# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2004


data_global
_journal_name_full               'New J.Chem.(Nouv.J.Chim.)'

_journal_coden_Cambridge         0440

_publ_contact_author_name        'Prof John Smith'
_publ_contact_author_address     
;
Department of Chemistry
King's College London
Strand
London
WC2R 2LS
UNITED KINGDOM
;

_publ_contact_author_email       JOHN.SMITH@KCL.AC.UK

_publ_section_title              
;
The Unusual Solid State Structure of Heroin
Hydrochloride Monohydrate and its Selective Detection Using NQR
Spectroscopy.
;
loop_
_publ_author_name
'John Smith'
'Elizabeth Balchin'
'Mike Bearpark'
'Anthony J. Horsewill'
'D. Malcolme-Lawes'
;
M.Rowe
;
'Jonathan Steed'
'David Stephenson'
'Weimin Wu'

data_HHCL4121.CIF
_database_code_depnum_ccdc_archive 'CCDC 242245'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            hhcl
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C21 H26 Cl N O6'
_chemical_formula_weight         423.88

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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   P41212

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y+1/2, x+1/2, z+1/4'
'-x, -y, z+1/2'
'y+1/2, -x+1/2, z+3/4'
'x+1/2, -y+1/2, -z+3/4'
'-x+1/2, y+1/2, -z+1/4'
'y, x, -z'
'-y, -x, -z+1/2'

_cell_length_a                   7.5335(11)
_cell_length_b                   7.5335(11)
_cell_length_c                   71.976(14)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     4084.9(12)
_cell_formula_units_Z            8
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       ?
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.1
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.378
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1792
_exptl_absorpt_coefficient_mu    0.225
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      173(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  KappaCCD
_diffrn_measurement_method       \w
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        0
_diffrn_reflns_number            3478
_diffrn_reflns_av_R_equivalents  0.0854
_diffrn_reflns_av_sigmaI/netI    0.2445
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -85
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_theta_min         3.35
_diffrn_reflns_theta_max         24.98
_reflns_number_total             2808
_reflns_number_gt                1328
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Nonius Collect'
_computing_cell_refinement       DENZO-SMN
_computing_data_reduction        DENZO-SMN
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'XSeed interface to POVRay'
_computing_publication_material  'CIFTAB (Sheldrick, 1997)'

