Polythia-zide.

The crystal structure of the title compound, C(11)H(13)ClF(3)N(3)O(4)S(3) (systematic name: 6-chloro-2-methyl-3-{[(2,2,2-trifluoro-eth-yl)sulfan-yl]meth-yl}-3,4-dihydro-2H-1,2,4-benzothia-diazine-7-sul-f-on-amide 1,1-diox-ide; CRN: 346-18-9), exhibits a two-dimensional network of hydrogen-bonded mol-ecules parallel to (01). The NH and NH(2) groups act as donor sites and the sulfonyl O atoms as acceptor sites in N-H⋯O hydrogen bonds, and a C-H⋯O interaction also occurs. The thiadiazine ring adopts an envelope conformation with the N atom bonded to sulfur at the tip of the flap, and the methyl substituent is in an axial position.

Related literature

For the preparation of polythia­zide, see: McManus (1961 ▶). For a comprehensive description of polythia­zide, see: Negendra Vara et al. (1991 ▶). For a preliminary crystallographic study at room temperature, see Dupont & Dideberg (1970 ▶). For crystal structures of polymorphs and solvates of related thia­zide compounds, see: Zhou et al. (2006 ▶); Johnston et al. (2007a ▶,b ▶); Johnston et al. (2007 ▶); Fernandes, Florence et al. (2006 ▶); Fernandes, Shankland et al. (2007 ▶); Johnston et al. (2008 ▶); Fabbiani et al. (2007 ▶); Fernandes, Johnston et al. (2007 ▶); Fernandes, Leech et al. (2007 ▶).

Experimental

Crystal data

C11H13ClF3N3O4S3

M = 439.87

Monoclinic,

a = 14.6659 (7) Å

b = 9.5498 (6) Å

c = 13.6720 (7) Å

β = 116.149 (3)°

V = 1718.87 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.64 mm−1

T = 120 K

0.12 × 0.10 × 0.06 mm

Data collection

Bruker-Nonius Roper CCD camera on κ-goniostat diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.927, T max = 0.963

9021 measured reflections

3197 independent reflections

2768 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.098

S = 1.06

3197 reflections

239 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.41 e Å−3

Absolute structure: Flack (1983 ▶), 1504 Friedel pairs

Flack parameter: 0.12 (8)

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810022105/kj2150sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810022105/kj2150Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C11H13ClF3N3O4S3	F(000) = 896
Mr = 439.87	Dx = 1.700 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 11202 reflections
a = 14.6659 (7) Å	θ = 2.9–27.5°
b = 9.5498 (6) Å	µ = 0.64 mm−1
c = 13.6720 (7) Å	T = 120 K
β = 116.149 (3)°	Plate, colourless
V = 1718.87 (16) Å3	0.12 × 0.10 × 0.06 mm
Z = 4

Bruker-Nonius Roper CCD camera on κ-goniostat diffractometer	3197 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2768 reflections with I > 2σ(I)
graphite	Rint = 0.055
Detector resolution: 9.091 pixels mm-1	θmax = 26.0°, θmin = 3.3°
φ & ω scans	h = −17→18
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −11→11
Tmin = 0.927, Tmax = 0.963	l = −15→16
9021 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.098	w = 1/[σ2(Fo2) + (0.0435P)2 + 0.009P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3197 reflections	Δρmax = 0.32 e Å−3
239 parameters	Δρmin = −0.41 e Å−3
5 restraints	Absolute structure: Flack (1983), 1504 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.12 (8)

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.

