Chloro­thia­zide–pyridine (1/3)

Johnston, A.; Florence, A.J.; Kennedy, A.R.

doi:10.1107/S1600536808014360

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Pages o1105-o1106

doi:10.1107/S1600536808014360

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Chlorothiazide–pyridine (1/3)

Andrea Johnston,^a Alastair J. Florence ^a ^* and Alan R. Kennedy ^b

^aSolid-State Research Group, Strathclyde Institute of Pharmacy and Biomedical Sciences, The John Arbuthnott Building, University of Strathclyde, 27 Taylor Street, Glasgow G4 0NR, Scotland, and ^bWestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland
^*Correspondence e-mail: alastair.florence@strath.ac.uk

(Received 30 April 2008; accepted 13 May 2008; online 17 May 2008)

In the title compound, C₇H₆ClN₃O₄S₂·3C₅H₅N, (systematic name: 6-chloro-2H-1,2,4-benzothiadiazine-7-sulfonamide 1,1-dioxide pyridine trisolvate), chlorothiazide forms a 1:3 solvate with pyridine. The crystal structure is stabilized by strong intermolecular N—H⋯N hydrogen bonds.

Related literature

For details on experimental methods used to obtain this form, see: Florence et al. (2003 , 2006 ). For previous studies on the non-solvated form of chlorothaizide, see: Dupont & Dideberg (1970 ); Shankland et al. (1997 ). For solvated forms see: Johnston et al. (2007a ,b ); Johnston, Florence & Kennedy (2007 ); Fernandes, Florence et al. (2006 ); Fernandes, Shankland et al. (2007 ). For studies of intermolecular interactions in the related thiazide diuretic, hydrochlorothiazide, see: Johnston, Florence, Shankland et al. (2007 ). For additional literature on related thiazide compounds, see: Fabbiani et al. (2007 ); Fernandes, Johnston et al. (2007 ); Fernandes, Leech et al. (2007 ).

Experimental

Crystal data

C₇H₆ClN₃O₄S₂·3C₅H₅N
M_r = 533.02
Triclinic, $[P \overline 1]$
a = 9.0697 (15) Å
b = 11.863 (2) Å
c = 11.875 (2) Å
α = 100.691 (7)°
β = 98.667 (8)°
γ = 98.134 (7)°
V = 1222.1 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 123 (2) K
0.18 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
14598 measured reflections
4219 independent reflections
2998 reflections with I > 2σ(I)
R_int = 0.085

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.103
S = 1.04
4219 reflections
328 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N2S	0.91 (4)	1.86 (4)	2.774 (4)	177 (4)
N1—H5⋯N1Sⁱ	0.85 (4)	2.07 (4)	2.900 (4)	165 (4)
N1—H6⋯N3S	0.83 (3)	2.13 (4)	2.946 (4)	170 (3)
Symmetry code: (i) x-1, y, z.

Data collection: DENZO (Otwinowski & Minor, 1997 ) and COLLECT (Hooft, 1998 ); cell refinement: DENZO and COLLECT; data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014360/bx2144sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014360/bx2144Isup2.hkl

checkCIF report

Comment top

Chlorothiazide (CT) is a thiazide diuretic drug that is known to crystallize in at least one non-solvated form (Dupont & Dideberg, 1970; Shankland et al., 1997). The title compound was produced as part of an automated parallel crystallization study (Florence et al., 2006) of CT as part of a wider investigation that couples automated parallel crystallization with crystal structure prediction methodology to investigate the basic science underlying the solid-state diversity of thiazide diuretics including hydrochlorothiazide (Johnston et al., 2007), hydroflumethiazide (Fernandes, Johnston, A., et al., 2007), trichlormethiazide (Fernandes, P., Leech, C.K. et al., 2007), bendroflumethaizide (Fabbiani et al., 2007) and CT. The sample was identified as a novel form using multi-sample foil transmission X-ray powder diffraction analysis (Florence et al., 2003). Subsequent manual recrystallization from a saturated pyridine solution by slow evaporation at 278 K yielded a sample suitable for single-crystal X-ray diffraction (Fig. 1).