_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^)+(0.0169P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_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   -0.3(2)
_refine_ls_number_reflns         2808
_refine_ls_number_parameters     273
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.2057
_refine_ls_R_factor_gt           0.0778
_refine_ls_wR_factor_ref         0.1267
_refine_ls_wR_factor_gt          0.0943
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_restrained_S_all      1.000
_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 0.9724(2) 0.0653(3) 0.11243(2) 0.0393(7) Uani 1 1 d . . .
O1 O 0.4909(7) -0.5932(7) 0.19070(7) 0.0419(17) Uani 1 1 d . . .
N1 N 1.1420(8) 0.0758(9) 0.15128(7) 0.0317(19) Uani 1 1 d . . .
H1 H 1.0785 0.0692 0.1402 0.038 Uiso 1 1 calc R . .
C1 C 0.5423(10) -0.5795(9) 0.22355(9) 0.050(3) Uani 1 1 d . . .
H1A H 0.4980 -0.4871 0.2319 0.074 Uiso 1 1 calc R . .
H1B H 0.6638 -0.6115 0.2271 0.074 Uiso 1 1 calc R . .
H1C H 0.4659 -0.6845 0.2244 0.074 Uiso 1 1 calc R . .
O2 O 0.6039(7) -0.3430(8) 0.20314(6) 0.0341(16) Uani 1 1 d . . .
C2 C 0.5413(11) -0.5117(13) 0.20404(12) 0.040(2) Uani 1 1 d . . .
O3 O 0.9066(7) -0.4449(7) 0.18989(6) 0.0345(16) Uani 1 1 d . . .
C3 C 0.6291(11) -0.2693(11) 0.18481(10) 0.030(2) Uani 1 1 d . . .
H3 H 0.5298 -0.3129 0.1768 0.036 Uiso 1 1 calc R . .
O4 O 1.1017(7) -0.5069(7) 0.22490(6) 0.0382(17) Uani 1 1 d . . .
C4 C 0.6085(10) -0.0736(12) 0.18676(9) 0.030(2) Uani 1 1 d . . .
H4 H 0.5202 -0.0307 0.1950 0.036 Uiso 1 1 calc R . .
O5 O 0.9181(8) -0.4023(7) 0.24718(7) 0.0514(19) Uani 1 1 d . . .
C5 C 0.7048(11) 0.0430(12) 0.17776(9) 0.040(3) Uani 1 1 d . . .
H5 H 0.6761 0.1653 0.1790 0.048 Uiso 1 1 calc R . .
C6 C 0.8577(10) -0.0083(11) 0.16568(10) 0.030(2) Uani 1 1 d . . .
H6 H 0.8138 -0.0181 0.1526 0.036 Uiso 1 1 calc R . .
C7 C 1.0064(11) 0.1312(9) 0.16613(9) 0.030(2) Uani 1 1 d . . .
H7 H 0.9542 0.2476 0.1623 0.036 Uiso 1 1 calc R . .
C8 C 1.2816(10) 0.2149(10) 0.14810(9) 0.035(2) Uani 1 1 d . . .
H8A H 1.3572 0.2243 0.1591 0.052 Uiso 1 1 calc R . .
H8B H 1.2243 0.3295 0.1457 0.052 Uiso 1 1 calc R . .
H8C H 1.3542 0.1817 0.1374 0.052 Uiso 1 1 calc R . .
C9 C 1.2181(11) -0.1060(10) 0.15418(9) 0.034(2) Uani 1 1 d . . .
H9A H 1.2923 -0.1070 0.1655 0.041 Uiso 1 1 calc R . .
H9B H 1.2942 -0.1383 0.1435 0.041 Uiso 1 1 calc R . .
C10 C 1.0689(11) -0.2398(9) 0.15612(9) 0.027(2) Uani 1 1 d . . .
H10A H 1.1196 -0.3574 0.1592 0.033 Uiso 1 1 calc R . .
H10B H 1.0059 -0.2506 0.1441 0.033 Uiso 1 1 calc R . .
C11 C 0.9367(12) -0.1858(11) 0.17122(10) 0.029(2) Uani 1 1 d . . .
C12 C 0.8074(11) -0.3388(10) 0.17614(10) 0.028(2) Uani 1 1 d . . .
H12 H 0.7821 -0.4119 0.1648 0.034 Uiso 1 1 calc R . .
C13 C 1.0139(11) -0.3203(12) 0.19906(11) 0.034(2) Uani 1 1 d . . .
C14 C 1.0250(10) -0.1670(12) 0.18947(10) 0.027(2) Uani 1 1 d . . .