	x	y	z	Uiso*/Ueq
Cl1	0.88627 (8)	0.03391 (10)	0.90846 (8)	0.0280 (2)
S1	0.94030 (7)	0.63949 (10)	0.76867 (7)	0.0226 (2)
S2	0.77245 (7)	0.12532 (10)	0.65142 (8)	0.0241 (2)
S3	1.04262 (8)	0.75479 (12)	1.17195 (8)	0.0262 (2)
O1	0.9673 (2)	0.6291 (3)	0.6804 (2)	0.0285 (7)
O2	0.8556 (2)	0.7293 (3)	0.7536 (2)	0.0272 (7)
O3	0.7388 (2)	0.2033 (3)	0.5523 (2)	0.0348 (7)
O4	0.6988 (2)	0.0628 (3)	0.6808 (2)	0.0344 (7)
N1	1.0394 (2)	0.6927 (4)	0.8780 (3)	0.0228 (7)
N2	1.0131 (3)	0.5322 (3)	0.9992 (3)	0.0214 (7)
H1N	1.043 (4)	0.502 (6)	1.067 (2)	0.052 (16)*
N3	0.8417 (3)	−0.0017 (4)	0.6449 (3)	0.0255 (8)
H2N	0.892 (3)	0.022 (5)	0.631 (4)	0.050 (16)*
H3N	0.856 (4)	−0.066 (4)	0.696 (3)	0.041 (15)*
C1	1.0167 (3)	0.6786 (4)	0.9736 (3)	0.0233 (9)
H1	0.9479	0.7195	0.9531	0.028*
C2	0.9619 (3)	0.4380 (4)	0.9200 (3)	0.0192 (8)
C3	0.9196 (3)	0.4722 (4)	0.8079 (3)	0.0193 (8)
C4	0.8626 (3)	0.3757 (4)	0.7286 (3)	0.0188 (8)
H4	0.8328	0.4027	0.6541	0.023*
C5	0.8483 (3)	0.2403 (4)	0.7563 (3)	0.0199 (8)
C6	0.8960 (3)	0.2032 (4)	0.8677 (3)	0.0192 (8)
C7	0.9523 (3)	0.2976 (4)	0.9475 (3)	0.0206 (8)
H7	0.9849	0.2686	1.0215	0.025*
C8	1.1391 (3)	0.6397 (5)	0.8917 (3)	0.0289 (10)
H8A	1.1933	0.6981	0.9447	0.043*
H8B	1.1421	0.6430	0.8216	0.043*
H8C	1.1480	0.5428	0.9180	0.043*
C9	1.0919 (3)	0.7580 (4)	1.0712 (3)	0.0251 (9)
H9A	1.0985	0.8557	1.0509	0.030*
H9B	1.1595	0.7129	1.1004	0.030*
C10	1.1529 (3)	0.8004 (6)	1.2942 (3)	0.0360 (11)
H10A	1.1519	0.7472	1.3558	0.043*
H10B	1.2143	0.7715	1.2865	0.043*
C11	1.1605 (4)	0.9502 (6)	1.3201 (4)	0.0438 (13)
F1	1.2461 (3)	0.9823 (5)	1.4089 (3)	0.0842 (14)
F2	1.1618 (3)	1.0300 (4)	1.2398 (3)	0.0708 (10)
F3	1.0838 (2)	0.9967 (4)	1.3395 (3)	0.0656 (10)

	U11	U22	U33	U12	U13	U23
Cl1	0.0427 (6)	0.0181 (5)	0.0234 (5)	−0.0054 (4)	0.0147 (4)	−0.0008 (4)
S1	0.0297 (5)	0.0179 (5)	0.0215 (5)	0.0026 (4)	0.0125 (4)	0.0038 (4)
S2	0.0276 (5)	0.0226 (6)	0.0185 (5)	−0.0012 (5)	0.0069 (4)	−0.0028 (4)
S3	0.0322 (5)	0.0254 (6)	0.0257 (5)	−0.0050 (4)	0.0172 (4)	−0.0072 (4)
O1	0.0404 (17)	0.0296 (17)	0.0201 (15)	−0.0011 (13)	0.0175 (13)	0.0038 (12)
O2	0.0278 (15)	0.0215 (16)	0.0331 (17)	0.0057 (13)	0.0141 (13)	0.0059 (13)
O3	0.0458 (18)	0.0267 (17)	0.0168 (15)	0.0028 (14)	0.0000 (12)	−0.0001 (12)
O4	0.0300 (16)	0.0406 (19)	0.0346 (18)	−0.0126 (15)	0.0161 (14)	−0.0130 (15)
N1	0.0321 (19)	0.0193 (18)	0.0214 (18)	−0.0022 (15)	0.0157 (15)	−0.0036 (14)
N2	0.0327 (18)	0.0143 (17)	0.0176 (18)	−0.0026 (14)	0.0116 (15)	0.0015 (13)
N3	0.034 (2)	0.020 (2)	0.025 (2)	0.0027 (16)	0.0156 (16)	−0.0014 (15)
C1	0.036 (2)	0.017 (2)	0.021 (2)	−0.0040 (18)	0.0165 (17)	−0.0021 (16)
C2	0.0214 (19)	0.019 (2)	0.017 (2)	0.0023 (16)	0.0083 (16)	−0.0020 (16)
C3	0.024 (2)	0.016 (2)	0.019 (2)	0.0041 (16)	0.0111 (16)	0.0020 (16)
C4	0.0179 (18)	0.019 (2)	0.017 (2)	0.0053 (16)	0.0061 (15)	0.0013 (16)
C5	0.022 (2)	0.019 (2)	0.019 (2)	−0.0006 (17)	0.0092 (17)	−0.0054 (16)
C6	0.0242 (19)	0.017 (2)	0.018 (2)	0.0004 (16)	0.0109 (16)	0.0005 (16)
C7	0.028 (2)	0.019 (2)	0.0131 (19)	−0.0031 (17)	0.0075 (15)	0.0003 (15)
C8	0.021 (2)	0.041 (3)	0.025 (2)	0.0011 (19)	0.0104 (17)	0.0052 (19)
C9	0.032 (2)	0.023 (2)	0.021 (2)	0.0007 (18)	0.0118 (17)	−0.0009 (17)
C10	0.033 (2)	0.054 (3)	0.020 (2)	0.004 (2)	0.0101 (18)	−0.002 (2)
C11	0.040 (3)	0.054 (4)	0.044 (3)	−0.020 (2)	0.024 (2)	−0.021 (3)
F1	0.066 (2)	0.128 (4)	0.062 (2)	−0.063 (2)	0.0310 (18)	−0.056 (2)
F2	0.095 (2)	0.052 (2)	0.072 (2)	−0.0414 (19)	0.043 (2)	−0.0140 (18)
F3	0.069 (2)	0.052 (2)	0.095 (3)	−0.0182 (17)	0.053 (2)	−0.0440 (19)

