Hydro­chloro­thia­zide dimethyl sulfoxide solvate

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

doi:10.1107/S1600536806016734

organic compounds

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ISSN: 2056-9890

Volume 62| Part 6| June 2006| Pages o2288-o2290

https://doi.org/10.1107/S1600536806016734

Hydrochlorothiazide dimethyl sulfoxide solvate

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

^aDepartment of Pharmaceutical Sciences, 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 23 March 2006; accepted 6 May 2006; online 12 May 2006)

Hydrochlorothiazide forms a 1:1 solvate with dimethyl sulfoxide, C₇H₈ClN₃O₄S₂·C₂H₆OS. The crystal structure contains a hydrogen-bonding network comprising three N—H⋯O contacts.

Comment

Hydrochlorothiazide (HCT) is a thiazide diuretic which is known to crystallize in at least two non-solvated forms; form I (Dupont & Dideberg, 1972 ) and form II (Florence et al., 2005 ). The dimethyl sulfoxide (DMSO) solvate, (I), was produced during an automated parallel crystallization polymorph search on HCT. The sample was identified as a new form using multi-sample X-ray powder diffraction analysis of all recrystallized samples (Florence et al., 2003 ). Subsequent manual recrystallization by slow evaporation of a saturated DMSO solution at 278 K yielded samples of (I) suitable for single-crystal X-ray analysis (Fig. 1).

In (I), the six-membered ring N1—S1—C3—C2—N2—C1 in HCT displays a puckered conformation, atom N1 having a deviation of 0.622 (2) Å from the least-squares plane through atoms C2–C7. The sulfonamide side chain adopts an N3—S2—C5—C6 torsion angle of −62.0 (2)°, such that O3 eclipses H4, and atoms O4 and N3 are staggered with respect to Cl1.

The crystal structure is stabilized by three N—H⋯O hydrogen bonds interconnecting (a) HCT molecules (Fig. 2, contact 1) and forming an R₂²(8) (Etter, 1990 ) centrosymmetric dimer (Fig. 3), and (b) HCT and two DMSO molecules (Fig. 2, contacts 2 and 3).

The aromatic ring formed by atoms C2–C7 is involved in two offset face-to-face π–π interactions between nearest-neighbour HCT molecules with centroid–centroid distances/perpendicular distances between the corresponding planes equal to 4.354 (2)/3.58 Å (centroid at −x, 1 − y, 2 − z) and 4.466 (2)/3.57 Å (centroid at 1 − x, 1 − y, 2 − z). The HCT aromatic rings form a stacked arrangement in the direction of the a axis. The structure also contains three C—H⋯O contacts between HCT and HCT (Fig.2, contact 4) and between HCT and DMSO (contacts 5 and 6).

Figure 1
Plot of the asymmetric-unit contents with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Intermolecular interactions in (I)

. Dashed lines indicate hydrogen bonds and unique contacts are labelled as follows: 1 = N3⋯O4, 3.004 (3)Å, O4 in the molecule at (−x, 2 − y, 2 − z); 2 = N2⋯O5, 2.806 (3)Å, O5 in the molecule at (1 − x, 1 − y, 2 − z); 3 = N3⋯O5, 2.776 (3)Å; O5 in the molecule at (−1 + x, y, z); 4 = C1⋯O4, 3.347 (3)Å, O4 in the molecule at (x, −1 + y, z); 5 = C7⋯O5, 3.289 (3)Å, O5 in the molecule at (1 − x, 1 − y, 2 − z); 6 = C8⋯O3, 3.228 (4)Å, O3 in the molecule at (1 − x, 2 − y, 1 − z). Contacts calculated and illustrated using PLATON (Spek, 2003

; program version 150306)

Figure 3
The R₂²(8) hydrogen-bonded motif in the crystal structure of (I)

Experimental

A single-crystal sample of the title compound was recrystallized by slow evaporation of a dimethyl sulfoxide solution at 278 K.

