Hydro­chloro­thia­zide–1,4-dioxane (1/1)

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

doi:10.1107/S1600536805022464

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 8| August 2005| Pages o2573-o2575

https://doi.org/10.1107/S1600536805022464

Hydrochlorothiazide–1,4-dioxane (1/1)

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 and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland
^*Correspondence e-mail: alastair.florence@strath.ac.uk

(Received 5 July 2005; accepted 13 July 2005; online 16 July 2005)

Hydrochlorothiazide forms a 1:1 solvate with 1,4-dioxane, C₇H₈ClN₃O₄S₂·C₄H₈O₂ [systematic name: 6-chloro-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide 1,1-dioxide–1,4-dioxane ( [{1/1}] )]. The asymmetric unit comprises one molecule of hydrochlorothiazide and halves of two solvent molecules arranged around inversion centres. The structure contains a hydrogen-bonding network comprising three N—H⋯O and one N—H⋯N hydrogen bonds.

Comment

Hydrochlorothiazide (HCT) is a thiazide diuretic which is known to crystallize in at least one non-solvated form (Dupont & Dideberg, 1972 ). The title compound, (I), was produced during an automated parallel crystallization polymorph screen on HCT. The sample was identified as a novel form using multi-sample X-ray powder diffraction analysis of all recrystallized samples (Florence et al., 2003 ). Subsequent manual recrystallization from a saturated 1:1 acetone/dioxane solution, by slow evaporation at 298 K, yielded samples of the HCT 1,4-dioxane solvate suitable for single-crystal X-ray analysis (Fig. 1).

In (I), the six-membered S1/N1/C1/N2/C2/C7 ring in HCT displays a half-chair conformation, atoms C1 and N1 having deviations of −0.134 (2) and 0.554 (2) Å, respectively, from the least-squares plane through atoms C2–C7. The sulfonamide side chain adopts an N3—S2—C5—C4 torsion angle of 57.55 (18)°, such that atom O3 eclipses atom H6, and atoms O4 and N3 are staggered with respect to atom Cl1. In the non-solvated structure, this group is rotated by approximately 120° compared with that in (I), such that the amine group lies on the opposite side of the benzothiadiazine ring system. Both centrosymmetric solvent molecules adopt chair conformations, with puckering parameters (Cremer & Pople, 1975 ) for rings A and B of Q = 0.564 (2) and 0.566 (2) Å, θ = 2.11 (1) and 0.00° and φ = 0 and 0°, respectively.

The crystal structure is stabilized by a network of hydrogen bonds interconnecting (a) HCT molecules (Fig. 2, contacts 1 and 2), (b) HCT and solvent molecule A (contact 3), and (c) HCT and solvent molecule B (contact 4). Contact 1 forms an infinite chain of HCT molecules, which combine with contact 2 to form layers of HCT molecules in the ab plane. Each HCT layer is connected to parallel layers of 1,4-dioxane (via contacts 3 and 4) and HCT molecules. Hydrophobic interactions between layers of HCT include offset face-to-face (off) π–π stacking between the ring formed by atoms C2–C7 [centroid–centroid distance = 4.192 (1) Å]. Compound (I) therefore adopts a stacked structure with alternating double layers of HCT, with single layers of solvent stacked in the c direction (Fig. 3). Three C—H⋯O contacts also exist between HCT molecules (Fig. 2, contacts 5–7), with a fourth connecting 1,4-dioxane molecule B to atom O3 of HCT (contact 8).

Figure 1
The asymmetric unit contents, expanded to complete the solvent molecules, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen-bond contacts. [Symmetry codes: (i) 1 – x, −y, 1 − z; (ii) –x, 1 − y, 1 − z].

Figure 2
Intermolecular interactions in (I)

. Dashed lines indicate hydrogen bonds and unique contacts are labelled as follows: (1) N3⋯N1(−1 + x, 1 + y, z) = 3.097 (3) Å; (2) N2⋯O2(−1 + x, y, z) = 3.032 (2) Å; (3) N3⋯O5 = 2.879 (2) Å; (4) N1⋯O6 = 2.848 (2) Å; (5) C1⋯O2(2 − x, −y, −z) = 3.304 (2) Å; (6) C1⋯O4(x, −1 + y, z) = 3.220 (2) Å; (7) C3⋯O2(−1 + x, y, z) = 3.285 (2) Å; (8) C11⋯O3(x, −1 + y, z) = 3.412 (2) Å. Contacts calculated and illustrated using PLATON (Spek, 2003

; program version 280604)

Figure 3
The crystal packing in the structure of (I)

; view down the a axis, showing the alternating layers of HCT and 1,4-dioxane molecules stacked along c. Hydrogen bonds are shown as dashed lines.

