Powder study of hydrochlorothiazide form II

organic papers
Powder study of hydrochlorothiazide form II
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
Alastair Florence,a* Andrea
Johnston,a Philippe Fernandes,a
Kenneth Shankland,b
Howard N. E. Stevens,a
Sigrunn Osmundsena and
Alexander B. Mullena
a
Department of Pharmaceutical Sciences,
University of Strathclyde, 27 Taylor Street,
Glasgow G4 0NR, Scotland, and bISIS Facility,
Rutherford Appleton Laboratory, Chilton,
Didcot, Oxon OX11 0QX, England
The crystal structure of hydrochlorothiazide form II,
C7H8ClN3O4S2, was solved by simulated annealing from
laboratory X-ray powder diffraction data collected at room
temperature to 1.76 Å resolution. Subsequent Rietveld
refinement yielded an Rwp of 0.0376 to 1.49 Å resolution.
The molecules crystallize in the space group P21/c with one
molecule in the asymmetric unit. The structure is stabilized by
three N—H N and one N—H O hydrogen-bonded
intermolecular interaction.
Received 14 July 2005
Accepted 25 July 2005
Online 6 August 2005
Comment
Hydrochlorothiazide (HCT) is a thiazide diuretic which is
known to crystallize in at least one non-solvated form (Dupont
& Dideberg, 1972). A polycrystalline sample of a second
polymorph of HCT, form II, (I), was produced using a modified precipitation technique in which an acetone solution of
HCT was added to distilled water containing hydroxypropylmethylcellulose (grade E5LV, Dow Chemicals, USA) under
Correspondence e-mail:
alastair.florence@strath.ac.uk
Key indicators
Powder X-ray study
T = 298 K
Mean (C–C) = 0.002 Å
R factor = 0.033
wR factor = 0.038
Data-to-parameter ratio = 3.85
For details of how these key indicators were
automatically derived from the article, see
http://journals.iucr.org/e.
agitation. The resulting precipitate was immediately isolated
from solution by membrane filtration. The sample was identified as a new form using multisample X-ray powder
diffraction analysis (Florence et al., 2003). The sample was
Figure 1
# 2005 International Union of Crystallography
Printed in Great Britain – all rights reserved
o2798
Florence et al.
C7H8ClN3O4S2
Final observed (points), calculated (line) and difference [(yobs ycalc)/
(yobs)] profiles for the Rietveld refinement of the title compound.
doi:10.1107/S1600536805023640
Acta Cryst. (2005). E61, o2798–o2800
organic papers
Figure 2
The molecular structure with the atom-numbering scheme. Isotropic
displacement spheres are shown at the 50% probability level.
Figure 4
(Top) The R22 (8) (labelled A) and R44 (24) (labelled B) motifs within the
structure of (I). (Bottom left) The R24 (20) motif, shown with atoms not
involved in the motif omitted for clarity.
Figure 3
Packing diagram illustrating intermolecular contacts (dashed lines) in the
structure of (I). Unique contacts are labelled as follows: 1: N2 O3 =
2.905 (4) Å, O3 in the molecule at (x, 1 y, z); 2: N1 O1 =
2.920 (3) Å, O1 in the molecule at (x,1/2 y,-12 + z); 3: N3 O1 =
3.121 (3) Å, O1 in the molecule at (1 x, 12 + y, 12 z); 4: N3 N2 =
3.214 (2) Å, N2 in the molecule at (1 + x, 12 y, 12 + z); 5: C3 O2 =
3.416 (3) Å, O2 in the molecule at (x, 12 + y, 12 z). Contacts calculated
and illustrated using PLATON (Spek, 2003; program version 280604).
found to contain a trace amount of HCT form I (Dupont &
Dideberg, 1972).
The crystal structure of (I) was solved by simulated
annealing using laboratory X-ray powder diffraction data
(Fig. 1). The compound crystallizes in space group P21/c with
one molecule in the asymmetric unit (Fig. 2). In (I), the N2/S1/
C1/C2/N1/C3 ring in HCT displays a non-planar conformation, atoms N2 and C3 having the largest deviations [0.458 (1)
and 0.266 (1) Å, respectively] from the least-squares plane
through the aromatic ring. The sulfonamide side chain adopts
a torsion angle N3—S2—C5—C6 = 59.53 (19) , such that O1
eclipses H4, and atoms O4 and N3 are staggered with respect
to Cl1. In HCT form I (Dupont & Dideberg, 1972), this group
is rotated by approximately 120 compared with (I), such that
the amine group lies on the opposite side of the benzothiadiazine ring system.
