Two polymorphs of chlorpropamide: the [delta]-form and the high-temperature [epsilon]-form

The [epsilon]-form of chlorpropamide [systematic name: 4-chloro-N-(propyl­amino­carbonyl)benzene­sulfonamide], C₁₀H₁₃ClN₂O₃S, has been obtained as single crystals from solution (and not as a polycrystalline sample by heating the [alpha]-, [gamma]- or [delta]-forms). The results of anisotropic structure refinements for the [epsilon]- and [delta]-forms are reported. The density of the [delta]-polymorph is the highest, and that of the [epsilon]-polymorph the lowest, among the five known chlorpropamide polymorphs. The main inter­molecular hydrogen-bonding pattern in polymorphs [delta] and [epsilon] is the same as in polymorphs [alpha], [beta] and [gamma], but the conformations differ. The densities of the polymorphs were found to depend on the mol­ecular conformations.

S1. Comment

Chlorpropamide, 4-chloro-N-(propylaminocarbonyl)benzenesulfonamide, (I), is an antidiabetic drug and the crystal structures have been reported for three polymorphs, α (Koo et al., 1980), β (Drebushchak et al., 2006) and γ (Drebushchak et al., 2007). This work reports the crystal structures of two additional polymorphs, δ and ε. The latter has previously only been obtained by heating of the α-, γ- or δ-forms as a polycrystalline sample. Although the structure of this form was claimed to be solved from powder diffraction data, the atomic coordinates were not published (Wildfong et al., 2007). Our work reports the results of a single-crystal structure determination of ε-chlorpropamide, which became possible after this polymorph was obtained for the first time as single crystals from solution. The δ-form is a new polymorph first described by Drebushchak et al. (2008), where the structure was refined isotropically to R[F² > 2σ(F²)] = 0.187 because of the poor quality of the crystals available. The quality of the data was, however, sufficiently good to establish reliably the gauche conformation of the alkyl tail. All polymorphs were characterized by differential scanning calorimetry (Drebushchak et al., 2008) and FT–IR spectroscopy (Chesalov et al., 2008).

The asymmetric unit of both the δ- and ε-forms contains only one molecule, like the other polymorphs do (Fig. 1). Bond lengths and angles in all the polymorphs are similar, and agree with statistical data from Mogul [Bruno et al., 2004; Cambridge Structural Database, Version 5.29 (Allen, 2002)]. The conformations are different (Table 1; Fig. 1). In the δ-polymorph, the –CH₂—CH₃ alkyl tail and the benzene ring are on opposite sides of the N1/C7/O3/N2/C8 plane, as in the α-polymorph (orientation I), whereas in the ε-form they are on the same side, as in the β- and γ-forms (orientation II). The δ-form differs from all other polymorphs in the gauche conformation of the propyl tail (compare the N2—C8—C9—C10 torsion angle in Table 1 with the values close to 180° observed for this angle in all the other forms). The ε-form differs significantly from the other polymorphs in the angle between the planes of the benzene ring and atoms N1/C7/O3/N2/C8.

In all the chlorpropamide polymorphs to date, the molecules are linked via N—H···O hydrogen bonds (Table 2) to form infinite ribbons. The N1—H1N···O3ⁱ hydrogen bond [symmetry code: (i) x-1/2, -y+3/2, -z+1] in the ε-polymorph (Table 2) is the shortest of all the hydrogen bonds observed in the chlorpropamide polymorphs, although the ε-form is the least dense. The structural motif in the δ- and ε-polymorphs is the same as in the α- and γ-forms (Z-shaped), in contrast with the π-shaped motif observed in the β-form (Fig. 2). Despite having the same Z-shaped motif, the ribbons in the α-, γ-, δ- and ε-polymorphs pack in different ways. Orientation II of the alkyl tails does not allow the Z-shaped ribbons to pack in dense piles (Fig. 3), which is why structures with tail orientation I are denser. The difference between the highest (δ-form, tail orientation I) and lowest (ε-form, tail orientation II) density values is 5.6%.