Experimental

A single-crystal sample of the title compound was recrystallized from a 1:1 acetone/1,4-dioxane solution by slow evaporation at 298 K.

Crystal data

C₇H₈ClN₃O₄S₂·C₄H₈O₂
M_r = 385.84
Triclinic, $[P \overline 1]$
a = 6.6684 (2) Å
b = 9.8585 (3) Å
c = 12.9149 (4) Å
α = 87.046 (2)°
β = 78.017 (2)°
γ = 70.872 (2)°
V = 784.55 (4) Å³
Z = 2
D_x = 1.633 Mg m⁻³
Mo Kα radiation
Cell parameters from 3105 reflections
θ = 1.0–27.1°
μ = 0.54 mm⁻¹
T = 123 (2) K
Plate, colourless
0.50 × 0.20 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: none
12343 measured reflections
3445 independent reflections
2879 reflections with I > 2σ(I)
R_int = 0.035
θ_max = 27.1°
h = −8 → 8
k = −12 → 12
l = −16 → 15

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.078
S = 1.03
3445 reflections
224 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0335P)² + 0.4818P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O6	0.82 (2)	2.04 (2)	2.848 (2)	170 (2)
N2—H2N⋯O2ⁱ	0.81 (2)	2.28 (3)	3.032 (2)	154 (2)
N3—H3N⋯N1ⁱⁱ	0.81 (2)	2.35 (2)	3.097 (3)	155 (2)
N3—H4N⋯O5	0.87 (3)	2.02 (3)	2.879 (2)	170 (3)
C1—H1A⋯O2	0.99	2.60	2.980 (2)	103
C1—H1A⋯O2ⁱⁱⁱ	0.99	2.55	3.304 (2)	133
C1—H1B⋯O4^iv	0.99	2.41	3.220 (2)	139
C3—H3⋯O2ⁱ	0.95	2.56	3.285 (2)	133
C6—H6⋯O3	0.95	2.38	2.800 (2)	107
C11—H11B⋯O3^iv	0.99	2.50	3.412 (2)	153
Symmetry codes: (i) x-1, y, z; (ii) x-1, y+1, z; (iii) -x+2, -y, -z; (iv) x, y-1, z.

The amine H atoms were located in difference syntheses and were refined isotropically. All other H atoms were constrained to an idealized geometry using a riding model with U_iso(H) = 1.2U_eq(C); for CH₂ groups, C—H = 0.99 Å, whilst for CH groups, C—H = 0.95 Å.

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/S1600536805022464/dn6237sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805022464/dn6237Isup2.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.

6-chloro-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide 1,1-dioxide–1,4-dioxane (1/1) top

Crystal data top

C₇H₈ClN₃O₄S₂·C₄H₈O₂	Z = 2
M_r = 385.84	F(000) = 400
Triclinic, P1	D_x = 1.633 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6684 (2) Å	Cell parameters from 3105 reflections
b = 9.8585 (3) Å	θ = 1.0–27.1°
c = 12.9149 (4) Å	µ = 0.54 mm⁻¹
α = 87.046 (2)°	T = 123 K
β = 78.017 (2)°	Flattened (Plate?), colourless
γ = 70.872 (2)°	0.50 × 0.20 × 0.08 mm
V = 784.55 (4) Å³

Data collection top

Nonius KappaCCD diffractometer	2879 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 27.1°, θ_min = 1.6°
ω and φ scans	h = −8→8
12343 measured reflections	k = −12→12
3445 independent reflections	l = −16→15

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0335P)² + 0.4818P] where P = (F_o² + 2F_c²)/3
3445 reflections	(Δ/σ)_max < 0.001
224 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

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	0.07843 (7)	0.65012 (5)	0.09254 (4)	0.01908 (12)
S1	0.88826 (7)	0.17340 (4)	0.20012 (4)	0.01332 (11)
S2	0.42002 (7)	0.73615 (4)	0.20612 (4)	0.01410 (11)
O1	0.9318 (2)	0.20556 (13)	0.29836 (11)	0.0206 (3)
O2	1.05861 (19)	0.14951 (13)	0.10752 (10)	0.0168 (3)
O3	0.5917 (2)	0.72299 (13)	0.26103 (11)	0.0193 (3)
O4	0.4063 (2)	0.82446 (13)	0.11418 (10)	0.0200 (3)
O5	0.1010 (2)	0.58970 (15)	0.43701 (11)	0.0260 (3)
O6	0.5231 (2)	0.09459 (16)	0.41565 (11)	0.0258 (3)
N1	0.8111 (3)	0.03091 (16)	0.21498 (13)	0.0151 (3)
N2	0.5155 (3)	0.12683 (16)	0.12386 (13)	0.0148 (3)
N3	0.1942 (3)	0.79977 (18)	0.28862 (14)	0.0173 (3)
C1	0.7164 (3)	0.01179 (18)	0.12586 (15)	0.0153 (4)
H1A	0.8206	0.0098	0.0586	0.018*
H1B	0.6886	−0.0813	0.1322	0.018*
C2	0.5001 (3)	0.26611 (18)	0.13433 (13)	0.0130 (4)
C3	0.3216 (3)	0.37838 (19)	0.11015 (14)	0.0140 (4)
H3	0.2157	0.3563	0.0814	0.017*
C4	0.2995 (3)	0.51923 (19)	0.12782 (14)	0.0136 (4)
C5	0.4490 (3)	0.55796 (18)	0.17218 (14)	0.0128 (4)
C6	0.6283 (3)	0.44909 (18)	0.19318 (14)	0.0140 (4)
H6	0.7334	0.4725	0.2218	0.017*
C7	0.6567 (3)	0.30640 (18)	0.17301 (14)	0.0129 (4)
C8	0.1831 (3)	0.5178 (2)	0.52605 (17)	0.0273 (5)
H8A	0.2506	0.5768	0.5576	0.033*
H8B	0.2958	0.4247	0.5025	0.033*
C9	0.0039 (4)	0.4925 (2)	0.60737 (16)	0.0296 (5)
H9A	0.0635	0.4404	0.6676	0.035*
H9B	−0.1035	0.5859	0.6345	0.035*
C10	0.3289 (3)	0.0572 (2)	0.44691 (17)	0.0271 (5)
H10A	0.2641	0.0582	0.3844	0.032*
H10B	0.2226	0.1290	0.4991	0.032*
C11	0.3771 (4)	−0.0892 (2)	0.49485 (16)	0.0267 (5)
H11A	0.2409	−0.1122	0.5177	0.032*
H11B	0.4753	−0.1620	0.4411	0.032*
H3N	0.095 (4)	0.837 (2)	0.2591 (18)	0.021 (6)*
H1N	0.730 (4)	0.039 (2)	0.2727 (18)	0.022 (6)*
H2N	0.416 (4)	0.108 (2)	0.1080 (17)	0.020 (6)*
H4N	0.172 (4)	0.741 (3)	0.339 (2)	0.039 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0167 (2)	0.0153 (2)	0.0241 (3)	−0.00054 (17)	−0.00968 (19)	0.00146 (18)
S1	0.0128 (2)	0.0109 (2)	0.0167 (2)	−0.00285 (17)	−0.00548 (17)	0.00024 (17)
S2	0.0154 (2)	0.0108 (2)	0.0156 (2)	−0.00413 (17)	−0.00203 (18)	−0.00034 (17)
O1	0.0239 (7)	0.0184 (7)	0.0214 (7)	−0.0040 (6)	−0.0132 (6)	−0.0006 (6)
O2	0.0118 (6)	0.0151 (6)	0.0226 (7)	−0.0036 (5)	−0.0025 (5)	−0.0007 (5)
O3	0.0181 (7)	0.0162 (6)	0.0247 (7)	−0.0050 (5)	−0.0066 (6)	−0.0032 (5)
O4	0.0274 (7)	0.0154 (6)	0.0176 (7)	−0.0095 (6)	−0.0017 (6)	0.0035 (5)
O5	0.0361 (8)	0.0293 (8)	0.0194 (7)	−0.0191 (7)	−0.0085 (6)	0.0080 (6)
O6	0.0289 (8)	0.0357 (8)	0.0152 (7)	−0.0130 (7)	−0.0062 (6)	0.0033 (6)
N1	0.0156 (8)	0.0127 (7)	0.0168 (8)	−0.0046 (6)	−0.0033 (7)	0.0017 (6)
N2	0.0136 (8)	0.0129 (7)	0.0201 (8)	−0.0056 (6)	−0.0061 (7)	−0.0004 (6)
N3	0.0165 (8)	0.0144 (8)	0.0179 (8)	−0.0009 (7)	−0.0034 (7)	0.0010 (7)
C1	0.0142 (9)	0.0119 (8)	0.0195 (9)	−0.0036 (7)	−0.0031 (7)	−0.0018 (7)
C2	0.0138 (8)	0.0147 (9)	0.0101 (8)	−0.0048 (7)	−0.0011 (7)	−0.0008 (7)
C3	0.0134 (9)	0.0168 (9)	0.0130 (9)	−0.0060 (7)	−0.0038 (7)	0.0002 (7)
C4	0.0110 (8)	0.0145 (9)	0.0121 (9)	−0.0010 (7)	−0.0011 (7)	0.0022 (7)
C5	0.0136 (9)	0.0110 (8)	0.0131 (9)	−0.0038 (7)	−0.0019 (7)	0.0008 (7)
C6	0.0125 (8)	0.0152 (9)	0.0148 (9)	−0.0057 (7)	−0.0016 (7)	−0.0010 (7)
C7	0.0111 (8)	0.0124 (8)	0.0139 (9)	−0.0025 (7)	−0.0015 (7)	0.0003 (7)
C8	0.0301 (11)	0.0320 (12)	0.0257 (11)	−0.0151 (9)	−0.0116 (9)	0.0062 (9)
C9	0.0424 (13)	0.0379 (13)	0.0184 (10)	−0.0241 (11)	−0.0115 (10)	0.0070 (9)
C10	0.0215 (10)	0.0382 (12)	0.0208 (11)	−0.0070 (9)	−0.0073 (9)	0.0009 (9)
C11	0.0298 (11)	0.0380 (12)	0.0168 (10)	−0.0158 (10)	−0.0068 (9)	−0.0003 (9)

