# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2014

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#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
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#  data retrieval see:
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#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
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data_1
#TrackingRef '13gyte244_CCA_24.cif'

_chemical_name_systematic        ?
_chemical_name_common            phthalonitrile
_chemical_formula_moiety         ' C18 H17 N3 O2 S '
_chemical_formula_sum            'C18 H17 N3 O2 S'
_chemical_formula_iupac          ?
_chemical_formula_weight         339.41
_chemical_absolute_configuration ?

_chemical_melting_point          ?

_space_group_crystal_system      orthorhombic
_space_group_name_H-M_alt        'P c a 21'
_space_group_name_Hall           'P 2c -2ac'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z+1/2'
'x+1/2, -y, z'
'-x+1/2, y, z+1/2'

_cell_length_a                   8.5105(6)
_cell_length_b                   8.8219(6)
_cell_length_c                   21.8277(14)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1638.80(19)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    114
_cell_measurement_theta_min      4.3525
_cell_measurement_theta_max      26.6224
_cell_measurement_temperature    130.(2)

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.130
_exptl_crystal_size_min          0.070
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             712

_exptl_absorpt_coefficient_mu    0.213
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS V2012/1 (Bruker AXS)'
_exptl_absorpt_correction_T_min  0.76
_exptl_absorpt_correction_T_max  0.99

_exptl_special_details           
;
;

_diffrn_ambient_temperature      130.(2)

_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              ImuS

_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_monochromator  'multilayer QUAZAR mirrors'

_diffrn_measurement_device_type  
'Bruker APEX II QUAZAR three-circle diffractometer'
_diffrn_measurement_method       'φ and ω scans'

_diffrn_detector_area_resol_mean 8.3333

_diffrn_reflns_number            11431
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_sigmaI/netI    0.0341
_diffrn_reflns_theta_min         2.97
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25

_refine_special_details          
;
Refinement of F² against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F², conventional R-factors R are based
on F, with F set to zero for negative F². The threshold expression of
F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F² are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;

_reflns_number_total             2837
_reflns_number_gt                2713
_reflns_threshold_expression     >2sigma(I)

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_R_factor_all          0.0319
_refine_ls_R_factor_gt           0.0295
_refine_ls_wR_factor_gt          0.0724
_refine_ls_wR_factor_ref         0.0742
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_restrained_S_all      1.060
_refine_ls_number_reflns         2837
_refine_ls_number_parameters     223
_refine_ls_number_restraints     2
_refine_ls_hydrogen_treatment    mixed
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0401P)²+0.3418P] where P=(Fo²+2Fc²)/3'

_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap

_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_diff_density_max         0.206
_refine_diff_density_min         -0.288
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.01(6)

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_computing_data_collection       'APEX2 (Bruker, 2007)'
_computing_cell_refinement       'APEX2 v2012.10-0 (Bruker AXS)'
_computing_data_reduction        'SAINT V8.27B (Bruker AXS, 2009)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'MERCURY (Macrae et al., 2006)'
_computing_publication_material  
'PLATON V1.16 (Spek, 2009), SHELXTL V6.14 (Bruker, 2001)'