The structural data obtained for the ε-form explain the peculiar behaviour of the β-form with increasing temperature, compared with that of the α-, γ- and δ-polymorphs. In contrast with the other forms, which are converted into the ε-form on heating, samples of the β-form often melt prior to transformation into the ε-form (Drebushchak et al., 2008). The preservation of the packing motif is more important for these structural transformations than the similarity or difference in the molecular conformations. The Z-shaped motif is inherited after α → ε, γ → ε and δ → ε polymorphic transitions, while the conformation of the molecules changes significantly. The flexible alkyl tail rotates during the transitions α → ε and δ → ε, changing its orientation from type I to type II. The –CH₂—CH₂—CH₃ tail changes its conformation from gauche to trans in the transition δ → ε. However, these transitions do not require the breaking of intermolecular hydrogen bonds or rotation of the molecules to a noticeable extent with respect to each other. On the contrary, the β → ε transformation is related to a change from the π-shaped motif to the Z-shaped one, requiring a change in the orientation of every second molecule in the ribbon (Fig. 2). Therefore, this process seems kinetically hindered in the solid state.

The chlorpropamide polymorphs can be obtained by crystallization from the same solvents under different conditions, and are often present as mixtures in the same batch. The different conformations and packing motifs of nearest neighbours in the different polymorphs might reflect the different conformations and molecular aggregates co-existing in solution, giving rise to different crystal structures depending on the crystallization conditions (Gavezzotti, 2007).

Related literature

For related literature, see: Allen (2002); Bruno et al. (2004); Chesalov et al. (2008); Drebushchak et al. (2006, 2007, 2008); Gavezzotti (2007); Koo et al. (1980); Sheldrick (2008); Wildfong et al. (2007).

S2. Experimental

Single crystals of the δ-form were obtained by recrystallization of a commercial sample of chlorpropamide from a heptane–ethylacetate [Solvent ratio?] solution on rapid cooling, as described by Drebushchak et al. (2008). Powder diffraction did not reveal the presence of any other polymorphs in this sample. Single crystals of the ε-polymorph were obtained by dissolving a commercial sample of chlorpropamide (30 mg) in chloroform (0.5 ml) and keeping it at 373 K until complete evaporation of the solvent. According to X-ray powder diffraction, the batch contained a mixture of the ε-form as the dominant phase and the α- and β-forms as minor admixtures. Single crystals of the ε-form for X-ray diffraction study could be selected from the batch.

S3. Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 (aromatic), 0.96 (CH₃) or 0.97 Å (CH₂) and N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(C,N). A DFIX restraint (SHELXL97; Sheldrick, 2008) was used to refine atom C10. The δ- and ε-polymorphs show poor diffraction properties, which may be a result of the high mobility of the alkyl chains, manifested by the large values of the atomic displacement parameters for C9 and C10 (Fig. 1). The same was observed previously for the β-polymorph (Drebushchak et al., 2006).

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999) and publCIF (Westrip, 2007).

Figures

	Fig. 1. The molecular structure of (a) δ-chlorpropamide and (b) ε-chlorpropamide, viewed along the O3—C7 bond, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The hydrogen-bonded ribbons: (a) in the δ-form of chlorpropamide viewed along the a axis (Z-shaped motif); (b) in the ε-form, viewed along the c axis (Z-shaped motif); (c) in the β-form, viewed along the b axis (π-shaped motif) (Drebushchak et al., 2006).
	Fig. 3. Comparative views of the crystal packing of the polymorphs of chlorpropamide, showing (a) the δ-form, viewed along the a axis, and (b) the ε-form, viewed along the c axis. Hydrogen bonds are shown as dashed lines. Broad arrows mark the distances between neighbouring hydrogen-bonded ribbons.