Crystal data

C₇H₈ClN₃O₄S₂·C₂H₆OS
M_r = 375.86
Triclinic, $[P \overline 1]$
a = 7.5068 (4) Å
b = 9.8272 (5) Å
c = 10.7311 (6) Å
α = 85.639 (3)°
β = 73.896 (3)°
γ = 80.246 (3)°
V = 749.23 (7) Å³
Z = 2
D_x = 1.666 Mg m⁻³
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 123 (2) K
Cut fragment, colourless
0.28 × 0.28 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: none
10594 measured reflections
3267 independent reflections
2669 reflections with I > 2σ(I)
R_int = 0.055
θ_max = 27.2°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.110
S = 1.03
3267 reflections
208 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0592P)² + 0.534P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H4N⋯O4ⁱ	0.80 (3)	2.27 (3)	3.004 (3)	153 (3)
N2—H2N⋯O5ⁱⁱ	0.81 (3)	2.02 (3)	2.806 (3)	164 (3)
N3—H3N⋯O5ⁱⁱⁱ	0.83 (3)	1.95 (3)	2.776 (3)	172 (3)
C1—H1A⋯O4^iv	0.99	2.46	3.347 (3)	149
C7—H7⋯O5ⁱⁱ	0.95	2.56	3.289 (3)	134
C8—H8B⋯O3^v	0.98	2.53	3.228 (4)	128
Symmetry codes: (i) -x, -y+2, -z+2; (ii) -x+1, -y+1, -z+2; (iii) x-1, y, z; (iv) x, y-1, z; (v) -x+1, -y+2, -z+1.

H atoms bonded to N atoms were found in difference maps and refined isotropically, but all other H atoms were constrained to idealized geometry using a riding model; U_iso(H) = 1.2U_eq(C) and C—H = 0.95 (CH group) or 0.99 Å (CH₂ groups).

Data collection: COLLECT (Hooft, 1988 ) and DENZO (Otwinowski & Minor, 1997 ); cell refinement: DENZO and COLLECT; data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806016734/dn2020sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806016734/dn2020Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1988) and DENZO (Otwinowski & Minor, 1997); cell refinement: DENZO and COLLECT; data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Hydrochlorothiazide dimethyl sulfoxide solvate top

Crystal data top

C₇H₈ClN₃O₄S₂·C₂H₆OS	Z = 2
M_r = 375.86	F(000) = 388
Triclinic, P1	D_x = 1.666 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5068 (4) Å	Cell parameters from 2971 reflections
b = 9.8272 (5) Å	θ = 2.9–27.1°
c = 10.7311 (6) Å	µ = 0.70 mm⁻¹
α = 85.639 (3)°	T = 123 K
β = 73.896 (3)°	Cut fragment, colourless
γ = 80.246 (3)°	0.28 × 0.28 × 0.10 mm
V = 749.23 (7) Å³

Data collection top

Nonius KappaCCD diffractometer	2669 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.055
Graphite monochromator	θ_max = 27.2°, θ_min = 2.9°
φ and ω scans	h = −9→9
10594 measured reflections	k = −11→12
3267 independent reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0592P)² + 0.534P] where P = (F_o² + 2F_c²)/3
3267 reflections	(Δ/σ)_max = 0.001
208 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Special details top

Experimental. Although no formal absorption correction was applied, the standard Kappa CCD methodology involves collecting a large number of redundant reflections and processing via SCALEPACK. This effectively introduces a multi-scan type correction suitable for weakly absorbing molecules.