loop_
_atom_site_type_symbol
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C C1 0.8592(2) -0.2035(2) 0.45272(10) 0.0209(5) Uani d . 1 . .
C C2 1.0132(2) -0.4528(2) 0.38858(9) 0.0201(4) Uani d . 1 . .
C C3 1.0485(2) -0.2972(2) 0.37481(10) 0.0176(4) Uani d . 1 . .
C C4 1.1548(3) -0.2650(2) 0.32810(10) 0.0206(5) Uani d . 1 . .
H H4 1.2051 -0.346 0.3072 0.025 Uiso calc R 1 . .
C C5 1.1884(2) -0.1167(2) 0.31165(9) 0.0188(4) Uani d . 1 . .
H H5 1.2608 -0.0965 0.2796 0.023 Uiso calc R 1 . .
C C6 1.1154(2) 0.0027(2) 0.34233(9) 0.0160(4) Uani d . 1 . .
C C7 1.0093(2) -0.0276(2) 0.38959(9) 0.0170(4) Uani d . 1 . .
H H7 0.9605 0.0537 0.4109 0.02 Uiso calc R 1 . .
C C8 0.9751(2) -0.1762(2) 0.40543(9) 0.0176(4) Uani d . 1 . .
C C9 1.0696(2) 0.2443(2) 0.21368(9) 0.0165(4) Uani d . 1 . .
C C10 0.9566(2) 0.3572(2) 0.22065(9) 0.0184(4) Uani d . 1 . .
H H10 0.9622 0.4265 0.2539 0.022 Uiso calc R 1 . .
C C11 0.8364(2) 0.3664(2) 0.17847(9) 0.0193(4) Uani d . 1 . .
H H11 0.759 0.4432 0.1833 0.023 Uiso calc R 1 . .
C C12 0.8244(2) 0.2672(2) 0.12908(10) 0.0179(4) Uani d . 1 . .
C C13 0.9396(2) 0.1567(3) 0.12314(10) 0.0242(5) Uani d . 1 . .
H H13 0.9346 0.088 0.0897 0.029 Uiso calc R 1 . .
C C14 1.0623(2) 0.1440(3) 0.16501(10) 0.0234(5) Uani d . 1 . .
H H14 1.14 0.0676 0.1602 0.028 Uiso calc R 1 . .
C C15 0.6877(3) 0.2851(2) 0.08379(10) 0.0220(5) Uani d . 1 . .
C C16 0.5315(3) 0.2747(3) 0.11891(11) 0.0260(5) Uani d . 1 . .
H H16A 0.4438 0.2791 0.0899 0.039 Uiso calc R 1 . .
H H16B 0.5237 0.3596 0.1477 0.039 Uiso calc R 1 . .
H H16C 0.5275 0.1788 0.1415 0.039 Uiso calc R 1 . .
C C17 0.6883(3) 0.1644(3) 0.03402(11) 0.0317(5) Uani d . 1 . .
H H17A 0.7863 0.1712 0.0106 0.048 Uiso calc R 1 . .
H H17B 0.5987 0.1803 0.0066 0.048 Uiso calc R 1 . .
H H17C 0.6804 0.0639 0.0529 0.048 Uiso calc R 1 . .
C C18 0.6977(3) 0.4423(3) 0.05371(12) 0.0380(6) Uani d . 1 . .
H H18A 0.7965 0.4507 0.0309 0.057 Uiso calc R 1 . .
H H18B 0.6941 0.5207 0.0855 0.057 Uiso calc R 1 . .
H H18C 0.609 0.4557 0.0256 0.057 Uiso calc R 1 . .
H H1N 1.090(3) 0.226(3) 0.3510(12) 0.046 Uiso d D 1 . .
N N1 0.7642(3) -0.2202(2) 0.48896(11) 0.0341(5) Uani d . 1 . .
N N2 0.9886(2) -0.5786(2) 0.39683(8) 0.0261(4) Uani d . 1 . .
N N3 1.1454(2) 0.15609(19) 0.33014(7) 0.0177(4) Uani d D 1 . .
O O1 1.26024(16) 0.38223(15) 0.28665(7) 0.0213(3) Uani d . 1 . .
O O2 1.34011(15) 0.13238(15) 0.24522(7) 0.0215(3) Uani d . 1 . .
S S1 1.22195(5) 0.23207(5) 0.26784(2) 0.01635(12) Uani d . 1 . .


_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_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
C1 N1 . 1.141(3) ?
C1 C8 . 1.448(3) ?
C2 N2 . 1.143(3) ?
C2 C3 . 1.437(3) ?
C3 C4 . 1.392(3) ?
C3 C8 . 1.406(3) ?
C4 C5 . 1.387(3) ?
C4 H4 . 0.95 ?
C5 C6 . 1.394(3) ?
C5 H5 . 0.95 ?
C6 C7 . 1.397(3) ?
C6 N3 . 1.402(3) ?
C7 C8 . 1.387(3) ?
C7 H7 . 0.95 ?
C9 C14 . 1.384(3) ?
C9 C10 . 1.393(3) ?
C9 S1 . 1.7581(19) ?
C10 C11 . 1.378(3) ?
C10 H10 . 0.95 ?
C11 C12 . 1.392(3) ?
C11 H11 . 0.95 ?
C12 C13 . 1.389(3) ?
C12 C15 . 1.535(3) ?
C13 C14 . 1.392(3) ?
C13 H13 . 0.95 ?
C14 H14 . 0.95 ?
C15 C17 . 1.521(3) ?
C15 C16 . 1.537(3) ?
C15 C18 . 1.537(3) ?
C16 H16A . 0.98 ?
C16 H16B . 0.98 ?
C16 H16C . 0.98 ?
C17 H17A . 0.98 ?
C17 H17B . 0.98 ?
C17 H17C . 0.98 ?
C18 H18A . 0.98 ?
C18 H18B . 0.98 ?
C18 H18C . 0.98 ?
N3 S1 . 1.6503(17) ?
N3 H1N . 0.898(17) ?
O1 S1 . 1.4246(14) ?
O2 S1 . 1.4242(14) ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
N1 C1 C8 . . 177.2(2) ?
N2 C2 C3 . . 176.6(2) ?
C4 C3 C8 . . 118.80(18) ?
C4 C3 C2 . . 118.96(19) ?
C8 C3 C2 . . 122.19(19) ?
C5 C4 C3 . . 121.09(19) ?
C5 C4 H4 . . 119.5 ?
C3 C4 H4 . . 119.5 ?
C4 C5 C6 . . 119.79(19) ?
C4 C5 H5 . . 120.1 ?
C6 C5 H5 . . 120.1 ?
C5 C6 C7 . . 119.87(19) ?
C5 C6 N3 . . 123.86(18) ?
C7 C6 N3 . . 116.24(17) ?
C8 C7 C6 . . 120.04(18) ?
C8 C7 H7 . . 120.0 ?
C6 C7 H7 . . 120.0 ?
C7 C8 C3 . . 120.41(18) ?
C7 C8 C1 . . 118.51(19) ?
C3 C8 C1 . . 121.05(19) ?
C14 C9 C10 . . 120.67(19) ?
C14 C9 S1 . . 120.65(16) ?
C10 C9 S1 . . 118.68(15) ?
C11 C10 C9 . . 118.80(19) ?
C11 C10 H10 . . 120.6 ?
C9 C10 H10 . . 120.6 ?
C10 C11 C12 . . 122.28(19) ?
C10 C11 H11 . . 118.9 ?
C12 C11 H11 . . 118.9 ?
C13 C12 C11 . . 117.53(19) ?
C13 C12 C15 . . 123.2(2) ?
C11 C12 C15 . . 119.30(18) ?
C12 C13 C14 . . 121.6(2) ?
C12 C13 H13 . . 119.2 ?
C14 C13 H13 . . 119.2 ?
C9 C14 C13 . . 119.1(2) ?
C9 C14 H14 . . 120.5 ?
C13 C14 H14 . . 120.5 ?
C17 C15 C12 . . 112.65(18) ?
C17 C15 C16 . . 108.53(18) ?
C12 C15 C16 . . 109.16(18) ?
C17 C15 C18 . . 109.04(19) ?
C12 C15 C18 . . 109.00(17) ?
C16 C15 C18 . . 108.37(19) ?
C15 C16 H16A . . 109.5 ?
C15 C16 H16B . . 109.5 ?
H16A C16 H16B . . 109.5 ?
C15 C16 H16C . . 109.5 ?
H16A C16 H16C . . 109.5 ?
H16B C16 H16C . . 109.5 ?
C15 C17 H17A . . 109.5 ?
C15 C17 H17B . . 109.5 ?
H17A C17 H17B . . 109.5 ?
C15 C17 H17C . . 109.5 ?
H17A C17 H17C . . 109.5 ?
H17B C17 H17C . . 109.5 ?
C15 C18 H18A . . 109.5 ?
C15 C18 H18B . . 109.5 ?
H18A C18 H18B . . 109.5 ?
C15 C18 H18C . . 109.5 ?
H18A C18 H18C . . 109.5 ?
H18B C18 H18C . . 109.5 ?
C6 N3 S1 . . 128.31(14) ?
C6 N3 H1N . . 118.1(19) ?
S1 N3 H1N . . 110.2(19) ?
O2 S1 O1 . . 120.84(8) ?
O2 S1 N3 . . 108.28(9) ?
O1 S1 N3 . . 103.33(9) ?
O2 S1 C9 . . 109.00(9) ?
O1 S1 C9 . . 107.78(9) ?
N3 S1 C9 . . 106.73(9) ?

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_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion
_geom_torsion_publ_flag
N2 C2 C3 C4 . . . . -14.(4) ?
N2 C2 C3 C8 . . . . 164.(4) ?
C8 C3 C4 C5 . . . . -0.1(3) ?
C2 C3 C4 C5 . . . . 177.67(19) ?
C3 C4 C5 C6 . . . . 0.2(3) ?
C4 C5 C6 C7 . . . . 0.2(3) ?
C4 C5 C6 N3 . . . . 178.06(18) ?
C5 C6 C7 C8 . . . . -0.8(3) ?
N3 C6 C7 C8 . . . . -178.81(17) ?
C6 C7 C8 C3 . . . . 1.0(3) ?
C6 C7 C8 C1 . . . . -177.21(18) ?
C4 C3 C8 C7 . . . . -0.5(3) ?
C2 C3 C8 C7 . . . . -178.18(19) ?
C4 C3 C8 C1 . . . . 177.59(19) ?
C2 C3 C8 C1 . . . . -0.1(3) ?
N1 C1 C8 C7 . . . . 41.(5) ?
N1 C1 C8 C3 . . . . -138.(5) ?
C14 C9 C10 C11 . . . . 0.6(3) ?
S1 C9 C10 C11 . . . . -179.59(15) ?
C9 C10 C11 C12 . . . . -0.2(3) ?
C10 C11 C12 C13 . . . . -0.3(3) ?
C10 C11 C12 C15 . . . . -179.70(19) ?
C11 C12 C13 C14 . . . . 0.4(3) ?
C15 C12 C13 C14 . . . . 179.8(2) ?
C10 C9 C14 C13 . . . . -0.4(3) ?
S1 C9 C14 C13 . . . . 179.74(16) ?
C12 C13 C14 C9 . . . . -0.1(3) ?
C13 C12 C15 C17 . . . . 2.8(3) ?
C11 C12 C15 C17 . . . . -177.83(19) ?
C13 C12 C15 C16 . . . . 123.4(2) ?
C11 C12 C15 C16 . . . . -57.2(2) ?
C13 C12 C15 C18 . . . . -118.4(2) ?
C11 C12 C15 C18 . . . . 61.0(3) ?
C5 C6 N3 S1 . . . . 20.5(3) ?
C7 C6 N3 S1 . . . . -161.52(15) ?
C6 N3 S1 O2 . . . . -36.84(19) ?
C6 N3 S1 O1 . . . . -166.11(16) ?
C6 N3 S1 C9 . . . . 80.37(18) ?
C14 C9 S1 O2 . . . . 12.08(19) ?
C10 C9 S1 O2 . . . . -167.77(15) ?
C14 C9 S1 O1 . . . . 144.91(17) ?
C10 C9 S1 O1 . . . . -34.94(18) ?
C14 C9 S1 N3 . . . . -104.66(18) ?
C10 C9 S1 N3 . . . . 75.50(17) ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_publ_flag
N3 H1N N2 1_565 0.898(17) 2.174(18) 3.062(3) 170.(3) ?
_database_code_depnum_ccdc_archive 'CCDC 925679'