The molecules crystallize in space group P1 with one CT and three pyridine molecules in the asymmetric unit. The structure contains three unique N—H···N contacts (Table 1) between CT and solvent molecules whereby all hydrogen bond donors in CT, N1—H5, N1—H6 and N2—H2, are connected to a distinct pyridine molecule. The crystal structure is further stabilized by extensive offset face-to-face π^···^π interactions. All contacts combine to form a layered structure with layers comprising CT plus pyridine (residue B, Fig 1) alternating with pyridine residues C and D stacking in the [001] direction (Fig. 2).

Related literature top

For details on experimental methods used to obtain this form, see: Florence et al. (2003, 2006). For previous studies on the non-solvated form of chlorothaizide, see: Dupont & Dideberg (1970); Shankland et al. (1997). For solvated forms see: Johnston et al. (2007a,b); Johnston, Florence & Kennedy (2007); Fernandes, Florence et al. (2006); Fernandes, Shankland et al. (2007). For studies of intermolecular interactions in the related thiazide diuretic, hydrochlorothiazide, see: Johnston, Florence, Shankland et al. (2007). For additional literature on related thiazide compounds, see: Fabbiani et al. (2007); Fernandes, Johnston et al. (2007); Fernandes, Leech et al. (2007).

Experimental top

A single-crystal sample of the title compound was recrystallized from a saturated pyridine solution by isothermal solvent evaporation at 278 ^oK.

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure and atomic labelling of CT pyridine (1/3), showing 50% probablility displacement ellipsoids. 'S' in atomic labelling refers to solvent molecule.
	Fig. 2. The crystal packing in CT pyridine (1/3), viewed down the a-axis. Residues A, B, C and D are coloured green, blue, red and black.

6-chloro-2H-1,2,4-benzothiadiazine-7-sulfonamide 1,1-dioxide pyridine trisolvate top

Crystal data top

C₇H₆ClN₃O₄S₂·3C₅H₅N	Z = 2
M_r = 533.02	F(000) = 552
Triclinic, P1	D_x = 1.448 Mg m⁻³
Hall symbol: P -1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0697 (15) Å	Cell parameters from 3968 reflections
b = 11.863 (2) Å	θ = 1.0–27.1°
c = 11.875 (2) Å	µ = 0.37 mm⁻¹
α = 100.691 (7)°	T = 123 K
β = 98.667 (8)°	Cut fragment, colourless
γ = 98.134 (7)°	0.18 × 0.10 × 0.05 mm
V = 1222.1 (4) Å³

Data collection top

Nonius KappaCCD diffractometer	2998 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.085
Graphite monochromator	θ_max = 25.3°, θ_min = 1.8°
ϕ and ω scans	h = −10→0
14598 measured reflections	k = −13→14
4219 independent reflections	l = −13→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.059	w = 1/[σ²(F_o²) + (0.0253P)² + 1.8286P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.103	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.34 e Å⁻³
4219 reflections	Δρ_min = −0.49 e Å⁻³
328 parameters

Crystal data top

C₇H₆ClN₃O₄S₂·3C₅H₅N	γ = 98.134 (7)°
M_r = 533.02	V = 1222.1 (4) Å³
Triclinic, P1	Z = 2
a = 9.0697 (15) Å	Mo Kα radiation
b = 11.863 (2) Å	µ = 0.37 mm⁻¹
c = 11.875 (2) Å	T = 123 K
α = 100.691 (7)°	0.18 × 0.10 × 0.05 mm
β = 98.667 (8)°