The crystal structure is stabilized by a series of intermolecular contacts including three N—H N hydrogen bonds
Acta Cryst. (2005). E61, o2798–o2800
(contacts 1–3, Fig. 3), one N—H O hydrogen bond (contact
4) and a C—H O contact (contact 5). Contact 1 forms a
centrosymmetric R22 (8) dimer motif (Fig. 4, A), whilst contacts
3 and 4 produce a larger R44 (24) motif (Fig. 4, B) connecting
four molecules of HCT. Contacts 2 and 3 also combine to
produce an R24 (20) ring motif (Fig. 4, C).
Experimental
A sample of (I), obtained using the method described in the
Comment, was lightly ground in a mortar, loaded into a 0.7 mm
borosilicate glass capillary and mounted on the diffractometer. Data
were collected from a sample in a rotating 0.7 mm borosilicate glass
capillary using a variable count time scheme (Shankland et al., 1997;
Hill & Madsen, 2002).
Crystal data
Dx = 1.799 Mg m3
Cu K1 radiation
= 6.75 mm1
T = 298 K
Specimen shape: cylinder
12 0.7 mm
Specimen prepared at 298 K
Particle morphology: visual
estimate, prisms, white
C7H8ClN3O4S2
Mr = 297.75
Monoclinic, P21 =c
a = 9.4884 (5) Å
b = 8.3334 (4) Å
c = 15.1309 (7) Å
= 113.2087 (19)
V = 1099.59 (9) Å3
Z=4
Data collection
Bruker AXS D8 Advance
diffractometer
Specimen mounting: 0.7 mm
borosilicate capillary
Specimen mounted in transmission
mode
Scan method: step
Absorption correction: none
2min = 5.0, 2max = 65.0
Increment in 2 = 0.017
Florence et al.
C7H8ClN3O4S2
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organic papers
Refinement
355 reflections
92 parameters
Only H-atom coordinates refined
Weighting scheme based on
measured s.u.’s 1/(Yobs)2
(/)max = 0.005
Preferred orientation correction: a
spherical harmonics-based
preferred orientation correction
was applied with TOPAS during
the Rietveld refinement
Refinement on Inet
Rp = 0.033
Rwp = 0.038
Rexp = 0.023
RB = 0.013
S = 1.64
Excluded region(s): 62.1 to 65.0%
due to poor signal-to-noise
Profile function: fundamental
parameters with axial
divergence correction
Table 1
Selected geometric parameters (Å, ).
Cl1—C6
S1—O2
S1—O3
S1—N2
S1—C1
S2—O1
1.730 (2)
1.425 (3)
1.426 (2)
1.6438 (16)
1.7650 (17)
1.428 (2)
S2—O4
S2—N3
S2—C5
N1—C2
N1—C3
N2—C3
1.429
1.633
1.772
1.358
1.473
1.441
(3)
(2)
(2)
(2)
(2)
(2)
O2—S1—O3
O2—S1—N2
O2—S1—C1
O3—S1—N2
O3—S1—C1
N2—S1—C1
O1—S2—O4
O1—S2—N3
O1—S2—C5
O4—S2—N3
O4—S2—C5
N3—S2—C5
119.4 (2)
110.42 (13)
108.92 (17)
106.39 (18)
109.25 (10)
100.90 (10)
122.35 (19)
106.27 (14)
105.68 (13)
107.67 (14)
108.82 (13)
104.75 (10)
C2—N1—C3
S1—N2—C3
S1—C1—C2
S1—C1—C4
N1—C2—C1
N1—C2—C7
N1—C3—N2
S2—C5—C4
S2—C5—C6
Cl1—C6—C5
Cl1—C6—C7
123.27
113.58
119.80
119.55
121.84
120.34
108.10
117.40
124.83
121.28
117.16
(16)
(11)
(11)
(11)
(13)
(13)
(11)
(12)
(13)
(16)
(14)
Table 2
ment and exhibited no significant misfit to the data. Prior to Rietveld
refinement, atoms H7 and H8 were set to positions which satisfied the
hydrogen bonding contacts within the structure. The solved structure
was subsequently refined with data in the range 6.0–62.1 2 using a
restrained Rietveld (1969) method, as implemented in TOPAS
(Coelho, 2003), with the Rwp falling to 0.038 during the refinement. A
joint refinement strategy was implemented, in which the structure of
HCT form I (Dupont & Dideberg, 1972) was included to take account
of the impurity peaks arising from the presence of a small amount
(estimated at less than 5%) of this polymorph in the sample. In the
course of the refinement, the form I unit-cell and peak-shape parameters were allowed to vary, whilst all atomic coordinates were fixed.
All atomic positions (including H atoms) for the form II structure
were refined, subject to a series of restraints on bond lengths, bond
angles and planarity. Uiso(H) values were set at 0.044 Å2. A spherical
harmonics correction of intensities for preferred orientation was
applied in the final refinement. The observed and calculated
diffraction patterns for the refined crystal structure are shown in
Fig. 1.
Data collection: DIFFRAC plus XRD Commander (Kienle &
Jacob, 2003); cell refinement: TOPAS (Coelho, 2003); data reduction:
DASH (David et al., 2001); program(s) used to solve structure:
DASH; program(s) used to refine structure: TOPAS; molecular
graphics: PLATON (Spek, 2003); software used to prepare material
for publication: enCIFer (Allen et al., 2004).
We thank the Basic Technology programme of the UK
Research Councils for funding under the project Control and
Prediction of the Organic Solid State (http://www.cposs.org.uk). We also thank the CCLRC Centre for Molecular
Structure and Dynamics and Pharmaceutics International Inc.
(Baltimore, USA) for studentship funding for PF and SO,
respectively, and the EPSRC for grant GR/N07462/01.
Hydrogen-bond geometry (Å, ).
D—H A
i
N2—H5 O3
N1—H6 O1ii
N3—H7 O1iii
N3—H8 N2iv
C3—H1 O2v
C4—H4 O1
D—H
H A
D A
D—H A
References
0.95
0.94
0.95
0.95
0.95
0.95
2.03
2.02
2.21
2.37
2.56
2.37
2.905
2.920
3.121
3.214
3.416
2.803
152
159
161
149
150
108
Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J.
Appl. Cryst. 37, 335–338.
Boultif, A. & Louer, D. (1991). J. Appl. Cryst. 24, 987–993.
Coelho, A. A. (2003). TOPAS User Manual. Version 3.1. Bruker AXS GmbH,
Karlsruhe, Germany.
David, W. I. F., Shankland, K., Cole, J., Maginn, S., Motherwell, W. D. S. &
Taylor, R. (2001). DASH. Version 3.0 User Manual. Cambridge Crystallographic Data Centre, England.
David, W. I. F., Shankland, K. & Shankland, N. (1998). Chem. Commun. pp.
931–932.
Dupont, L. & Dideberg, O. (1972). Acta Cryst. B28, 2340–2347. (In French.)
Florence, A. J., Baumgartner, B., Weston, C., Shankland, N., Kennedy, A. R.,
Shankland, K. & David, W. I. F. (2003). J. Pharm. Sci. 92, 1930–1938.
Hill, R. J. & Madsen, I. C. (2002). Structure Determination from Powder
Diffraction Data, edited by W. I. F. David, K. Shankland, L. B. McCusker &
Ch. Baerlocher, pp.114–116. Oxford University Press.
Kienle, M. & Jacob, M. (2003). DIFFRAC plus XRD Commander. Version 2.3.
Bruker AXS GmbH, Karlsruhe, Germany.
Markvardsen, A. J., David, W. I. F., Johnson, J. C. & Shankland, K. (2001). Acta
Cryst. A57, 47–54.
Pawley, G. S. (1981). J. Appl. Cryst. 14, 357–361.
Rietveld, H. M. (1969). J. Appl. Cryst. 2, 65–71.
Shankland, K., David, W. I. F. & Sivia, D. S. (1997). J. Mater. Chem. 7, 569–572.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(4)
(3)
(3)
(2)
(3)
(3)
(1)
(1)
(1)
(1)
(1)
(1)
Symmetry codes: (i) x; y þ 1; z; (ii) x; y þ 12; þz 12; (iii) x þ 1; þy þ 12; z þ 12;
(iv) x þ 1; y þ 12; þz þ 12; (v) x; þy þ 12; z 12.
The diffraction pattern indexed to a monoclinic cell [M(20) = 25.9,
F(20) = 70.7; DICVOL-91; Boultif & Louer, 1991), and space group
P21/c was assigned from volume considerations and a statistical
consideration of the systematic absences (Markvardsen et al., 2001).
The data set was background subtracted and truncated to 52.2 2 for
Pawley (1981) fitting (2Pawley = 5.17) and the structure was solved
using the simulated annealing (SA) global optimization procedure
(David et al., 1998), which is now implemented in the DASH
computer program (David et al., 1998). The SA structure solution
involved the optimization of one molecule of HCT, totaling 7 degrees
of freedom. The best SA solution had a favourable
2SA/2Pawley ratio of 2.6, a chemically reasonable packing arrange-
o2800
Florence et al.
C7H8ClN3O4S2
Acta Cryst. (2005). E61, o2798–o2800
supporting information
supporting information
Acta Cryst. (2005). E61, o2798–o2800
[doi:10.1107/S1600536805023640]
Powder study of hydrochlorothiazide form II
Alastair Florence, Andrea Johnston, Philippe Fernandes, Kenneth Shankland, Howard N. E.
Stevens, Sigrunn Osmundsen and Alexander B. Mullen
S1. Comment
Hydrochlorothiazide (HCT) is a thiazide diuretic which is known to crystallize as a monoclinic non-solvated form
(Dupont & Dideberg, 1972). A polycrystalline sample of a second polymorph of HCT, form II, (I), was produced using a
modified precipitation technique in which an acetone solution of HCT was added to distilled water containing hydroxypropylmethylcellulose (grade E5LV, Dow Chemicals, USA) under agitation. The resuling precipitate was immediately
isolated from solution by membrane filtration. The sample was identified as a novel form using multisample X-ray
powder diffraction analysis (Florence et al., 2003). The sample was found to contain a trace amount of form I HCT
(Dupont & Dideberg, 1972).
The crystal structure of (I) was solved by simulated annealing using laboratory X-ray powder diffraction data (Fig. 1).
The compound crystallizes in space group P21/c with one molecule in the asymmetric unit (Fig. 2). In (I), the
N2/S1/C1/C2/N1/C3 ring in HCT displays a non-planar conformation, atoms N2 and C3 having the largest deviations
[0.458 (1) and −0.266 (1) Å, respectively] from the least squares plane through the aromatic ring. The sulfonamide side
chain adopts a torsion angle N3—S2—C5—C6 = 59.53 (19)°, such that O1 eclipses H4, and atoms O4 and N3 are
staggered with respect to Cl1. In form I HCT (Dupont & Dideberg, 1972), this group is rotated by approximately 120°
compared with (I), such that the amine group lies on the opposite side of the benzothiadiazine moiety.
The crystal structure is stabilized by a series of intermolecular contacts including three N—H···N hydrogen bonds
(contacts 1–3, Fig 3), one N—H···O hydrogen bond (contact 4) and a C—H···O contact (contact 5). Contact 1 forms a
centrosymmetric R22(8) dimer motif (Fig. 4, A), whilst contacts 3 and 4 produce a larger R44(24) motif (Fig. 4, B)
connecting four molecules of HCT. Contacts 2 and 3 also combine to produce an R24(20) ring motif (Fig. 4, C).
S2. Experimental
The raw material was lightly ground in a mortar, loaded into a 0.7 mm borosilicate glass capillary and mounted on the
diffractometer. Data were collected from a sample in a rotating 0.7 mm borosilicate glass capillary using a variable count
time scheme (Shankland et al., 1997; Hill & Madsen, 2002).