(d-form) 4-chloro-N-(propylaminocarbonyl)benzenesulfonamide

Crystal data

C10H13ClN2O3S	Dx = 1.455 Mg m^−3
Mr = 276.73	Melting point: Kinetic phase transition (Drebushchak et al., 2008) K
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1546 reflections
a = 9.3198 (4) Å	θ = 4.3–67.0°
b = 10.3218 (3) Å	µ = 4.24 mm^−1
c = 26.2663 (10) Å	T = 295 K
V = 2526.74 (16) Å^3	Plate, colourless
Z = 8	0.22 × 0.14 × 0.03 mm
F(000) = 1152

Data collection

Oxford Diffraction KM4 CCD diffractometer	2159 independent reflections
Radiation source: Ultra (Cu) X-ray Source	1318 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.074
Detector resolution: 10.3457 pixels mm^-1	θmax = 66.6°, θmin = 5.8°
ω scans	h = −10→10
Absorption correction: multi-scan CrysAlis RED (Oxford Diffraction, 2008)	k = −12→12
Tmin = 0.432, Tmax = 0.883	l = −17→31
6522 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.062	H-atom parameters constrained
wR(F^2) = 0.169	w = 1/[σ^2(Fo^2) + (0.1038P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max < 0.001
2159 reflections	Δρmax = 0.35 e Å^−3
156 parameters	Δρmin = −0.38 e Å^−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0015 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1637 (6)	0.6441 (5)	0.29327 (18)	0.0748 (14)
C2	0.0520 (6)	0.7283 (6)	0.2962 (2)	0.0883 (17)
H2	−0.0166	0.7316	0.2705	0.106*
C3	0.0419 (5)	0.8098 (5)	0.33845 (19)	0.0723 (13)
H3	−0.0332	0.8687	0.3411	0.087*
C4	0.1438 (4)	0.8024 (4)	0.37608 (14)	0.0489 (9)
C5	0.2565 (5)	0.7192 (4)	0.37148 (16)	0.0622 (11)
H5	0.3262	0.7163	0.3968	0.075*
C6	0.2684 (6)	0.6392 (5)	0.32948 (18)	0.0743 (14)
H6	0.3460	0.5833	0.3260	0.089*
C7	0.1512 (4)	0.7253 (4)	0.50360 (14)	0.0478 (9)
C8	0.1343 (5)	0.5476 (5)	0.56420 (18)	0.0658 (12)
H8A	0.2368	0.5440	0.5580	0.079*
H8B	0.0940	0.4643	0.5548	0.079*
C9	0.1095 (9)	0.5695 (7)	0.6193 (3)	0.126 (3)