Data collection top

Nonius KappaCCD diffractometer	2998 reflections with I > 2σ(I)
14598 measured reflections	R_int = 0.085
4219 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.34 e Å⁻³
4219 reflections	Δρ_min = −0.49 e Å⁻³
328 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	−0.11042 (9)	0.34675 (7)	0.54702 (7)	0.0161 (2)
S1	0.24543 (9)	−0.02698 (7)	0.33227 (7)	0.0127 (2)
S2	−0.16390 (10)	0.25714 (7)	0.26176 (7)	0.0134 (2)
O3	0.3649 (3)	0.0349 (2)	0.2890 (2)	0.0213 (6)
O1	0.1454 (3)	−0.1213 (2)	0.2501 (2)	0.0230 (6)
O2	−0.1320 (3)	0.20934 (19)	0.14895 (19)	0.0185 (6)
O4	−0.3120 (2)	0.2257 (2)	0.28715 (19)	0.0197 (6)
N3	0.3205 (3)	−0.0768 (2)	0.4406 (2)	0.0145 (7)
N2	0.2459 (3)	0.0587 (2)	0.5857 (3)	0.0121 (7)
N1	−0.1235 (4)	0.3939 (3)	0.2847 (3)	0.0178 (7)
C3	0.3177 (4)	−0.0285 (3)	0.5481 (3)	0.0137 (8)
H3	0.3730	−0.0587	0.6068	0.016*
C2	0.1548 (3)	0.1084 (3)	0.5117 (3)	0.0093 (7)
C7	0.1389 (3)	0.0736 (3)	0.3908 (3)	0.0098 (7)
C1	0.0429 (3)	0.1218 (3)	0.3176 (3)	0.0101 (7)
H1	0.0320	0.0968	0.2356	0.012*
C5	−0.0367 (3)	0.2054 (3)	0.3622 (3)	0.0098 (7)
C6	−0.0171 (4)	0.2406 (3)	0.4846 (3)	0.0108 (8)
C4	0.0752 (4)	0.1928 (3)	0.5575 (3)	0.0103 (7)
H4	0.0851	0.2173	0.6396	0.012*
N1S	0.7057 (3)	0.5432 (2)	0.4150 (3)	0.0195 (7)
C1S	0.6985 (4)	0.5848 (3)	0.5263 (3)	0.0202 (9)
H1S	0.7624	0.5608	0.5850	0.024*
C2S	0.6037 (4)	0.6605 (3)	0.5610 (3)	0.0242 (9)
H2S	0.6020	0.6870	0.6413	0.029*
C3S	0.5120 (4)	0.6967 (3)	0.4769 (4)	0.0291 (10)
H3S	0.4469	0.7500	0.4981	0.035*
C4S	0.5158 (4)	0.6547 (3)	0.3615 (4)	0.0308 (10)
H4S	0.4520	0.6769	0.3014	0.037*
C5S	0.6150 (4)	0.5793 (3)	0.3352 (3)	0.0255 (9)
H5S	0.6186	0.5516	0.2555	0.031*
N2S	0.2984 (3)	0.1270 (2)	0.8267 (2)	0.0200 (7)
C6S	0.2000 (4)	0.1232 (3)	0.9002 (3)	0.0237 (9)
H6S	0.0953	0.1160	0.8698	0.028*
C7S	0.2439 (5)	0.1292 (3)	1.0180 (3)	0.0335 (11)
H7S	0.1705	0.1246	1.0669	0.040*
C8S	0.3955 (5)	0.1419 (3)	1.0634 (3)	0.0319 (11)
H8S	0.4288	0.1467	1.1441	0.038*
C9S	0.4979 (4)	0.1475 (3)	0.9891 (3)	0.0263 (10)
H9S	0.6035	0.1570	1.0177	0.032*
C10S	0.4444 (4)	0.1391 (3)	0.8729 (3)	0.0237 (9)
H10S	0.5159	0.1420	0.8223	0.028*
N3S	0.1270 (3)	0.4933 (3)	0.1813 (3)	0.0245 (8)
C11S	0.2125 (4)	0.4257 (3)	0.1287 (3)	0.0302 (10)
H11S	0.2221	0.3542	0.1517	0.036*
C12S	0.2882 (4)	0.4540 (4)	0.0421 (3)	0.0336 (10)
H12S	0.3486	0.4034	0.0071	0.040*
C13S	0.2739 (4)	0.5576 (4)	0.0079 (3)	0.0313 (10)
H13S	0.3233	0.5792	−0.0520	0.038*
C14S	0.1872 (4)	0.6288 (3)	0.0617 (3)	0.0261 (9)
H14S	0.1760	0.7008	0.0403	0.031*
C15S	0.1165 (4)	0.5939 (3)	0.1478 (3)	0.0222 (9)
H15S	0.0573	0.6440	0.1851	0.027*
H2	0.261 (4)	0.083 (3)	0.665 (3)	0.034 (12)*