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	0.02575 (8)	0.73342 (6)	1.11711 (6)	0.02319 (16)
S1	0.51163 (9)	0.34312 (6)	0.67153 (6)	0.02145 (16)
S2	0.15774 (9)	0.85850 (6)	0.81869 (6)	0.02141 (16)
S3	0.69526 (9)	0.76246 (6)	0.63385 (6)	0.02243 (17)
O1	0.6400 (3)	0.41391 (19)	0.57579 (18)	0.0319 (4)
O2	0.3873 (3)	0.27152 (19)	0.63320 (18)	0.0300 (4)
O3	0.2162 (3)	0.86589 (18)	0.67974 (17)	0.0295 (4)
O4	0.2406 (3)	0.93652 (17)	0.89048 (18)	0.0267 (4)
O5	0.7163 (3)	0.7637 (2)	0.77073 (17)	0.0322 (4)
N1	0.6358 (3)	0.2308 (2)	0.7473 (2)	0.0245 (5)
N2	0.4255 (3)	0.2776 (2)	0.9606 (2)	0.0225 (5)
N3	−0.0632 (3)	0.9093 (2)	0.8633 (2)	0.0248 (5)
C1	0.5231 (4)	0.1724 (2)	0.8661 (2)	0.0236 (5)
H1A	0.4299	0.1247	0.8446	0.028*
H1B	0.6056	0.1030	0.9050	0.028*
C2	0.3507 (3)	0.4058 (2)	0.9263 (2)	0.0182 (5)
C3	0.3807 (3)	0.4550 (2)	0.7960 (2)	0.0181 (5)
C4	0.3152 (3)	0.5911 (2)	0.7652 (2)	0.0190 (5)
H4	0.3415	0.6224	0.6770	0.023*
C5	0.2114 (3)	0.6819 (2)	0.8622 (2)	0.0179 (5)
C6	0.1710 (3)	0.6301 (2)	0.9914 (2)	0.0192 (5)
C7	0.2385 (3)	0.4977 (2)	1.0242 (2)	0.0193 (5)
H7	0.2103	0.4671	1.1127	0.023*
C8	0.6947 (6)	0.9341 (3)	0.5754 (3)	0.0489 (9)
H8A	0.5787	0.9911	0.6223	0.073*
H8B	0.7023	0.9384	0.4826	0.073*
H8C	0.8029	0.9687	0.5888	0.073*
C9	0.9207 (5)	0.6894 (4)	0.5400 (3)	0.0517 (10)
H9A	1.0142	0.7440	0.5485	0.078*
H9B	0.9206	0.6894	0.4487	0.078*
H9C	0.9518	0.5942	0.5710	0.078*
H1N	0.729 (5)	0.264 (3)	0.758 (3)	0.036 (9)*
H2N	0.407 (4)	0.261 (3)	1.038 (3)	0.023 (7)*
H3N	−0.131 (4)	0.872 (3)	0.831 (3)	0.023 (8)*
H4N	−0.107 (4)	0.923 (3)	0.939 (3)	0.026 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0229 (3)	0.0246 (3)	0.0208 (3)	0.0002 (2)	−0.0042 (2)	−0.0075 (2)
S1	0.0253 (3)	0.0181 (3)	0.0191 (3)	0.0034 (2)	−0.0060 (2)	−0.0041 (2)
S2	0.0236 (3)	0.0151 (3)	0.0238 (3)	0.0000 (2)	−0.0048 (2)	−0.0020 (2)
S3	0.0241 (3)	0.0226 (3)	0.0207 (3)	−0.0030 (2)	−0.0065 (2)	−0.0015 (2)
O1	0.0332 (11)	0.0284 (10)	0.0257 (10)	0.0020 (8)	0.0022 (8)	−0.0011 (8)
O2	0.0321 (10)	0.0292 (10)	0.0316 (10)	−0.0003 (8)	−0.0132 (8)	−0.0109 (8)
O3	0.0374 (11)	0.0212 (9)	0.0238 (10)	0.0024 (8)	−0.0035 (8)	0.0026 (7)
O4	0.0271 (10)	0.0185 (8)	0.0346 (10)	−0.0042 (7)	−0.0066 (8)	−0.0057 (7)
O5	0.0353 (11)	0.0433 (11)	0.0196 (9)	−0.0103 (9)	−0.0088 (8)	0.0038 (8)
N1	0.0244 (11)	0.0207 (10)	0.0276 (12)	0.0008 (9)	−0.0076 (9)	−0.0026 (9)
N2	0.0292 (12)	0.0183 (10)	0.0194 (11)	−0.0009 (8)	−0.0075 (9)	−0.0001 (8)
N3	0.0245 (12)	0.0245 (11)	0.0262 (13)	0.0015 (9)	−0.0100 (10)	−0.0064 (9)
C1	0.0305 (14)	0.0148 (11)	0.0252 (13)	−0.0007 (10)	−0.0089 (11)	0.0001 (9)
C2	0.0172 (11)	0.0178 (11)	0.0214 (12)	−0.0040 (9)	−0.0068 (9)	−0.0022 (9)
C3	0.0195 (11)	0.0159 (11)	0.0189 (12)	−0.0012 (9)	−0.0058 (9)	−0.0024 (9)
C4	0.0196 (12)	0.0189 (11)	0.0177 (11)	−0.0017 (9)	−0.0045 (9)	−0.0012 (9)
C5	0.0184 (11)	0.0156 (11)	0.0189 (11)	−0.0015 (9)	−0.0042 (9)	−0.0019 (9)
C6	0.0168 (11)	0.0211 (11)	0.0209 (12)	−0.0047 (9)	−0.0043 (9)	−0.0064 (9)
C7	0.0208 (12)	0.0203 (11)	0.0173 (11)	−0.0047 (9)	−0.0048 (9)	−0.0014 (9)
C8	0.086 (3)	0.0267 (15)	0.0400 (18)	−0.0107 (16)	−0.0281 (18)	0.0061 (13)
C9	0.0374 (18)	0.072 (2)	0.0395 (19)	0.0171 (17)	−0.0091 (15)	−0.0262 (17)