Geometric parameters (Å, º) top

Cl1—C4	1.7372 (18)	C1—H1B	0.9900
S1—O1	1.4316 (13)	C2—C3	1.412 (2)
S1—O2	1.4373 (13)	C2—C7	1.416 (2)
S1—N1	1.6371 (15)	C3—C4	1.373 (2)
S1—C7	1.7541 (17)	C3—H3	0.9500
S2—O3	1.4357 (13)	C4—C5	1.406 (2)
S2—O4	1.4362 (13)	C5—C6	1.386 (2)
S2—N3	1.6060 (16)	C6—C7	1.388 (2)
S2—C5	1.7713 (17)	C6—H6	0.9500
O5—C8	1.431 (2)	C8—C9	1.497 (3)
O5—C9ⁱ	1.435 (2)	C8—H8A	0.9900
O6—C10	1.434 (2)	C8—H8B	0.9900
O6—C11ⁱⁱ	1.439 (2)	C9—O5ⁱ	1.435 (2)
N1—C1	1.470 (2)	C9—H9A	0.9900
N1—H1N	0.82 (2)	C9—H9B	0.9900
N2—C2	1.355 (2)	C10—C11	1.502 (3)
N2—C1	1.448 (2)	C10—H10A	0.9900
N2—H2N	0.81 (2)	C10—H10B	0.9900
N3—H3N	0.81 (2)	C11—O6ⁱⁱ	1.439 (2)
N3—H4N	0.87 (3)	C11—H11A	0.9900
C1—H1A	0.9900	C11—H11B	0.9900