H5	−0.166 (4)	0.433 (3)	0.334 (3)	0.036 (13)*
H6	−0.046 (4)	0.420 (3)	0.262 (3)	0.014 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0195 (5)	0.0159 (5)	0.0153 (5)	0.0021 (4)	0.0067 (4)	0.0090 (4)
S1	0.0133 (5)	0.0150 (5)	0.0108 (5)	0.0021 (4)	0.0024 (4)	0.0065 (4)
S2	0.0141 (5)	0.0152 (5)	0.0120 (5)	0.0059 (4)	−0.0002 (4)	0.0045 (4)
O3	0.0187 (14)	0.0303 (15)	0.0237 (15)	0.0147 (12)	0.0141 (12)	0.0108 (11)
O1	0.0245 (15)	0.0209 (14)	0.0180 (14)	−0.0067 (11)	−0.0053 (11)	0.0089 (11)
O2	0.0274 (14)	0.0209 (14)	0.0083 (13)	0.0029 (10)	0.0014 (11)	0.0101 (11)
O4	0.0137 (13)	0.0261 (14)	0.0191 (14)	0.0106 (11)	−0.0027 (11)	0.0014 (11)
N3	0.0125 (16)	0.0176 (16)	0.0158 (18)	0.0070 (13)	0.0019 (13)	0.0067 (13)
N2	0.0136 (16)	0.0164 (16)	0.0066 (18)	0.0049 (13)	−0.0016 (13)	0.0037 (13)
N1	0.0214 (19)	0.0163 (17)	0.022 (2)	0.0100 (14)	0.0121 (16)	0.0064 (15)
C3	0.0083 (18)	0.0125 (18)	0.020 (2)	0.0083 (16)	0.0000 (16)	−0.0016 (15)
C2	0.0046 (17)	0.0105 (17)	0.012 (2)	0.0037 (14)	0.0000 (15)	−0.0015 (14)
C7	0.0072 (18)	0.0103 (17)	0.011 (2)	0.0013 (14)	0.0008 (15)	−0.0012 (14)
C1	0.0107 (18)	0.0127 (17)	0.0054 (19)	0.0002 (14)	0.0006 (15)	−0.0001 (14)
C5	0.0070 (18)	0.0113 (18)	0.010 (2)	0.0038 (14)	−0.0009 (15)	−0.0006 (14)
C6	0.0084 (18)	0.0083 (17)	0.016 (2)	0.0009 (14)	0.0062 (15)	0.0008 (14)
C4	0.0108 (18)	0.0115 (17)	0.0081 (19)	0.0037 (14)	0.0016 (15)	−0.0013 (14)
N1S	0.0182 (17)	0.0141 (16)	0.026 (2)	0.0021 (14)	0.0053 (15)	0.0029 (13)
C1S	0.020 (2)	0.016 (2)	0.024 (2)	0.0078 (17)	−0.0011 (17)	−0.0004 (16)
C2S	0.022 (2)	0.018 (2)	0.032 (2)	0.0007 (17)	0.0116 (19)	−0.0018 (17)
C3S	0.015 (2)	0.012 (2)	0.060 (3)	0.004 (2)	0.009 (2)	0.0043 (17)
C4S	0.019 (2)	0.026 (2)	0.044 (3)	0.017 (2)	−0.011 (2)	−0.0025 (18)
C5S	0.028 (2)	0.023 (2)	0.023 (2)	0.0068 (18)	0.0018 (19)	−0.0024 (18)
N2S	0.0232 (19)	0.0243 (18)	0.0105 (17)	0.0013 (13)	−0.0039 (15)	0.0077 (14)
C6S	0.018 (2)	0.021 (2)	0.026 (3)	−0.0027 (17)	0.0002 (18)	−0.0032 (17)
C7S	0.042 (3)	0.034 (2)	0.021 (3)	0.0019 (18)	0.017 (2)	−0.011 (2)
C8S	0.053 (3)	0.025 (2)	0.012 (2)	0.0080 (17)	−0.002 (2)	−0.006 (2)
C9S	0.027 (2)	0.022 (2)	0.025 (3)	0.0052 (17)	−0.011 (2)	0.0027 (18)
C10S	0.024 (2)	0.029 (2)	0.019 (2)	0.0038 (17)	0.0054 (19)	0.0084 (18)
N3S	0.031 (2)	0.0234 (18)	0.0208 (19)	0.0043 (14)	0.0106 (15)	0.0060 (15)
C11S	0.038 (3)	0.024 (2)	0.031 (3)	0.0078 (18)	0.008 (2)	0.0084 (19)
C12S	0.036 (3)	0.041 (3)	0.029 (3)	0.007 (2)	0.016 (2)	0.012 (2)
C13S	0.033 (2)	0.043 (3)	0.019 (2)	0.009 (2)	0.011 (2)	−0.001 (2)
C14S	0.033 (2)	0.024 (2)	0.021 (2)	0.0096 (17)	0.0016 (19)	0.0002 (19)
C15S	0.026 (2)	0.020 (2)	0.019 (2)	0.0021 (17)	0.0019 (18)	0.0035 (17)

Geometric parameters (Å, º) top

Cl1—C6	1.730 (3)	C2S—H2S	0.9500
S1—O3	1.435 (2)	C3S—C4S	1.376 (6)
S1—O1	1.439 (2)	C3S—H3S	0.9500
S1—N3	1.613 (3)	C4S—C5S	1.384 (5)
S1—C7	1.749 (3)	C4S—H4S	0.9500
S2—O4	1.434 (2)	C5S—H5S	0.9500
S2—O2	1.443 (2)	N2S—C10S	1.332 (4)
S2—N1	1.575 (3)	N2S—C6S	1.340 (4)
S2—C5	1.785 (3)	C6S—C7S	1.381 (5)
N3—C3	1.304 (4)	C6S—H6S	0.9500
N2—C3	1.342 (4)	C7S—C8S	1.376 (5)
N2—C2	1.383 (4)	C7S—H7S	0.9500
N2—H2	0.91 (4)	C8S—C9S	1.377 (5)
N1—H5	0.85 (4)	C8S—H8S	0.9500
N1—H6	0.83 (3)	C9S—C10S	1.372 (5)
C3—H3	0.9500	C9S—H9S	0.9500
C2—C4	1.393 (4)	C10S—H10S	0.9500
C2—C7	1.398 (4)	N3S—C11S	1.330 (5)
C7—C1	1.392 (4)	N3S—C15S	1.338 (4)
C1—C5	1.381 (4)	C11S—C12S	1.384 (5)
C1—H1	0.9500	C11S—H11S	0.9500
C5—C6	1.413 (4)	C12S—C13S	1.381 (5)
C6—C4	1.368 (4)	C12S—H12S	0.9500
C4—H4	0.9500	C13S—C14S	1.371 (5)
N1S—C5S	1.331 (5)	C13S—H13S	0.9500
N1S—C1S	1.337 (4)	C14S—C15S	1.381 (5)
C1S—C2S	1.380 (5)	C14S—H14S	0.9500
C1S—H1S	0.9500	C15S—H15S	0.9500
C2S—C3S	1.372 (5)