C15 C 1.1100(10) -0.0171(12) 0.19633(10) 0.030(2) Uani 1 1 d . . .
C16 C 1.0929(10) 0.1559(10) 0.18552(9) 0.034(2) Uani 1 1 d . . .
H16A H 1.2124 0.2085 0.1839 0.041 Uiso 1 1 calc R . .
H16B H 1.0206 0.2405 0.1928 0.041 Uiso 1 1 calc R . .
C17 C 1.1940(10) -0.0346(12) 0.21328(10) 0.036(2) Uani 1 1 d . . .
H17 H 1.2556 0.0637 0.2185 0.043 Uiso 1 1 calc R . .
C18 C 1.1888(10) -0.1953(13) 0.22283(10) 0.035(3) Uani 1 1 d . . .
H18 H 1.2483 -0.2062 0.2344 0.042 Uiso 1 1 calc R . .
C19 C 1.0984(12) -0.3385(13) 0.21569(11) 0.034(3) Uani 1 1 d . . .
C20 C 1.0113(12) -0.5172(12) 0.24145(11) 0.039(3) Uani 1 1 d . . .
C21 C 1.0404(11) -0.6940(11) 0.25095(9) 0.063(3) Uani 1 1 d . . .
H21A H 1.1612 -0.6988 0.2560 0.095 Uiso 1 1 calc R . .
H21B H 1.0241 -0.7902 0.2419 0.095 Uiso 1 1 calc R . .
H21C H 0.9547 -0.7076 0.2611 0.095 Uiso 1 1 calc R . .
O1S O 0.9214(10) 0.4352(10) 0.13022(12) 0.057(2) Uani 1 1 d . . .
H1S H 0.898(14) 0.361(14) 0.1203(12) 0.16(6) Uiso 1 1 d . . .
H2S H 0.837(13) 0.438(16) 0.1366(12) 0.13(6) Uiso 1 1 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
Cl1 0.0399(17) 0.0406(17) 0.0374(11) 0.0002(11) -0.0025(10) 0.0029(14)
O1 0.040(4) 0.034(4) 0.052(4) -0.001(3) -0.003(3) -0.007(3)
N1 0.028(5) 0.036(5) 0.031(4) 0.011(4) 0.005(3) -0.015(4)
C1 0.043(7) 0.056(7) 0.050(6) 0.022(5) -0.003(5) -0.011(6)
O2 0.034(4) 0.030(4) 0.038(3) 0.005(3) 0.002(3) -0.002(4)
C2 0.026(7) 0.039(8) 0.055(6) -0.006(6) 0.007(5) 0.005(6)
O3 0.034(4) 0.032(4) 0.037(3) 0.000(3) -0.002(3) 0.001(4)
C3 0.017(7) 0.043(7) 0.030(5) 0.003(4) -0.001(4) -0.007(5)
O4 0.048(5) 0.034(4) 0.032(3) 0.002(3) 0.015(3) 0.009(4)
C4 0.031(7) 0.028(7) 0.032(5) -0.006(5) 0.004(4) 0.010(6)
O5 0.057(5) 0.040(5) 0.057(4) -0.002(3) 0.015(4) 0.005(4)
C5 0.026(7) 0.047(8) 0.047(6) 0.003(5) -0.001(5) 0.019(6)
C6 0.023(6) 0.029(6) 0.038(5) -0.005(5) 0.000(4) 0.000(5)
C7 0.033(6) 0.029(6) 0.027(5) 0.002(4) 0.009(4) 0.000(5)
C8 0.029(7) 0.039(7) 0.037(5) 0.011(4) -0.005(4) -0.015(5)
C9 0.053(7) 0.013(6) 0.036(5) 0.001(4) 0.007(4) 0.002(5)
C10 0.029(6) 0.018(6) 0.035(5) 0.004(4) -0.010(5) -0.004(5)
C11 0.040(7) 0.019(6) 0.030(5) 0.001(4) 0.007(5) 0.001(5)
C12 0.024(6) 0.024(7) 0.038(5) -0.005(4) -0.009(5) -0.015(5)
C13 0.034(7) 0.041(7) 0.027(5) -0.004(5) -0.003(5) 0.002(6)
C14 0.020(6) 0.038(7) 0.022(5) 0.007(5) -0.001(4) 0.002(5)
C15 0.029(6) 0.033(7) 0.029(5) -0.009(5) -0.003(4) 0.000(5)
C16 0.032(6) 0.036(6) 0.036(5) -0.002(4) 0.003(5) -0.003(5)
C17 0.033(6) 0.039(8) 0.035(5) -0.003(5) 0.003(4) -0.008(5)
C18 0.023(7) 0.050(8) 0.031(5) 0.001(5) -0.006(4) -0.001(6)
C19 0.034(7) 0.033(7) 0.037(6) 0.016(5) 0.011(5) 0.008(6)
C20 0.031(8) 0.037(8) 0.051(7) -0.013(5) -0.007(5) -0.004(6)
C21 0.078(9) 0.054(8) 0.058(6) 0.019(5) 0.016(6) 0.023(7)
O1S 0.052(6) 0.057(5) 0.062(5) -0.015(4) -0.008(4) 0.002(5)