H9A	0.0089	0.5527	0.6260	0.151*
H9B	0.1639	0.5045	0.6377	0.151*
C10	0.1437 (10)	0.6939 (8)	0.6413 (3)	0.192 (5)
H10A	0.2441	0.7114	0.6369	0.231*
H10B	0.1212	0.6929	0.6770	0.231*
H10C	0.0885	0.7601	0.6248	0.231*
N1	0.0706 (3)	0.8150 (3)	0.47570 (12)	0.0522 (9)
H1N	−0.0185	0.8230	0.4836	0.063*
N2	0.0718 (3)	0.6471 (3)	0.53210 (13)	0.0558 (9)
H2N	−0.0199	0.6557	0.5315	0.067*
O1	0.0195 (3)	0.9955 (3)	0.41986 (11)	0.0597 (8)
O2	0.2709 (3)	0.9501 (3)	0.44145 (11)	0.0563 (8)
O3	0.2821 (3)	0.7228 (3)	0.50048 (11)	0.0575 (8)
S1	0.13079 (10)	0.90580 (9)	0.42946 (4)	0.0487 (4)
Cl1	0.1775 (2)	0.54007 (18)	0.24117 (6)	0.1281 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.094 (4)	0.076 (3)	0.054 (3)	−0.013 (3)	0.003 (3)	−0.006 (2)
C2	0.073 (4)	0.118 (4)	0.074 (3)	−0.006 (3)	−0.018 (3)	−0.020 (3)
C3	0.051 (3)	0.096 (3)	0.070 (3)	0.007 (3)	−0.009 (2)	−0.008 (3)
C4	0.041 (2)	0.056 (2)	0.049 (2)	−0.0021 (19)	0.0012 (19)	0.0094 (18)
C5	0.065 (3)	0.069 (3)	0.053 (2)	0.013 (2)	−0.006 (2)	0.002 (2)
C6	0.093 (4)	0.071 (3)	0.059 (3)	0.017 (3)	0.002 (3)	0.000 (2)
C7	0.037 (2)	0.060 (2)	0.046 (2)	0.003 (2)	0.0002 (18)	−0.0057 (18)
C8	0.063 (3)	0.068 (2)	0.066 (3)	0.001 (2)	−0.003 (2)	0.012 (2)
C9	0.152 (6)	0.149 (6)	0.076 (4)	0.039 (6)	−0.027 (4)	0.030 (4)
C10	0.203 (9)	0.232 (10)	0.142 (7)	0.117 (8)	−0.090 (7)	−0.098 (8)
N1	0.0331 (17)	0.067 (2)	0.056 (2)	0.0077 (16)	0.0051 (15)	0.0059 (16)
N2	0.0381 (18)	0.071 (2)	0.059 (2)	0.0010 (17)	0.0028 (16)	0.0101 (18)
O1	0.0481 (16)	0.0558 (14)	0.0752 (19)	0.0118 (14)	0.0052 (14)	0.0082 (14)
O2	0.0383 (16)	0.0602 (15)	0.0705 (18)	−0.0106 (13)	0.0000 (13)	−0.0031 (14)
O3	0.0322 (15)	0.0715 (18)	0.0687 (18)	0.0010 (13)	0.0008 (13)	0.0111 (15)
S1	0.0384 (6)	0.0532 (5)	0.0544 (6)	0.0019 (5)	0.0027 (5)	0.0028 (5)
Cl1	0.1794 (19)	0.1276 (13)	0.0775 (10)	−0.0071 (13)	−0.0020 (10)	−0.0391 (10)