O3—S1—O1	116.53 (15)	C3S—C2S—C1S	118.5 (4)
O3—S1—N3	108.29 (14)	C3S—C2S—H2S	120.8
O1—S1—N3	108.71 (14)	C1S—C2S—H2S	120.8
O3—S1—C7	108.12 (14)	C2S—C3S—C4S	119.0 (4)
O1—S1—C7	109.09 (14)	C2S—C3S—H3S	120.5
N3—S1—C7	105.55 (15)	C4S—C3S—H3S	120.5
O4—S2—O2	119.51 (14)	C3S—C4S—C5S	118.3 (4)
O4—S2—N1	108.62 (17)	C3S—C4S—H4S	120.8
O2—S2—N1	108.54 (16)	C5S—C4S—H4S	120.8
O4—S2—C5	106.13 (14)	N1S—C5S—C4S	124.0 (4)
O2—S2—C5	104.48 (14)	N1S—C5S—H5S	118.0
N1—S2—C5	109.16 (16)	C4S—C5S—H5S	118.0
C3—N3—S1	121.8 (2)	C10S—N2S—C6S	116.7 (3)
C3—N2—C2	123.4 (3)	N2S—C6S—C7S	123.0 (4)
C3—N2—H2	115 (2)	N2S—C6S—H6S	118.5
C2—N2—H2	122 (2)	C7S—C6S—H6S	118.5
S2—N1—H5	118 (3)	C8S—C7S—C6S	119.0 (4)
S2—N1—H6	115 (2)	C8S—C7S—H7S	120.5
H5—N1—H6	125 (3)	C6S—C7S—H7S	120.5
N3—C3—N2	127.6 (3)	C7S—C8S—C9S	118.5 (4)
N3—C3—H3	116.2	C7S—C8S—H8S	120.7
N2—C3—H3	116.2	C9S—C8S—H8S	120.7
N2—C2—C4	120.0 (3)	C10S—C9S—C8S	118.6 (4)
N2—C2—C7	120.9 (3)	C10S—C9S—H9S	120.7
C4—C2—C7	119.1 (3)	C8S—C9S—H9S	120.7
C1—C7—C2	120.1 (3)	N2S—C10S—C9S	124.1 (3)
C1—C7—S1	120.3 (2)	N2S—C10S—H10S	118.0
C2—C7—S1	119.6 (2)	C9S—C10S—H10S	118.0
C5—C1—C7	121.2 (3)	C11S—N3S—C15S	116.9 (3)
C5—C1—H1	119.4	N3S—C11S—C12S	123.5 (4)
C7—C1—H1	119.4	N3S—C11S—H11S	118.2
C1—C5—C6	117.7 (3)	C12S—C11S—H11S	118.2
C1—C5—S2	118.0 (2)	C13S—C12S—C11S	118.4 (4)
C6—C5—S2	124.2 (2)	C13S—C12S—H12S	120.8
C4—C6—C5	121.7 (3)	C11S—C12S—H12S	120.8
C4—C6—Cl1	117.8 (2)	C14S—C13S—C12S	118.9 (3)
C5—C6—Cl1	120.5 (2)	C14S—C13S—H13S	120.6
C6—C4—C2	120.1 (3)	C12S—C13S—H13S	120.6
C6—C4—H4	119.9	C13S—C14S—C15S	118.7 (3)
C2—C4—H4	119.9	C13S—C14S—H14S	120.6
C5S—N1S—C1S	116.3 (3)	C15S—C14S—H14S	120.6
N1S—C1S—C2S	124.0 (3)	N3S—C15S—C14S	123.4 (3)
N1S—C1S—H1S	118.0	N3S—C15S—H15S	118.3
C2S—C1S—H1S	118.0	C14S—C15S—H15S	118.3