Geometric parameters (Å, º) top

Cl1—C6	1.749 (2)	N3—H4N	0.80 (3)
S1—O2	1.4195 (19)	C1—H1A	0.9900
S1—O1	1.427 (2)	C1—H1B	0.9900
S1—N1	1.638 (2)	C2—C3	1.413 (3)
S1—C3	1.758 (2)	C2—C7	1.422 (3)
S2—O3	1.4327 (19)	C3—C4	1.393 (3)
S2—O4	1.4443 (19)	C4—C5	1.394 (3)
S2—N3	1.595 (2)	C4—H4	0.9500
S2—C5	1.771 (2)	C5—C6	1.409 (3)
S3—O5	1.5213 (18)	C6—C7	1.371 (3)
S3—C8	1.754 (3)	C7—H7	0.9500
S3—C9	1.774 (3)	C8—H8A	0.9800
N1—C1	1.458 (3)	C8—H8B	0.9800
N1—H1N	0.85 (3)	C8—H8C	0.9800
N2—C2	1.358 (3)	C9—H9A	0.9800
N2—C1	1.457 (3)	C9—H9B	0.9800
N2—H2N	0.81 (3)	C9—H9C	0.9800
N3—H3N	0.83 (3)

O2—S1—O1	119.64 (12)	N2—C2—C3	123.0 (2)
O2—S1—N1	107.28 (12)	N2—C2—C7	119.7 (2)
O1—S1—N1	107.26 (12)	C3—C2—C7	117.3 (2)
O2—S1—C3	108.77 (11)	C4—C3—C2	121.4 (2)
O1—S1—C3	110.26 (11)	C4—C3—S1	119.71 (18)
N1—S1—C3	102.16 (11)	C2—C3—S1	118.87 (17)
O3—S2—O4	118.94 (12)	C3—C4—C5	120.8 (2)
O3—S2—N3	107.80 (13)	C3—C4—H4	119.6
O4—S2—N3	106.60 (12)	C5—C4—H4	119.6
O3—S2—C5	105.53 (11)	C4—C5—C6	117.7 (2)
O4—S2—C5	107.25 (11)	C4—C5—S2	118.49 (18)
N3—S2—C5	110.66 (12)	C6—C5—S2	123.52 (17)
O5—S3—C8	105.16 (14)	C7—C6—C5	122.4 (2)
O5—S3—C9	104.42 (14)	C7—C6—Cl1	117.17 (19)
C8—S3—C9	99.1 (2)	C5—C6—Cl1	120.43 (18)
C1—N1—S1	113.31 (18)	C6—C7—C2	120.2 (2)
C1—N1—H1N	113 (2)	C6—C7—H7	119.9
S1—N1—H1N	111 (2)	C2—C7—H7	119.9
C2—N2—C1	122.8 (2)	S3—C8—H8A	109.5
C2—N2—H2N	116 (2)	S3—C8—H8B	109.5
C1—N2—H2N	121 (2)	H8A—C8—H8B	109.5
S2—N3—H3N	118 (2)	S3—C8—H8C	109.5
S2—N3—H4N	116 (2)	H8A—C8—H8C	109.5
H3N—N3—H4N	113 (3)	H8B—C8—H8C	109.5
N2—C1—N1	112.2 (2)	S3—C9—H9A	109.5