Cl1—C6	1.736 (4)	C2—C3	1.415 (5)
S1—O1	1.429 (3)	C2—C7	1.416 (6)
S1—O2	1.448 (3)	C3—C4	1.388 (5)
S1—N1	1.640 (3)	C4—C5	1.390 (5)
S1—C3	1.753 (4)	C4—H4	0.9500
S2—O3	1.430 (3)	C5—C6	1.412 (5)
S2—O4	1.437 (3)	C6—C7	1.375 (5)
S2—N3	1.610 (4)	C7—H7	0.9500
S2—C5	1.759 (4)	C8—H8A	0.9800
S3—C10	1.794 (4)	C8—H8B	0.9800
S3—C9	1.816 (4)	C8—H8C	0.9800
N1—C8	1.480 (5)	C9—H9A	0.9900
N1—C1	1.490 (5)	C9—H9B	0.9900
N2—C2	1.353 (5)	C10—C11	1.467 (7)
N2—C1	1.447 (5)	C10—H10A	0.9900
N2—H1N	0.88 (2)	C10—H10B	0.9900
N3—H2N	0.87 (2)	C11—F3	1.340 (6)
N3—H3N	0.884 (19)	C11—F2	1.343 (6)
C1—C9	1.508 (5)	C11—F1	1.343 (6)
C1—H1	1.0000
O1—S1—O2	117.39 (17)	C3—C4—H4	119.5
O1—S1—N1	109.12 (17)	C5—C4—H4	119.5
O2—S1—N1	107.83 (17)	C4—C5—C6	117.7 (3)
O1—S1—C3	110.15 (18)	C4—C5—S2	118.4 (3)
O2—S1—C3	109.29 (18)	C6—C5—S2	123.9 (3)
N1—S1—C3	101.91 (18)	C7—C6—C5	122.0 (4)
O3—S2—O4	119.56 (19)	C7—C6—Cl1	117.5 (3)
O3—S2—N3	107.61 (19)	C5—C6—Cl1	120.5 (3)
O4—S2—N3	105.8 (2)	C6—C7—C2	120.3 (3)
O3—S2—C5	106.11 (18)	C6—C7—H7	119.8
O4—S2—C5	108.34 (18)	C2—C7—H7	119.8
N3—S2—C5	109.11 (19)	N1—C8—H8A	109.5
C10—S3—C9	101.8 (2)	N1—C8—H8B	109.5
C8—N1—C1	116.6 (3)	H8A—C8—H8B	109.5
C8—N1—S1	116.0 (3)	N1—C8—H8C	109.5
C1—N1—S1	108.8 (2)	H8A—C8—H8C	109.5
C2—N2—C1	121.0 (3)	H8B—C8—H8C	109.5
C2—N2—H1N	118 (4)	C1—C9—S3	106.4 (3)
C1—N2—H1N	121 (4)	C1—C9—H9A	110.5
S2—N3—H2N	116 (4)	S3—C9—H9A	110.5
S2—N3—H3N	115 (3)	C1—C9—H9B	110.5
H2N—N3—H3N	115 (5)	S3—C9—H9B	110.5
N2—C1—N1	110.2 (3)	H9A—C9—H9B	108.6
N2—C1—C9	111.2 (3)	C11—C10—S3	113.7 (4)
N1—C1—C9	111.8 (3)	C11—C10—H10A	108.8
N2—C1—H1	107.8	S3—C10—H10A	108.8
N1—C1—H1	107.8	C11—C10—H10B	108.8
C9—C1—H1	107.8	S3—C10—H10B	108.8
N2—C2—C3	122.5 (4)	H10A—C10—H10B	107.7
N2—C2—C7	120.1 (3)	F3—C11—F2	106.8 (5)
C3—C2—C7	117.3 (3)	F3—C11—F1	106.1 (4)
C4—C3—C2	121.2 (4)	F2—C11—F1	105.4 (4)
C4—C3—S1	119.5 (3)	F3—C11—C10	113.0 (4)
C2—C3—S1	119.3 (3)	F2—C11—C10	112.5 (4)
C3—C4—C5	121.1 (3)	F1—C11—C10	112.5 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O4i	0.88 (2)	2.21 (4)	2.906 (4)	135 (4)
N2—H1N···O1ii	0.88 (2)	2.59 (4)	3.230 (4)	130 (4)
N3—H3N···O2iii	0.88 (2)	2.11 (3)	2.929 (5)	154 (5)
C10—H10B···O2iv	0.99	2.31	3.267 (5)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯O4i	0.88 (2)	2.21 (4)	2.906 (4)	135 (4)
N2—H1N⋯O1ii	0.88 (2)	2.59 (4)	3.230 (4)	130 (4)
N3—H3N⋯O2iii	0.88 (2)	2.11 (3)	2.929 (5)	154 (5)
C10—H10B⋯O2iv	0.99	2.31	3.267 (5)	163

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .