Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2005


data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182

_publ_contact_author_name        'J. M. Shreeve'
_publ_contact_author_address     
;
Department of Chemistry
University of Idaho
Box 442343
Moscow
ID
83844-2343
UNITED STATES OF AMERICA
;

_publ_contact_author_email       JSHREEVE@UIDAHO.EDU

_publ_section_title              
;
High energy density materials from azido
cyclophosphazenes
;
loop_
_publ_author_name
'J. M. Shreeve'
'K. Muralidharan'
'Banidele A. Omotowa'
'Crystal Piekarski'
'Brendan Twamley'

data_bt583
_database_code_depnum_ccdc_archive 'CCDC 278747'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            'subsitituted phosphazene'
_chemical_melting_point          ?
_chemical_formula_moiety         'C8 H20 Cl2 N18 P4'
_chemical_formula_sum            'C8 H20 Cl2 N18 P4'
_chemical_formula_weight         563.20

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'
Cl Cl 0.1484 0.1585 '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'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   C2/c
_symmetry_space_group_name_Hall  '-C 2yc'

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

_cell_length_a                   18.452(4)
_cell_length_b                   9.5500(19)
_cell_length_c                   14.060(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 103.67(3)
_cell_angle_gamma                90.00
_cell_volume                     2407.4(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    84(2)
_cell_measurement_reflns_used    5064
_cell_measurement_theta_min      2.41
_cell_measurement_theta_max      29.99

_exptl_crystal_description       fragment
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.03
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.554
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1152
_exptl_absorpt_coefficient_mu    0.574
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8030
_exptl_absorpt_correction_T_max  0.9836
_exptl_absorpt_process_details   'SADABS; Bruker, 2001'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      84(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'normal-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker/Siemens SMART APEX'
_diffrn_measurement_method       '\w scans'
_diffrn_detector_area_resol_mean 8.3
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            15727
_diffrn_reflns_av_R_equivalents  0.0233
_diffrn_reflns_av_sigmaI/netI    0.0193
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.27
_diffrn_reflns_theta_max         27.50
_reflns_number_total             2774
_reflns_number_gt                2591
_reflns_threshold_expression     I>2\s(I)

_computing_data_collection       'Bruker SMART v. 5.626'
_computing_cell_refinement       'Bruker SAINT+ v. 6.36a'
_computing_data_reduction        'Bruker SAINT+ v. 6.36a'
_computing_structure_solution    'XS, Bruker SHELXTL v. 6.12'
_computing_structure_refinement  'XL, Bruker SHELXTL v. 6.12'
_computing_molecular_graphics    'XP, Bruker SHELXTL v. 6.12'
_computing_publication_material  'XCIF, Bruker SHELXTL v. 6.12'

_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^)+(0.0583P)^2^+7.4982P] 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     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2774
_refine_ls_number_parameters     159
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0444
_refine_ls_wR_factor_ref         0.1157
_refine_ls_wR_factor_gt          0.1134
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_restrained_S_all      1.108
_refine_ls_shift/su_max          0.000
_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
Cl1 Cl 0.14229(3) 1.07377(7) 0.09734(4) 0.02628(17) Uani 1 1 d . . .
P1 P 0.06197(3) 0.93759(6) 0.12345(4) 0.01708(16) Uani 1 1 d . . .
P2 P 0.04073(3) 0.83348(6) -0.07086(4) 0.01771(16) Uani 1 1 d . . .
N1 N 0.05413(11) 0.8182(2) 0.04371(13) 0.0200(4) Uani 1 1 d . . .
N2 N -0.00930(10) 1.0285(2) 0.12583(13) 0.0191(4) Uani 1 1 d . . .
N3 N -0.00897(13) 0.6900(2) -0.12049(15) 0.0287(5) Uani 1 1 d . . .
N4 N -0.04664(13) 0.6323(2) -0.07114(17) 0.0316(5) Uani 1 1 d . . .
N5 N -0.08291(17) 0.5709(3) -0.0314(2) 0.0454(7) Uani 1 1 d . . .
N6 N 0.12006(12) 0.8103(2) -0.11026(15) 0.0267(4) Uani 1 1 d . . .
N7 N 0.15889(12) 0.7093(2) -0.07513(16) 0.0268(4) Uani 1 1 d . . .
N8 N 0.19900(14) 0.6220(3) -0.0474(2) 0.0378(6) Uani 1 1 d . . .
N9 N 0.09056(11) 0.8737(2) 0.23153(14) 0.0216(4) Uani 1 1 d . A .
H9 H 0.0746(16) 0.919(3) 0.269(2) 0.020(7) Uiso 1 1 d . . .
C1 C 0.14857(16) 0.7685(3) 0.27042(18) 0.0387(7) Uani 1 1 d D . .
C2A C 0.1057(3) 0.6241(5) 0.2519(3) 0.0486(9) Uani 0.744(6) 1 d PD A 1
H2AA H 0.0828 0.6139 0.1819 0.073 Uiso 0.744(6) 1 calc PR A 1
H2AB H 0.0669 0.6216 0.2888 0.073 Uiso 0.744(6) 1 calc PR A 1
H2AC H 0.1409 0.5472 0.2734 0.073 Uiso 0.744(6) 1 calc PR A 1
C3A C 0.1758(3) 0.7870(5) 0.3775(3) 0.0486(9) Uani 0.744(6) 1 d PD A 1
H3AA H 0.2058 0.8726 0.3908 0.073 Uiso 0.744(6) 1 calc PR A 1
H3AB H 0.2064 0.7063 0.4051 0.073 Uiso 0.744(6) 1 calc PR A 1
H3AC H 0.1331 0.7943 0.4076 0.073 Uiso 0.744(6) 1 calc PR A 1
C4A C 0.2094(3) 0.7661(6) 0.2152(3) 0.0486(9) Uani 0.744(6) 1 d PD A 1
H4AA H 0.2355 0.8562 0.2232 0.073 Uiso 0.744(6) 1 calc PR A 1
H4AB H 0.1874 0.7494 0.1456 0.073 Uiso 0.744(6) 1 calc PR A 1
H4AC H 0.2448 0.6910 0.2410 0.073 Uiso 0.744(6) 1 calc PR A 1
C2B C 0.1320(6) 0.6846(10) 0.3539(7) 0.0330(18) Uani 0.256(6) 1 d PD A 2
H2BA H 0.1177 0.7482 0.4010 0.050 Uiso 0.256(6) 1 calc PR A 2
H2BB H 0.1765 0.6318 0.3863 0.050 Uiso 0.256(6) 1 calc PR A 2
H2BC H 0.0910 0.6194 0.3283 0.050 Uiso 0.256(6) 1 calc PR A 2
C3B C 0.2117(5) 0.8743(10) 0.3317(7) 0.0330(18) Uani 0.256(6) 1 d PD A 2
H3BA H 0.2286 0.9372 0.2863 0.050 Uiso 0.256(6) 1 calc PR A 2
H3BB H 0.2541 0.8199 0.3687 0.050 Uiso 0.256(6) 1 calc PR A 2
H3BC H 0.1904 0.9297 0.3772 0.050 Uiso 0.256(6) 1 calc PR A 2
C4B C 0.1895(7) 0.7007(13) 0.2016(7) 0.0330(18) Uani 0.256(6) 1 d PD A 2
H4B1 H 0.1574 0.6303 0.1619 0.050 Uiso 0.256(6) 1 calc PR A 2
H4B2 H 0.2349 0.6556 0.2396 0.050 Uiso 0.256(6) 1 calc PR A 2
H4B3 H 0.2029 0.7721 0.1587 0.050 Uiso 0.256(6) 1 calc PR A 2