N2—C1—H1A	109.2	S3—C9—H9B	109.5
N1—C1—H1A	109.2	H9A—C9—H9B	109.5
N2—C1—H1B	109.2	S3—C9—H9C	109.5
N1—C1—H1B	109.2	H9A—C9—H9C	109.5
H1A—C1—H1B	107.9	H9B—C9—H9C	109.5

O2—S1—N1—C1	−63.1 (2)	S1—C3—C4—C5	−179.87 (18)
O1—S1—N1—C1	167.15 (17)	C3—C4—C5—C6	−1.8 (4)
C3—S1—N1—C1	51.2 (2)	C3—C4—C5—S2	172.14 (19)
C2—N2—C1—N1	37.5 (3)	O3—S2—C5—C4	8.1 (2)
S1—N1—C1—N2	−61.1 (3)	O4—S2—C5—C4	−119.65 (19)
C1—N2—C2—C3	−8.2 (4)	N3—S2—C5—C4	124.5 (2)
C1—N2—C2—C7	172.6 (2)	O3—S2—C5—C6	−178.3 (2)
N2—C2—C3—C4	−174.4 (2)	O4—S2—C5—C6	53.9 (2)
C7—C2—C3—C4	4.7 (3)	N3—S2—C5—C6	−62.0 (2)
N2—C2—C3—S1	3.1 (3)	C4—C5—C6—C7	3.7 (4)
C7—C2—C3—S1	−177.79 (17)	S2—C5—C6—C7	−169.91 (19)
O2—S1—C3—C4	−92.3 (2)	C4—C5—C6—Cl1	−174.82 (18)
O1—S1—C3—C4	40.7 (2)	S2—C5—C6—Cl1	11.6 (3)
N1—S1—C3—C4	154.5 (2)	C5—C6—C7—C2	−1.3 (4)
O2—S1—C3—C2	90.2 (2)	Cl1—C6—C7—C2	177.25 (18)
O1—S1—C3—C2	−136.8 (2)	N2—C2—C7—C6	176.3 (2)
N1—S1—C3—C2	−23.0 (2)	C3—C2—C7—C6	−2.9 (3)
C2—C3—C4—C5	−2.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H4N···O4ⁱ	0.80 (3)	2.27 (3)	3.004 (3)	153 (3)
N2—H2N···O5ⁱⁱ	0.81 (3)	2.02 (3)	2.806 (3)	164 (3)
N3—H3N···O5ⁱⁱⁱ	0.83 (3)	1.95 (3)	2.776 (3)	172 (3)
C1—H1A···O4^iv	0.99	2.46	3.347 (3)	149
C7—H7···O5ⁱⁱ	0.95	2.56	3.289 (3)	134
C8—H8B···O3^v	0.98	2.53	3.228 (4)	128

Symmetry codes: (i) −x, −y+2, −z+2; (ii) −x+1, −y+1, −z+2; (iii) x−1, y, z; (iv) x, y−1, z; (v) −x+1, −y+2, −z+1.

Acknowledgements

We 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 (URL: www.cposs.org.uk).

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