S3. Refinement
The diffraction pattern indexed to a monoclinic cell [M(20) = 25.9, F(20) = 70.7; DICVOL-91; Boultif & Louer, 1991),
and space group P21/c was assigned from volume considerations and a statistical consideration of the systematic absences
(Markvardsen et al., 2001). The data set was background subtracted and truncated to 52.2° 2θ for Pawley (1981) fitting
(χ2Pawley = 5.17) and the structure was solved using the simulated annealing (SA) global optimization procedure (David et
al., 1998 or???1988), which is now implemented in the DASH computer program (David et al., 2001). The SA structure
solution involved the optimization of one molecule of HCT totaling 7 degrees of freedom. The best SA solution had a
Acta Cryst. (2005). E61, o2798–o2800
sup-1
supporting information
favourable χ2SA/χ2Pawley ratio of 2.6, a chemically reasonable packing arrangement and exhibited no significant misfit to the
data. Prior to Rietveld refinement, atoms H7 and H8 were set to positions which satisfied the hydrogen bonding contacts
within the structure. The solved structure was subsequently refined against data in the range 6.0–62.1° 2θ using a
restrained Rietveld (1969) method, as implemented in TOPAS (Coelho, 2003), with the Rwp falling to 0.0376 during the
refinement. A joint refinement strategy was implemented, in which the structure of form I HCT (Dupont & Dideberg,
1972) was included to take account of the impurity peaks arising from the presence of a small amount (estimated at less
than 5%) of this polymorph in the sample. In the course of the refinement, the form I unit-cell and peak-shape parameters
were allowed to vary, whilst all atomic coordinates were fixed. All atomic positions (including H atoms) for the form II
structure were refined, subject to a series of restraints on bond lengths, bond angles and planarity. Uiso(H) values were set
at 0.044 Å2. A spherical harmonics correction of intensities for preferred orientation was applied in the final refinement.
The observed and calculated diffraction patterns for the refined crystal structure are shown in Fig. 1.
Figure 1
Final observed (points), calculated (line) and difference [(yobs-ycalc)/σ(yobs)] profiles for the Rietveld refinement of the title
compound.
Acta Cryst. (2005). E61, o2798–o2800
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supporting information
Figure 2
The atomic arrangement in (I), showing the contents of the asymmetric unit and the atom-numbering scheme. Isotropic
displacement ellipsoids are shown at the 50% probability level.
Figure 3
Packing diagram illustrating intermolecular contacts (dashed lines) in the structure of (I). Unique contacts are labelled as
follows: 1: N2···O3 = 2.905 (4) Å, O3 in the molecule at (−x, 1 − y, −z); 2: N1···O1 = 2.920 (3) Å, O1 in the molecule at
(x,1/2 − y,-1/2 + z); 3: N3···O1 = 3.121 (3) Å, O1 in the molecule at (1 − x, 1/2 + y, 1/2 − z); 4: N3···N2 = 3.214 (2) Å, N2
in the molecule at (1 + x, 1/2 − y, 1/2 + z); 5: C3···O2 = 3.416 (3) Å, O2 in the molecule at (−x, 1/2 + y, −1/2 − z).
Contacts calculated and illustrated using PLATON (Spek, 2003; program version 280604).
Acta Cryst. (2005). E61, o2798–o2800
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supporting information
Figure 4
(Top) The R22(8) (labelled A) and R44(24) (labelled B) motifs within the structure of (I). (Bottom left) The R24(20) motif,
shown with atoms not involved in the motif omitted for clarity.
(I)
Crystal data
C7H8ClN3O4S2
Mr = 297.75
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 9.4884 (5) Å
b = 8.3334 (4) Å
c = 15.1309 (7) Å
β = 113.2087 (19)°
V = 1099.59 (9) Å3
Z=4
Acta Cryst. (2005). E61, o2798–o2800
F(000) = 608.0
Dx = 1.799 Mg m−3
Cu Kα1 radiation, λ = 1.54056 Å
µ = 6.75 mm−1
T = 298 K
Particle morphology: visual estimate, prisms
white
cylinder, 12 × 0.7 mm
Specimen preparation: Prepared at 298 K
sup-4
supporting information
Data collection
Bruker AXS D8 Advance
diffractometer
Radiation source: sealed X-ray tube, BrukerAXS D8
Primary focussing, Ge 111 monochromator
Specimen mounting: 0.7 mm borosilicate
capillary
Data collection mode: transmission
Scan method: step
2θmin = 5.0°, 2θmax = 65.0°, 2θstep = 0.017°
Refinement
Least-squares matrix: selected elements only
Rp = 0.033
Rwp = 0.038
Rexp = 0.023
RBragg = 0.013
χ2 = 2.693
3529 data points
Excluded region(s): 62.1 to 65.0 due to poor
signal to noise
Profile function: Fundamental parameters with
axial divergence correction
92 parameters
47 restraints
1 constraint
Only H-atom coordinates refined
Weighting scheme based on measured s.u.'s
1/σ(Yobs)2
(Δ/σ)max = 0.005
Background function: Chebyshev polynomial
Preferred orientation correction: A spherical
harmonics-based preferred orientation
correction was applied with Topas during the
Rietveld refinement.
Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are
estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the
estimation of distances, angles and torsion angles
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
Cl1
S1
S2
O1
O2
O3
O4
N1
N2
N3
C1
C2
C3
C4
C5
C6
C7
H1
H2
H3
H4
H5
x
y
z
Uiso*/Ueq
0.75173 (15)
0.04110 (12)
0.53828 (12)
0.41184 (17)
−0.0243 (4)
−0.0117 (2)
0.6253 (3)
0.26907 (15)
0.02352 (17)
0.65720 (17)
0.24235 (12)
0.33184 (13)
0.10325 (14)
0.30954 (13)
0.46572 (15)
0.55492 (15)
0.49079 (13)
0.0814 (8)
0.0707 (10)
0.5541 (9)
0.2476 (9)
0.0555 (9)
0.1570 (3)
0.25043 (13)
−0.00769 (14)
−0.0340 (4)
0.1139 (3)
0.2956 (5)
−0.1367 (3)
0.3922 (3)
0.41019 (14)
0.10948 (14)
0.2284 (2)
0.3004 (2)
0.39732 (15)
0.1390 (2)
0.1121 (2)
0.1828 (3)
0.2748 (2)
0.4892 (11)
0.3011 (11)
0.3160 (10)
0.0937 (11)
0.5041 (11)
0.12511 (14)
−0.05257 (7)
0.22842 (7)
0.25537 (14)
−0.1111 (2)
0.02000 (11)
0.21308 (19)
−0.12379 (11)
−0.11982 (8)
0.31064 (14)
−0.00040 (9)
−0.04357 (9)
−0.18320 (9)
0.08259 (9)
0.12321 (12)
0.07942 (12)
−0.00157 (9)
−0.2234 (7)
−0.2187 (6)
−0.0320 (6)
0.1121 (6)
−0.0813 (6)
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.0269 (4)*
0.044*
0.044*
0.044*
0.044*
0.044*
Acta Cryst. (2005). E61, o2798–o2800
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supporting information
H6
H7
H8
0.3375 (9)
0.6580 (8)
0.7567 (9)
0.4321 (11)
0.2158 (10)
0.0647 (11)
−0.1498 (6)
0.2881 (6)
0.3389 (6)
0.044*
0.044*
0.044*
Geometric parameters (Å, º)
Cl1—C6
S1—O2
S1—O3
S1—N2
S1—C1
S2—O1
S2—O4
S2—N3
S2—C5
N1—C2
N1—C3
N2—C3
N1—H6
1.730 (2)
1.425 (3)
1.426 (2)
1.6438 (16)
1.7650 (17)
1.428 (2)
1.429 (3)
1.633 (2)
1.772 (2)
1.358 (2)
1.473 (2)
1.441 (2)
0.943 (9)
N2—H5
N3—H7
N3—H8
C1—C2
C1—C4
C2—C7
C4—C5
C5—C6
C6—C7
C3—H1
C3—H2
C4—H4
C7—H3
0.951 (9)
0.951 (8)
0.946 (9)
1.3946 (19)
1.381 (2)
1.4031 (19)
1.381 (2)
1.394 (2)
1.368 (2)
0.949 (9)
0.947 (9)
0.946 (9)
0.953 (9)
O2—S1—O3
O2—S1—N2
O2—S1—C1
O3—S1—N2
O3—S1—C1
N2—S1—C1
O1—S2—O4
O1—S2—N3
O1—S2—C5
O4—S2—N3
O4—S2—C5
N3—S2—C5
C2—N1—C3
S1—N2—C3
C2—N1—H6
C3—N1—H6
S1—N2—H5
C3—N2—H5
S2—N3—H7
S2—N3—H8
H7—N3—H8
C2—C1—C4
S1—C1—C2