O3—S1—N3—C3	104.1 (3)	C1—C5—C6—C4	−1.1 (4)
O1—S1—N3—C3	−128.4 (3)	S2—C5—C6—C4	176.0 (2)
C7—S1—N3—C3	−11.5 (3)	C1—C5—C6—Cl1	178.9 (2)
S1—N3—C3—N2	5.9 (5)	S2—C5—C6—Cl1	−4.1 (4)
C2—N2—C3—N3	3.1 (5)	C5—C6—C4—C2	0.9 (5)
C3—N2—C2—C4	175.3 (3)	Cl1—C6—C4—C2	−179.0 (2)
C3—N2—C2—C7	−3.5 (5)	N2—C2—C4—C6	−178.8 (3)
N2—C2—C7—C1	177.9 (3)	C7—C2—C4—C6	0.0 (4)
C4—C2—C7—C1	−0.9 (4)	C5S—N1S—C1S—C2S	0.4 (5)
N2—C2—C7—S1	−4.4 (4)	N1S—C1S—C2S—C3S	−0.7 (5)
C4—C2—C7—S1	176.8 (2)	C1S—C2S—C3S—C4S	1.2 (5)
O3—S1—C7—C1	72.7 (3)	C2S—C3S—C4S—C5S	−1.4 (5)
O1—S1—C7—C1	−54.9 (3)	C1S—N1S—C5S—C4S	−0.6 (5)
N3—S1—C7—C1	−171.6 (2)	C3S—C4S—C5S—N1S	1.1 (5)
O3—S1—C7—C2	−105.0 (3)	C10S—N2S—C6S—C7S	−1.1 (5)
O1—S1—C7—C2	127.4 (3)	N2S—C6S—C7S—C8S	1.3 (6)
N3—S1—C7—C2	10.7 (3)	C6S—C7S—C8S—C9S	−0.4 (6)
C2—C7—C1—C5	0.8 (4)	C7S—C8S—C9S—C10S	−0.6 (5)
S1—C7—C1—C5	−176.9 (2)	C6S—N2S—C10S—C9S	0.0 (5)
C7—C1—C5—C6	0.2 (4)	C8S—C9S—C10S—N2S	0.8 (6)
C7—C1—C5—S2	−177.0 (2)	C15S—N3S—C11S—C12S	−0.5 (6)
O4—S2—C5—C1	117.4 (2)	N3S—C11S—C12S—C13S	−0.4 (6)
O2—S2—C5—C1	−9.8 (3)	C11S—C12S—C13S—C14S	0.8 (6)
N1—S2—C5—C1	−125.7 (3)	C12S—C13S—C14S—C15S	−0.4 (6)
O4—S2—C5—C6	−59.7 (3)	C11S—N3S—C15S—C14S	0.9 (5)
O2—S2—C5—C6	173.2 (3)	C13S—C14S—C15S—N3S	−0.5 (6)
N1—S2—C5—C6	57.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N2S	0.91 (4)	1.86 (4)	2.774 (4)	177 (4)
N1—H5···N1Sⁱ	0.85 (4)	2.07 (4)	2.900 (4)	165 (4)
N1—H6···N3S	0.83 (3)	2.13 (4)	2.946 (4)	170 (3)

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₇H₆ClN₃O₄S₂·3C₅H₅N
M_r	533.02
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	9.0697 (15), 11.863 (2), 11.875 (2)
α, β, γ (°)	100.691 (7), 98.667 (8), 98.134 (7)
V (Å³)	1222.1 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.18 × 0.10 × 0.05

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14598, 4219, 2998
R_int	0.085
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.103, 1.04
No. of reflections	4219
No. of parameters	328
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.49

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N2S	0.91 (4)	1.86 (4)	2.774 (4)	177 (4)
N1—H5···N1Sⁱ	0.85 (4)	2.07 (4)	2.900 (4)	165 (4)
N1—H6···N3S	0.83 (3)	2.13 (4)	2.946 (4)	170 (3)

Symmetry code: (i) x−1, y, z.

Acknowledgements

The authors thank the Basic Technology programme of the UK Research Councils for funding this work under the project Control and Prediction of the Organic Solid State (www.cposs.org.uk).

References

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