Polythia­zide

Thomas Gelbrich; Mairi F Haddow; Ulrich J Griesser

doi:10.1107/S1600536810022105

. 2010 Jun 16;66(Pt 7):o1663–o1664. doi: 10.1107/S1600536810022105

Polythiazide

Thomas Gelbrich ^a,^*, Mairi F Haddow ^a,^‡, Ulrich J Griesser ^a

PMCID: PMC3006947 PMID: 21587890

Abstract

The crystal structure of the title compound, C₁₁H₁₃ClF₃N₃O₄S₃ (systematic name: 6-chloro-2-methyl-3-{[(2,2,2-trifluoroethyl)sulfanyl]methyl}-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide 1,1-dioxide; CRN: 346–18–9), exhibits a two-dimensional network of hydrogen-bonded molecules parallel to ( Inline graphic 01). The NH and NH₂ 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 _r = 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
Δρ_max = 0.32 e Å⁻³
Δρ_min = −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 ▶).

Supplementary Material

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

e-66-o1663-sup1.cif^{(17.6KB, cif)}

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

e-66-o1663-Isup2.hkl^{(156.9KB, hkl)}

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

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⋯O2^iv	0.99	2.31	3.267 (5)	163

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

supplementary crystallographic information

Comment

The title compound is a thiazide diuretic drug. The asymmetric unit contains a single molecule (see Fig. 1), and the lattice parameters are consistent with a preliminary crystallographic study (Dupont & Dideberg, 1970). The geometrical parameters of the thiazide unit are in concert with other structures of the same class of compounds (see section Related literature). The S2—N3 bond of the sulfonyl group is gauche with respect to the C5—C6 bond of the phenyl ring. The conformation of C—S—C—C side chain of the heterocyclic ring is characterized by the torsions angles N1—C1—C9—S3 = 170.8 (3)°, C1—C9 —S3—C10 = 162.6 (3)° and C9—S3—C10—C11 = 94.5 (4)°.

Each polythiazide molecule is N—H···O bonded to two neighbouring molecules so that a hydrogen bonded sheet parallel to (-101) is formed (see Fig. 2). The NH group and one sulfonamide O atom are engaged in an N2—H···O4(x + 1/2, -y + 1/2) interaction. An N3—H···O2(x, y - 1, z) bond links two molecules via the sulfonamide NH₂ group and a thiazide sulfonyl O atom. Each N—H···O bonded sheet contains an additional short C10—H···O2(x + 1/2, -y + 3/2, z + 1/2) contact (see Table 1). A longer N2—H···O1(x, -y + 1, z + 1/2) contact between neighbouring sheets, in which the NH group is involved again, is also worth mentioning. The closest intermolecular contact of the second NH₂ H atom is to the S atom of the side chain, H2N···S3(x, -y + 1, z - 1/2) = 2.93 (4) Å.

Experimental

The investigated crystals were obtained from a polythiazide sample from Pfizer (Brussels, Belgium).