119.4 (2)
110.42 (13)
108.92 (17)
106.39 (18)
109.25 (10)
100.90 (10)
122.35 (19)
106.27 (14)
105.68 (13)
107.67 (14)
108.82 (13)
104.75 (10)
123.27 (16)
113.58 (11)
116.1 (6)
118.7 (5)
110.9 (5)
110.2 (6)
112.6 (5)
112.0 (6)
112.5 (8)
120.66 (12)
119.80 (11)
S1—C1—C4
C1—C2—C7
N1—C2—C1
N1—C2—C7
N1—C3—N2
C1—C4—C5
S2—C5—C4
S2—C5—C6
C4—C5—C6
Cl1—C6—C5
Cl1—C6—C7
C5—C6—C7
C2—C7—C6
N1—C3—H1
N1—C3—H2
N2—C3—H1
N2—C3—H2
H1—C3—H2
C1—C4—H4
C5—C4—H4
C2—C7—H3
C6—C7—H3
119.55 (11)
117.82 (13)
121.84 (13)
120.34 (13)
108.10 (11)
121.48 (13)
117.40 (12)
124.83 (13)
117.77 (15)
121.28 (16)
117.16 (14)
121.56 (15)
120.67 (13)
109.0 (6)
110.7 (6)
109.1 (6)
107.5 (6)
112.3 (8)
119.6 (5)
118.9 (6)
119.7 (5)
119.5 (5)
O2—S1—N2—C3
O3—S1—N2—C3
C1—S1—N2—C3
O2—S1—C1—C2
−62.4 (2)
166.72 (13)
52.73 (12)
96.13 (19)
S1—N2—C3—N1
C2—C1—C4—C5
S1—C1—C2—C7
C4—C1—C2—N1
−66.39 (16)
−2.8 (2)
−177.71 (12)
−178.32 (17)
Acta Cryst. (2005). E61, o2798–o2800
sup-6
supporting information
O2—S1—C1—C4
O3—S1—C1—C2
O3—S1—C1—C4
N2—S1—C1—C2
N2—S1—C1—C4
O1—S2—C5—C4
O1—S2—C5—C6
O4—S2—C5—C4
O4—S2—C5—C6
N3—S2—C5—C4
N3—S2—C5—C6
C3—N1—C2—C7
C3—N1—C2—C1
C2—N1—C3—N2
−83.47 (19)
−131.9 (2)
48.5 (2)
−20.07 (15)
160.33 (13)
−7.5 (2)
171.5 (2)
125.57 (18)
−55.4 (2)
−119.51 (15)
59.5 (2)
166.79 (16)
−13.0 (3)
44.9 (2)
S1—C1—C2—N1
S1—C1—C4—C5
C4—C1—C2—C7
N1—C2—C7—C6
C1—C2—C7—C6
C1—C4—C5—S2
C1—C4—C5—C6
S2—C5—C6—C7
S2—C5—C6—Cl1
C4—C5—C6—Cl1
C4—C5—C6—C7
C5—C6—C7—C2
Cl1—C6—C7—C2
2.1 (2)
176.79 (13)
1.9 (2)
179.82 (19)
−0.4 (2)
−178.81 (13)
2.1 (3)
−179.59 (15)
0.7 (3)
179.73 (17)
−0.6 (3)
−0.3 (3)
179.46 (16)
Hydrogen-bond geometry (Å, º)
D—H···A
i
N2—H5···O3
N1—H6···O1ii
N3—H7···O1iii
N3—H8···N2iv
C3—H1···O2v
C4—H4···O1
D—H
H···A
D···A
D—H···A
0.95 (1)
0.94 (1)
0.95 (1)
0.95 (1)
0.95 (1)
0.95 (1)
2.03 (1)
2.02 (1)
2.21 (1)
2.37 (1)
2.56 (1)
2.37 (1)
2.905 (4)
2.920 (3)
3.121 (3)
3.214 (2)
3.416 (3)
2.803 (3)
152 (1)
159 (1)
161 (1)
149 (1)
150 (1)
108 (1)
Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x+1, −y+1/2, z+1/2; (v) −x, y+1/2, −z−1/2.
Acta Cryst. (2005). E61, o2798–o2800
sup-7
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