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
Cl1 0.0204(3) 0.0352(3) 0.0233(3) -0.0008(2) 0.0053(2) -0.0077(2)
P1 0.0162(3) 0.0235(3) 0.0113(3) 0.0006(2) 0.0026(2) -0.0001(2)
P2 0.0188(3) 0.0216(3) 0.0129(3) -0.0008(2) 0.0040(2) 0.0007(2)
N1 0.0233(9) 0.0234(10) 0.0129(8) 0.0012(7) 0.0037(7) 0.0010(7)
N2 0.0187(9) 0.0253(10) 0.0135(8) 0.0024(7) 0.0040(7) 0.0010(7)
N3 0.0369(12) 0.0291(11) 0.0204(10) -0.0042(8) 0.0076(9) -0.0031(9)
N4 0.0358(12) 0.0263(11) 0.0315(11) -0.0043(9) 0.0053(9) -0.0041(9)
N5 0.0509(16) 0.0363(14) 0.0537(17) 0.0006(12) 0.0218(13) -0.0126(12)
N6 0.0269(10) 0.0333(11) 0.0223(10) 0.0051(8) 0.0108(8) 0.0069(9)
N7 0.0250(10) 0.0316(11) 0.0271(10) -0.0030(9) 0.0126(8) 0.0003(9)
N8 0.0317(12) 0.0344(13) 0.0510(15) 0.0043(11) 0.0172(11) 0.0080(10)
N9 0.0232(10) 0.0296(11) 0.0118(8) 0.0011(8) 0.0038(7) 0.0076(8)
C1 0.0431(16) 0.0526(18) 0.0214(12) 0.0122(12) 0.0097(11) 0.0283(14)
C2A 0.0560(17) 0.0623(19) 0.0246(11) 0.0076(11) 0.0040(10) 0.0293(14)
C3A 0.0560(17) 0.0623(19) 0.0246(11) 0.0076(11) 0.0040(10) 0.0293(14)
C4A 0.0560(17) 0.0623(19) 0.0246(11) 0.0076(11) 0.0040(10) 0.0293(14)
C2B 0.038(4) 0.031(3) 0.028(3) 0.002(2) 0.004(3) 0.011(3)
C3B 0.038(4) 0.031(3) 0.028(3) 0.002(2) 0.004(3) 0.011(3)
C4B 0.038(4) 0.031(3) 0.028(3) 0.002(2) 0.004(3) 0.011(3)

_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
Cl1 P1 2.0687(9) . ?
P1 N1 1.582(2) . ?
P1 N2 1.583(2) . ?
P1 N9 1.606(2) . ?
P2 N2 1.568(2) 5_575 ?
P2 N1 1.5777(19) . ?
P2 N6 1.698(2) . ?
P2 N3 1.703(2) . ?
N2 P2 1.568(2) 5_575 ?
N3 N4 1.223(3) . ?
N4 N5 1.132(3) . ?
N6 N7 1.233(3) . ?
N7 N8 1.122(3) . ?
N9 C1 1.476(3) . ?
N9 H9 0.78(3) . ?
C1 C3A 1.481(4) . ?
C1 C4B 1.507(7) . ?
C1 C4A 1.509(5) . ?
C1 C2B 1.510(7) . ?
C1 C2A 1.581(5) . ?
C1 C3B 1.627(7) . ?
C2A H2AA 0.9800 . ?
C2A H2AB 0.9800 . ?
C2A H2AC 0.9800 . ?
C3A H3AA 0.9800 . ?
C3A H3AB 0.9800 . ?
C3A H3AC 0.9800 . ?
C4A H4AA 0.9800 . ?
C4A H4AB 0.9800 . ?
C4A H4AC 0.9800 . ?
C2B H2BA 0.9800 . ?
C2B H2BB 0.9800 . ?
C2B H2BC 0.9800 . ?
C3B H3BA 0.9800 . ?
C3B H3BB 0.9800 . ?
C3B H3BC 0.9800 . ?
C4B H4B1 0.9800 . ?
C4B H4B2 0.9800 . ?
C4B H4B3 0.9800 . ?

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
N1 P1 N2 118.23(11) . . ?
N1 P1 N9 110.57(11) . . ?
N2 P1 N9 106.08(10) . . ?
N1 P1 Cl1 106.07(8) . . ?
N2 P1 Cl1 107.02(8) . . ?
N9 P1 Cl1 108.53(8) . . ?
N2 P2 N1 122.11(10) 5_575 . ?
N2 P2 N6 101.28(10) 5_575 . ?
N1 P2 N6 112.45(11) . . ?
N2 P2 N3 111.94(11) 5_575 . ?
N1 P2 N3 106.44(11) . . ?
N6 P2 N3 100.59(11) . . ?
P2 N1 P1 128.53(13) . . ?
P2 N2 P1 131.52(13) 5_575 . ?
N4 N3 P2 116.93(18) . . ?
N5 N4 N3 174.3(3) . . ?
N7 N6 P2 115.82(17) . . ?
N8 N7 N6 173.6(3) . . ?
C1 N9 P1 131.02(17) . . ?
C1 N9 H9 119(2) . . ?
P1 N9 H9 109(2) . . ?
N9 C1 C3A 109.7(2) . . ?
N9 C1 C4B 119.0(5) . . ?
C3A C1 C4B 127.1(5) . . ?
N9 C1 C4A 112.5(3) . . ?
C3A C1 C4A 114.2(3) . . ?
N9 C1 C2B 112.8(4) . . ?
C3A C1 C2B 49.9(5) . . ?
C4B C1 C2B 119.6(6) . . ?
C4A C1 C2B 134.7(5) . . ?
N9 C1 C2A 104.0(2) . . ?
C3A C1 C2A 107.9(3) . . ?
C4B C1 C2A 80.0(6) . . ?
C4A C1 C2A 107.8(3) . . ?
C2B C1 C2A 58.7(5) . . ?
N9 C1 C3B 98.0(4) . . ?
C3A C1 C3B 50.1(5) . . ?
C4B C1 C3B 101.7(7) . . ?
C4A C1 C3B 75.9(5) . . ?
C2B C1 C3B 99.7(6) . . ?
C2A C1 C3B 153.8(4) . . ?
C1 C2A H2AA 109.5 . . ?
C1 C2A H2AB 109.5 . . ?
C1 C2A H2AC 109.5 . . ?
C1 C3A H3AA 109.5 . . ?
C1 C3A H3AB 109.5 . . ?
C1 C3A H3AC 109.5 . . ?
C1 C4A H4AA 109.5 . . ?
C1 C4A H4AB 109.5 . . ?
C1 C4A H4AC 109.5 . . ?
C1 C2B H2BA 109.5 . . ?
C1 C2B H2BB 109.5 . . ?
H2BA C2B H2BB 109.5 . . ?
C1 C2B H2BC 109.5 . . ?
H2BA C2B H2BC 109.5 . . ?
H2BB C2B H2BC 109.5 . . ?
C1 C3B H3BA 109.5 . . ?
C1 C3B H3BB 109.5 . . ?
H3BA C3B H3BB 109.5 . . ?
C1 C3B H3BC 109.5 . . ?
H3BA C3B H3BC 109.5 . . ?
H3BB C3B H3BC 109.5 . . ?
C1 C4B H4B1 109.5 . . ?
C1 C4B H4B2 109.5 . . ?
H4B1 C4B H4B2 109.5 . . ?
C1 C4B H4B3 109.5 . . ?
H4B1 C4B H4B3 109.5 . . ?
H4B2 C4B H4B3 109.5 . . ?

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
N9 H9 N2 0.78(3) 2.37(3) 3.143(3) 170(3) 2

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        27.50
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.856
_refine_diff_density_min         -0.836
_refine_diff_density_rms         0.096