
C9 C10 C11 120.05(18) . . ?
C9 C10 H10 120.0 . . ?
C11 C10 H10 120.0 . . ?
C10 C11 C12 119.85(17) . . ?
C10 C11 C14 121.43(18) . . ?
C12 C11 C14 118.72(18) . . ?
C13 C12 C11 119.75(18) . . ?
C13 C12 H12 120.1 . . ?
C11 C12 H12 120.1 . . ?
C12 C13 C8 120.67(18) . . ?
C12 C13 H13 119.7 . . ?
C8 C13 H13 119.7 . . ?
C15 C14 C11 176.8(2) . . ?
C14 C15 H15 180.0 . . ?

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
C4 N1 N2 N3 179.3(13) . . . . ?
C7 N4 C1 C2 -139.37(19) . . . . ?
C7 N4 C1 C6 47.4(3) . . . . ?
C6 C1 C2 F1 -178.11(16) . . . . ?
N4 C1 C2 F1 8.0(3) . . . . ?
C6 C1 C2 C3 0.5(3) . . . . ?
N4 C1 C2 C3 -173.42(17) . . . . ?
F1 C2 C3 F2 0.2(3) . . . . ?
C1 C2 C3 F2 -178.43(17) . . . . ?
F1 C2 C3 C4 179.66(17) . . . . ?
C1 C2 C3 C4 1.1(3) . . . . ?
F2 C3 C4 C5 178.05(16) . . . . ?
C2 C3 C4 C5 -1.4(3) . . . . ?
F2 C3 C4 N1 -3.7(3) . . . . ?
C2 C3 C4 N1 176.76(17) . . . . ?
N2 N1 C4 C5 -11.8(3) . . . . ?
N2 N1 C4 C3 170.25(19) . . . . ?
C3 C4 C5 F3 179.07(16) . . . . ?
N1 C4 C5 F3 1.1(3) . . . . ?
C3 C4 C5 C6 0.3(3) . . . . ?
N1 C4 C5 C6 -177.64(18) . . . . ?
F3 C5 C6 F4 -1.0(3) . . . . ?
C4 C5 C6 F4 177.77(17) . . . . ?
F3 C5 C6 C1 -177.51(17) . . . . ?
C4 C5 C6 C1 1.3(3) . . . . ?
C2 C1 C6 F4 -178.07(16) . . . . ?
N4 C1 C6 F4 -4.7(3) . . . . ?
C2 C1 C6 C5 -1.6(3) . . . . ?
N4 C1 C6 C5 171.74(18) . . . . ?
C1 N4 C7 C8 -179.05(17) . . . . ?
N4 C7 C8 C13 -0.4(3) . . . . ?
N4 C7 C8 C9 -179.39(18) . . . . ?
C13 C8 C9 C10 -1.1(3) . . . . ?
C7 C8 C9 C10 177.97(18) . . . . ?
C8 C9 C10 C11 0.2(3) . . . . ?
C9 C10 C11 C12 0.6(3) . . . . ?
C9 C10 C11 C14 -179.17(18) . . . . ?
C10 C11 C12 C13 -0.6(3) . . . . ?
C14 C11 C12 C13 179.20(18) . . . . ?
C11 C12 C13 C8 -0.3(3) . . . . ?
C9 C8 C13 C12 1.1(3) . . . . ?
C7 C8 C13 C12 -177.92(18) . . . . ?
C10 C11 C14 C15 177(4) . . . . ?
C12 C11 C14 C15 -3(4) . . . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        25.02
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.235
_refine_diff_density_rms         0.049