O1—S1—O2	118.26 (8)	C3—C4—Cl1	117.42 (14)
O1—S1—N1	108.70 (8)	C5—C4—Cl1	120.55 (13)
O2—S1—N1	107.54 (8)	C6—C5—C4	117.82 (16)
O1—S1—C7	110.05 (8)	C6—C5—S2	117.75 (13)
O2—S1—C7	108.81 (8)	C4—C5—S2	124.42 (13)
N1—S1—C7	102.26 (8)	C5—C6—C7	120.92 (16)
O3—S2—O4	118.54 (8)	C5—C6—H6	119.5
O3—S2—N3	107.75 (9)	C7—C6—H6	119.5
O4—S2—N3	106.87 (9)	C6—C7—C2	121.50 (16)
O3—S2—C5	105.19 (8)	C6—C7—S1	118.84 (14)
O4—S2—C5	110.01 (8)	C2—C7—S1	119.63 (13)
N3—S2—C5	108.10 (8)	O5—C8—C9	110.31 (17)
C8—O5—C9ⁱ	110.22 (15)	O5—C8—H8A	109.6
C10—O6—C11ⁱⁱ	110.16 (15)	C9—C8—H8A	109.6
C1—N1—S1	111.21 (12)	O5—C8—H8B	109.6
C1—N1—H1N	114.2 (16)	C9—C8—H8B	109.6
S1—N1—H1N	107.2 (15)	H8A—C8—H8B	108.1
C2—N2—C1	121.31 (15)	O5ⁱ—C9—C8	110.81 (17)
C2—N2—H2N	119.1 (15)	O5ⁱ—C9—H9A	109.5
C1—N2—H2N	119.0 (15)	C8—C9—H9A	109.5
S2—N3—H3N	112.0 (16)	O5ⁱ—C9—H9B	109.5
S2—N3—H4N	113.6 (17)	C8—C9—H9B	109.5
H3N—N3—H4N	116 (2)	H9A—C9—H9B	108.1
N2—C1—N1	111.09 (14)	O6—C10—C11	110.61 (17)
N2—C1—H1A	109.4	O6—C10—H10A	109.5
N1—C1—H1A	109.4	C11—C10—H10A	109.5
N2—C1—H1B	109.4	O6—C10—H10B	109.5
N1—C1—H1B	109.4	C11—C10—H10B	109.5
H1A—C1—H1B	108.0	H10A—C10—H10B	108.1
N2—C2—C3	121.02 (16)	O6ⁱⁱ—C11—C10	110.62 (17)
N2—C2—C7	122.07 (16)	O6ⁱⁱ—C11—H11A	109.5
C3—C2—C7	116.88 (15)	C10—C11—H11A	109.5
C4—C3—C2	120.68 (16)	O6ⁱⁱ—C11—H11B	109.5
C4—C3—H3	119.7	C10—C11—H11B	109.5
C2—C3—H3	119.7	H11A—C11—H11B	108.1
C3—C4—C5	122.04 (16)

O1—S1—N1—C1	166.87 (12)	N3—S2—C5—C4	57.55 (18)
O2—S1—N1—C1	−63.99 (13)	C4—C5—C6—C7	−1.3 (3)
C7—S1—N1—C1	50.51 (14)	S2—C5—C6—C7	177.15 (14)
C2—N2—C1—N1	47.3 (2)	C5—C6—C7—C2	−2.5 (3)
S1—N1—C1—N2	−66.28 (17)	C5—C6—C7—S1	179.43 (13)
C1—N2—C2—C3	166.39 (16)	N2—C2—C7—C6	−173.58 (17)
C1—N2—C2—C7	−15.7 (3)	C3—C2—C7—C6	4.4 (3)
N2—C2—C3—C4	175.51 (16)	N2—C2—C7—S1	4.4 (2)
C7—C2—C3—C4	−2.5 (3)	C3—C2—C7—S1	−177.61 (13)
C2—C3—C4—C5	−1.3 (3)	O1—S1—C7—C6	41.38 (17)
C2—C3—C4—Cl1	178.41 (13)	O2—S1—C7—C6	−89.67 (15)
C3—C4—C5—C6	3.2 (3)	N1—S1—C7—C6	156.76 (15)
Cl1—C4—C5—C6	−176.47 (13)	O1—S1—C7—C2	−136.70 (14)
C3—C4—C5—S2	−175.12 (14)	O2—S1—C7—C2	92.25 (15)
Cl1—C4—C5—S2	5.2 (2)	N1—S1—C7—C2	−21.32 (16)
O3—S2—C5—C6	−5.88 (16)	C9ⁱ—O5—C8—C9	−57.3 (3)
O4—S2—C5—C6	122.85 (14)	O5—C8—C9—O5ⁱ	57.7 (2)
N3—S2—C5—C6	−120.79 (15)	C11ⁱⁱ—O6—C10—C11	−57.4 (2)
O3—S2—C5—C4	172.46 (15)	O6—C10—C11—O6ⁱⁱ	57.7 (2)
O4—S2—C5—C4	−58.81 (17)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O6	0.82 (2)	2.04 (2)	2.848 (2)	170.4 (18)
N2—H2N···O2ⁱⁱⁱ	0.81 (2)	2.28 (3)	3.032 (2)	153.7 (18)
N3—H3N···N1^iv	0.81 (2)	2.35 (2)	3.097 (3)	154.5 (19)
N3—H4N···O5	0.87 (3)	2.02 (3)	2.879 (2)	170 (3)
C1—H1A···O2	0.99	2.60	2.980 (2)	103
C1—H1A···O2^v	0.99	2.55	3.304 (2)	133
C1—H1B···O4^vi	0.99	2.41	3.220 (2)	139
C3—H3···O2ⁱⁱⁱ	0.95	2.56	3.285 (2)	133
C6—H6···O3	0.95	2.38	2.800 (2)	107
C11—H11B···O3^vi	0.99	2.50	3.412 (2)	153

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

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 (https://www.cposs.org.uk).

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