Geometric parameters (Å, º)

C1—C2	1.359 (7)	C8—N2	1.450 (5)
C1—C6	1.363 (7)	C8—C9	1.483 (8)
C1—Cl1	1.744 (5)	C8—H8A	0.9700
C2—C3	1.395 (7)	C8—H8B	0.9700
C2—H2	0.9300	C9—C10	1.444 (9)
C3—C4	1.372 (6)	C9—H9A	0.9700
C3—H3	0.9300	C9—H9B	0.9700
C4—C5	1.363 (5)	C10—H10A	0.9600
C4—S1	1.766 (4)	C10—H10B	0.9600
C5—C6	1.383 (6)	C10—H10C	0.9600
C5—H5	0.9300	N1—S1	1.634 (3)
C6—H6	0.9300	N1—H1N	0.8600
C7—O3	1.223 (4)	N2—H2N	0.8600
C7—N2	1.326 (5)	O1—S1	1.413 (3)
C7—N1	1.399 (5)	O2—S1	1.419 (3)
C2—C1—C6	122.1 (5)	H8A—C8—H8B	107.7
C2—C1—Cl1	119.7 (4)	C10—C9—C8	119.5 (7)
C6—C1—Cl1	118.2 (4)	C10—C9—H9A	107.4
C1—C2—C3	118.8 (5)	C8—C9—H9A	107.4
C1—C2—H2	120.6	C10—C9—H9B	107.4
C3—C2—H2	120.6	C8—C9—H9B	107.4
C4—C3—C2	119.5 (4)	H9A—C9—H9B	107.0
C4—C3—H3	120.2	C9—C10—H10A	109.5
C2—C3—H3	120.2	C9—C10—H10B	109.5
C5—C4—C3	120.3 (4)	H10A—C10—H10B	109.5
C5—C4—S1	120.2 (3)	C9—C10—H10C	109.5
C3—C4—S1	119.4 (3)	H10A—C10—H10C	109.5
C4—C5—C6	120.6 (4)	H10B—C10—H10C	109.5
C4—C5—H5	119.7	C7—N1—S1	125.8 (3)
C6—C5—H5	119.7	C7—N1—H1N	117.1
C1—C6—C5	118.5 (5)	S1—N1—H1N	117.1
C1—C6—H6	120.7	C7—N2—C8	122.4 (3)
C5—C6—H6	120.7	C7—N2—H2N	118.8
O3—C7—N2	125.5 (4)	C8—N2—H2N	118.8
O3—C7—N1	120.9 (4)	O1—S1—O2	120.26 (17)
N2—C7—N1	113.5 (3)	O1—S1—N1	104.88 (16)
N2—C8—C9	113.4 (4)	O2—S1—N1	109.63 (17)
N2—C8—H8A	108.9	O1—S1—C4	107.72 (18)
C9—C8—H8A	108.9	O2—S1—C4	107.93 (17)
N2—C8—H8B	108.9	N1—S1—C4	105.49 (17)
C9—C8—H8B	108.9
C6—C1—C2—C3	−1.9 (8)	O3—C7—N2—C8	0.7 (6)
Cl1—C1—C2—C3	179.3 (4)	N1—C7—N2—C8	−179.6 (4)
C1—C2—C3—C4	−0.6 (8)	C9—C8—N2—C7	115.4 (6)
C2—C3—C4—C5	2.2 (7)	C7—N1—S1—O1	−169.5 (3)
C2—C3—C4—S1	180.0 (4)	C7—N1—S1—O2	−39.1 (4)
C3—C4—C5—C6	−1.4 (6)	C7—N1—S1—C4	76.9 (3)
S1—C4—C5—C6	−179.2 (4)	C5—C4—S1—O1	169.9 (3)
C2—C1—C6—C5	2.7 (8)	C3—C4—S1—O1	−7.9 (4)
Cl1—C1—C6—C5	−178.5 (4)	C5—C4—S1—O2	38.6 (4)
C4—C5—C6—C1	−1.0 (7)	C3—C4—S1—O2	−139.2 (3)
N2—C8—C9—C10	−50.9 (8)	C5—C4—S1—N1	−78.5 (4)
O3—C7—N1—S1	11.8 (5)	C3—C4—S1—N1	103.7 (4)
N2—C7—N1—S1	−167.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3^i	0.86	1.96	2.788 (4)	160
N2—H2N···O2^i	0.86	2.34	3.058 (4)	141
N2—H2N···O3^i	0.86	2.38	3.135 (4)	146

Symmetry code: (i) x−1/2, −y+3/2, −z+1.

(e-form) 4-chloro-N-((propylaminocarbonyl)benzenesulfonamide

Crystal data

C10H13ClN2O3S	Dx = 1.375 Mg m^−3
Mr = 276.73	Melting point: 401 K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2528 reflections
a = 19.9121 (10) Å	θ = 3.0–29.1°
b = 7.3459 (4) Å	µ = 0.44 mm^−1
c = 9.1384 (4) Å	T = 295 K
V = 1336.69 (12) Å^3	Plate, colourless
Z = 4	0.40 × 0.15 × 0.03 mm
F(000) = 576

Data collection

Oxford Diffraction KM4 CCD diffractometer	2447 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1556 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 10.3457 pixels mm^-1	θmax = 25.7°, θmin = 3.0°
ω scans	h = −24→21
Absorption correction: multi-scan CrysAlis RED (Oxford Diffraction, 2008)	k = −7→8
Tmin = 0.893, Tmax = 0.987	l = −11→10
6456 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0453P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.87	(Δ/σ)max < 0.001
2447 reflections	Δρmax = 0.33 e Å^−3
155 parameters	Δρmin = −0.26 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 1102 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (8)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.28064 (17)	0.3459 (5)	0.4054 (5)	0.0664 (10)
C2	0.3165 (2)	0.3293 (5)	0.2769 (4)	0.0656 (11)
H2	0.3165	0.4229	0.2083	0.079*
C3	0.35196 (19)	0.1731 (5)	0.2520 (4)	0.0618 (10)
H3	0.3764	0.1601	0.1659	0.074*
C4	0.35178 (16)	0.0354 (5)	0.3534 (3)	0.0456 (8)
C5	0.31681 (17)	0.0525 (5)	0.4813 (4)	0.0634 (10)
H5	0.3173	−0.0404	0.5504	0.076*
C6	0.2804 (2)	0.2111 (6)	0.5065 (4)	0.0762 (13)
H6	0.2560	0.2245	0.5925	0.091*
C7	0.50857 (15)	0.0304 (4)	0.3303 (3)	0.0424 (7)
C8	0.59407 (17)	0.2667 (4)	0.3088 (4)	0.0573 (9)
H8A	0.6344	0.2729	0.2494	0.069*
H8B	0.6074	0.2325	0.4071	0.069*
C9	0.5622 (2)	0.4508 (5)	0.3133 (6)	0.0958 (14)
H9A	0.5222	0.4456	0.3738	0.115*
H9B	0.5486	0.4852	0.2152	0.115*
C10	0.6087 (3)	0.5920 (7)	0.3728 (7)	0.141 (3)
H10A	0.6131	0.5764	0.4767	0.170*
H10B	0.5910	0.7108	0.3525	0.170*
H10C	0.6520	0.5796	0.3275	0.170*
N1	0.46851 (13)	−0.0948 (4)	0.2541 (3)	0.0469 (7)
H1N	0.4823	−0.1353	0.1710	0.056*
N2	0.54965 (13)	0.1249 (4)	0.2493 (3)	0.0480 (7)
H2N	0.5508	0.1034	0.1568	0.058*
O1	0.36688 (11)	−0.2571 (3)	0.19618 (19)	0.0549 (6)
O2	0.40594 (11)	−0.2620 (3)	0.4524 (2)	0.0527 (6)
O3	0.50327 (11)	0.0410 (3)	0.4653 (2)	0.0604 (6)
S1	0.39692 (4)	−0.16578 (10)	0.31776 (7)	0.0446 (2)
Cl1	0.23596 (6)	0.54549 (16)	0.43487 (18)	0.1049 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.053 (2)	0.058 (3)	0.089 (3)	−0.007 (2)	0.010 (2)	0.000 (2)
C2	0.085 (3)	0.053 (3)	0.059 (3)	0.001 (2)	0.006 (2)	0.0134 (19)
C3	0.081 (3)	0.058 (3)	0.0460 (17)	0.002 (2)	0.0147 (18)	0.005 (2)
C4	0.0494 (18)	0.046 (2)	0.042 (2)	−0.0117 (16)	0.0007 (14)	0.0002 (14)
C5	0.066 (2)	0.063 (3)	0.060 (2)	0.006 (2)	0.0237 (19)	0.0143 (19)
C6	0.070 (3)	0.083 (3)	0.076 (3)	0.009 (2)	0.030 (2)	−0.001 (2)
C7	0.0459 (17)	0.0469 (19)	0.0345 (17)	−0.0024 (16)	−0.0046 (16)	0.0052 (19)
C8	0.064 (2)	0.062 (2)	0.0460 (16)	−0.0154 (18)	−0.0071 (18)	0.000 (2)
C9	0.111 (3)	0.061 (3)	0.115 (3)	−0.002 (2)	−0.052 (3)	−0.022 (3)
C10	0.176 (6)	0.060 (3)	0.188 (7)	−0.009 (3)	−0.076 (5)	−0.020 (3)
N1	0.0483 (16)	0.0580 (19)	0.0343 (12)	−0.0063 (14)	0.0049 (11)	−0.0089 (13)
N2	0.0567 (17)	0.0551 (19)	0.0324 (12)	−0.0096 (15)	0.0025 (12)	0.0006 (13)
O1	0.0651 (16)	0.0533 (15)	0.0463 (13)	−0.0137 (12)	−0.0049 (11)	−0.0085 (11)
O2	0.0691 (14)	0.0504 (14)	0.0385 (12)	−0.0019 (12)	−0.0021 (11)	0.0126 (11)
O3	0.0733 (14)	0.0879 (18)	0.0201 (11)	−0.0272 (14)	−0.0005 (11)	−0.0042 (12)
S1	0.0537 (4)	0.0471 (4)	0.0331 (3)	−0.0078 (4)	−0.0019 (4)	0.0032 (5)
Cl1	0.0872 (7)	0.0628 (7)	0.1647 (13)	0.0110 (6)	0.0415 (8)	−0.0064 (8)

Geometric parameters (Å, º)

C1—C6	1.354 (5)	C8—N2	1.470 (4)
C1—C2	1.380 (5)	C8—C9	1.494 (5)
C1—Cl1	1.736 (4)	C8—H8A	0.9700
C2—C3	1.367 (5)	C8—H8B	0.9700
C2—H2	0.9300	C9—C10	1.492 (6)
C3—C4	1.372 (4)	C9—H9A	0.9700
C3—H3	0.9300	C9—H9B	0.9700
C4—C5	1.366 (4)	C10—H10A	0.9600
C4—S1	1.760 (4)	C10—H10B	0.9600
C5—C6	1.391 (5)	C10—H10C	0.9600
C5—H5	0.9300	N1—S1	1.626 (3)
C6—H6	0.9300	N1—H1N	0.8600
C7—O3	1.241 (4)	N2—H2N	0.8600
C7—N2	1.304 (4)	O1—S1	1.429 (2)
C7—N1	1.403 (4)	O2—S1	1.430 (2)
C6—C1—C2	121.2 (4)	H8A—C8—H8B	107.7
C6—C1—Cl1	120.7 (3)	C8—C9—C10	112.1 (4)
C2—C1—Cl1	118.2 (3)	C8—C9—H9A	109.2
C3—C2—C1	118.9 (3)	C10—C9—H9A	109.2
C3—C2—H2	120.6	C8—C9—H9B	109.2
C1—C2—H2	120.6	C10—C9—H9B	109.2
C2—C3—C4	120.4 (3)	H9A—C9—H9B	107.9
C2—C3—H3	119.8	C9—C10—H10A	109.5
C4—C3—H3	119.8	C9—C10—H10B	109.5
C5—C4—C3	120.8 (3)	H10A—C10—H10B	109.5
C5—C4—S1	119.7 (3)	C9—C10—H10C	109.5
C3—C4—S1	119.5 (2)	H10A—C10—H10C	109.5
C4—C5—C6	119.0 (3)	H10B—C10—H10C	109.5
C4—C5—H5	120.5	C7—N1—S1	122.1 (2)
C6—C5—H5	120.5	C7—N1—H1N	119.0
C1—C6—C5	119.9 (3)	S1—N1—H1N	119.0
C1—C6—H6	120.1	C7—N2—C8	123.0 (3)
C5—C6—H6	120.1	C7—N2—H2N	118.5
O3—C7—N2	125.8 (3)	C8—N2—H2N	118.5
O3—C7—N1	119.1 (3)	O1—S1—O2	119.32 (13)
N2—C7—N1	115.1 (3)	O1—S1—N1	103.84 (13)
N2—C8—C9	113.3 (3)	O2—S1—N1	110.87 (14)
N2—C8—H8A	108.9	O1—S1—C4	108.92 (14)
C9—C8—H8A	108.9	O2—S1—C4	108.64 (13)
N2—C8—H8B	108.9	N1—S1—C4	104.17 (14)
C9—C8—H8B	108.9
C6—C1—C2—C3	0.3 (6)	O3—C7—N2—C8	−3.0 (5)
Cl1—C1—C2—C3	180.0 (3)	N1—C7—N2—C8	178.0 (3)
C1—C2—C3—C4	0.0 (6)	C9—C8—N2—C7	−88.9 (5)
C2—C3—C4—C5	−0.7 (5)	C7—N1—S1—O1	168.1 (2)
C2—C3—C4—S1	179.1 (3)	C7—N1—S1—O2	−62.6 (3)
C3—C4—C5—C6	0.9 (5)	C7—N1—S1—C4	54.1 (3)
S1—C4—C5—C6	−178.8 (3)	C5—C4—S1—O1	114.0 (3)
C2—C1—C6—C5	0.0 (6)	C3—C4—S1—O1	−65.8 (3)
Cl1—C1—C6—C5	−179.7 (3)	C5—C4—S1—O2	−17.4 (3)
C4—C5—C6—C1	−0.6 (6)	C3—C4—S1—O2	162.8 (3)
N2—C8—C9—C10	−179.4 (4)	C5—C4—S1—N1	−135.7 (3)
O3—C7—N1—S1	25.3 (4)	C3—C4—S1—N1	44.6 (3)
N2—C7—N1—S1	−155.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3^i	0.86	2.02	2.727 (3)	138
N2—H2N···O2^i	0.86	2.36	3.026 (3)	134
N2—H2N···O3^i	0.86	2.31	3.054 (3)	145

Symmetry code: (i) −x+1, −y, z−1/2.