_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
O1 C2 1.201(8) . ?
N1 C9 1.500(8) . ?
N1 C8 1.502(7) . ?
N1 C7 1.536(8) . ?
C1 C2 1.495(9) . ?
O2 C2 1.357(9) . ?
O2 C3 1.444(7) . ?
O3 C13 1.403(8) . ?
O3 C12 1.476(7) . ?
C3 C4 1.489(9) . ?
C3 C12 1.571(9) . ?
O4 C20 1.374(8) . ?
O4 C19 1.432(8) . ?
C4 C5 1.310(8) . ?
O5 C20 1.188(9) . ?
C5 C6 1.495(9) . ?
C6 C11 1.517(9) . ?
C6 C7 1.536(9) . ?
C7 C16 1.552(8) . ?
C9 C10 1.516(9) . ?
C10 C11 1.529(8) . ?
C11 C14 1.480(9) . ?
C11 C12 1.550(9) . ?
C13 C14 1.349(9) . ?
C13 C19 1.363(9) . ?
C14 C15 1.389(9) . ?
C15 C17 1.380(8) . ?
C15 C16 1.524(8) . ?
C17 C18 1.393(9) . ?
C18 C19 1.375(10) . ?
C20 C21 1.513(9) . ?

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
C9 N1 C8 113.0(6) . . ?
C9 N1 C7 113.9(5) . . ?
C8 N1 C7 112.5(6) . . ?
C2 O2 C3 116.7(6) . . ?
O1 C2 O2 123.4(8) . . ?
O1 C2 C1 125.3(9) . . ?
O2 C2 C1 111.3(7) . . ?
C13 O3 C12 104.2(6) . . ?
O2 C3 C4 106.3(6) . . ?
O2 C3 C12 110.4(7) . . ?
C4 C3 C12 117.2(6) . . ?
C20 O4 C19 116.3(6) . . ?
C5 C4 C3 124.0(8) . . ?
C4 C5 C6 122.7(8) . . ?
C5 C6 C11 112.2(7) . . ?
C5 C6 C7 111.9(7) . . ?
C11 C6 C7 108.2(6) . . ?
C6 C7 N1 106.5(5) . . ?
C6 C7 C16 114.1(6) . . ?
N1 C7 C16 112.2(6) . . ?
N1 C9 C10 109.7(6) . . ?
C9 C10 C11 111.8(6) . . ?
C14 C11 C6 109.0(7) . . ?
C14 C11 C10 111.3(7) . . ?
C6 C11 C10 107.7(6) . . ?
C14 C11 C12 98.7(6) . . ?
C6 C11 C12 118.0(7) . . ?
C10 C11 C12 111.9(7) . . ?
O3 C12 C11 103.8(6) . . ?
O3 C12 C3 110.3(6) . . ?
C11 C12 C3 112.4(6) . . ?
C14 C13 C19 120.4(9) . . ?
C14 C13 O3 111.6(7) . . ?
C19 C13 O3 128.0(9) . . ?
C13 C14 C15 122.9(8) . . ?
C13 C14 C11 110.1(8) . . ?
C15 C14 C11 127.0(8) . . ?
C17 C15 C14 116.6(8) . . ?
C17 C15 C16 124.9(8) . . ?
C14 C15 C16 118.3(7) . . ?
C15 C16 C7 113.1(6) . . ?
C15 C17 C18 120.4(8) . . ?
C19 C18 C17 120.8(8) . . ?
C13 C19 C18 118.7(8) . . ?
C13 C19 O4 120.2(9) . . ?
C18 C19 O4 120.9(8) . . ?
O5 C20 O4 123.5(9) . . ?
O5 C20 C21 124.8(8) . . ?
O4 C20 C21 111.7(8) . . ?

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
N1 H1 Cl1 0.93 2.16 3.076(6) 170.5 .
O1S H1S Cl1 0.93(9) 2.36(10) 3.091(9) 135(8) .
O1S H2S Cl1 0.79(9) 2.52(10) 3.168(9) 141(11) 6_655

_diffrn_measured_fraction_theta_max 0.846
_diffrn_reflns_theta_full        24.98
_diffrn_measured_fraction_theta_full 0.846
_refine_diff_density_max         0.298
_refine_diff_density_min         -0.396
_refine_diff_density_rms         0.075