Hydro­chloro­thia­zide N,N-dimethyl­formamide solvate

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

doi:10.1107/S1600536806011391

organic compounds

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ISSN: 2056-9890

Volume 62| Part 5| May 2006| Pages o1730-o1732

https://doi.org/10.1107/S1600536806011391

Hydrochlorothiazide N,N-dimethylformamide 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 and 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 28 March 2006; online 7 April 2006)

Hydrochlorothiazide forms a 1:1 solvate with N,N-dimethylformamide (systematic name: 6-chloro-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide-1,1-dioxide dimethylformamide solvate), C₇H₈ClN₃O₄S₂·C₃H₇NO. The compound crystallizes with two molecules of hydrochlorothiazide and two solvent molecules in the asymmetric unit and displays an extensive hydrogen-bonding network.

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 ). Form (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 N,N-dimethylformamide (DMF):acetone solution by slow evaporation at 278 K yielded samples of the HCT DMF solvate suitable for a synchrotron microcrystal study (Cernik et al., 1997 , 2000 ).

The compound crystallizes as a 1:1 solvate with Z′ = 2 (Fig. 1). The benzothiadiazine ring of HCT adopts a non-planar conformation in both residues, with the largest deviations from the least-squares plane through atoms C2–C7 observed for atoms S1 and N1 in residue A [0.278 (1) and 0.770 (2) Å respectively] and atom N1A in residue B [0.6802 (2) Å]. In residue A, the sulphonamide side chain adopts a torsion angle N3—S2—C5—C6 of −57.7 (2)° such that the NH₂ group is located on the same side of the molecule as the H atom (H1N) bonded to N1, a similar arrangement to that in both of the non-solvated forms of HCT. The corresponding torsion angle in residue B is 60.76 (2)°, such that the NH₂ group lies on the opposite side of the molecule to the H atom (H5N) bonded to N1A.

The crystal structure is stabilized by a network of seven N—H⋯O and one N—H⋯N intermolecular hydrogen bonds (Table 1). These contacts interconnect (a) HCT molecules (Fig. 2, contacts 1, 2, 4 and 6) and (b) HCT and solvent molecules (Fig. 2 contacts 3, 4, 5, 7 and 8). Residues A and B form parallel C(8) (Etter, 1990 ) hydrogen-bonded chains in the direction of the b axis via contacts 2 and 6, respectively (Fig. 3), with the chains interconnected via C—H⋯O contacts to form layers in the ab plane. The layers stack along the c axis with solvent residue C lying between layers of HCT molecules, interconnected via contacts 3 and 6 to HCT residues A and B, respectively. The remaining solvent molecule (residue D) lies approximately perpendicular to the ab plane and forms hydrogen bonds with HCT residue B (Fig. 2, contacts 5 and 8). The structure is further stabilized by seven C—H⋯O contacts (Table 1).

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

Figure 2
A packing diagram illustrating hydrogen bonds in (I)

. Unique contacts are labelled as follow: 1 = N1⋯O2Aⁱ; 2 = N2⋯O4ⁱ; 3 = N3⋯O5; 4 = N3⋯O2Aⁱⁱ; 5 = N1A⋯O5Aⁱⁱⁱ; 6 = N2Aⁱ⋯N3A(x, −2 + y, z); 7 = N3A—H7N⋯O5^iv; 8 = N3A—H8N⋯O5A^iv (see Table 1

for symmetry codes and geometry). Contacts calculated and illustrated using PLATON (Spek, 2003

; program version 280604). Contact 6 is shown outwith the asymmetric unit for clarity.

Figure 3
The crystal packing in (I)

, viewed down the a axis, showing the alternating layers of HCT and DMF molecules stacked along c. Hydrogen bonds are shown as dashed lines.

Experimental

The sample of HCT used to prepare the solvate was used as received from Sigma–Aldrich. This was recrystallized from a 50:50 DMF/acetone solution by isothermal solvent evaporation at 278 K.

Crystal data

C₇H₈ClN₃O₄S₂·C₃H₇NO
M_r = 370.83
Triclinic, $[P \overline 1]$
a = 7.3028 (2) Å
b = 9.1492 (2) Å
c = 23.6989 (6) Å
α = 86.194 (1)°
β = 89.841 (1)°
γ = 72.855 (1)°
V = 1509.50 (7) Å³
Z = 4
D_x = 1.632 Mg m⁻³
Synchrotron radiation
λ = 0.8466 Å
μ = 0.56 mm⁻¹
T = 150 (2) K
Plate, colourless
0.18 × 0.10 × 0.03 mm

Data collection

Bruker SMART APEX2 CCD diffractometer
ω scans
Absorption correction: none
10824 measured reflections
4574 independent reflections
4311 reflections with I > 2σ(I)
R_int = 0.018
θ_max = 29.0°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.107
S = 1.05
4574 reflections
441 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0721P)² + 1.2599P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2Aⁱ	0.80 (3)	2.60 (3)	3.290 (3)	146 (3)
N2—H2N⋯O4ⁱ	0.74 (3)	2.47 (3)	3.023 (3)	134 (3)
N3—H3N⋯O5	0.90 (3)	2.07 (3)	2.954 (3)	165 (3)
N3—H4N⋯O2Aⁱⁱ	0.85 (4)	2.35 (4)	3.092 (3)	146 (3)
N1A—H5N⋯O5Aⁱⁱⁱ	0.78 (4)	2.12 (4)	2.882 (3)	167 (3)
N2A—H6N⋯N3Aⁱ	0.77 (4)	2.48 (4)	3.177 (3)	150 (3)
N3A—H7N⋯O5^iv	0.95 (4)	1.89 (4)	2.820 (3)	164 (3)
N3A—H8N⋯O5A^iv	0.86 (3)	2.12 (3)	2.942 (3)	163 (2)
C1A—H1A1⋯O3Aⁱ	0.99	2.42	3.157 (3)	131
C1—H1A⋯O3ⁱ	0.99	2.56	3.235 (3)	125
C1A—H1A2⋯O3	0.99	2.51	3.467 (3)	162
C7—H7⋯O2ⁱⁱ	0.95	2.56	3.466 (3)	159
C7A—H7A⋯O1Aⁱⁱ	0.95	2.45	3.163 (3)	132
C9—H9B⋯O1ⁱⁱ	0.98	2.54	3.442 (3)	152
C10—H10C⋯O1ⁱⁱ	0.98	2.51	3.323 (3)	141
Symmetry codes: (i) x, y-1, z; (ii) x-1, y, z; (iii) x+1, y, z; (iv) x, y+1, z.

The amine and aldehyde H atoms were located by difference synthesis and refined isotropically. The remaining H atoms were positioned geometrically and a riding model with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl) was used during the refinement process (C—H distances 0.95, 0.99 and 0.98 Å for CH, CH₂ and CH₃ groups, respectively).

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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/S1600536806011391/lh2032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806011391/lh2032Isup2.hkl

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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 dimethylformamide solvate top

Crystal data top

C₇H₈ClN₃O₄S₂·C₃H₇NO	Z = 4
M_r = 370.83	F(000) = 768
Triclinic, P1	D_x = 1.632 Mg m⁻³
a = 7.3028 (2) Å	Synchrotron radiation, λ = 0.8466 Å
b = 9.1492 (2) Å	Cell parameters from 7222 reflections
c = 23.6989 (6) Å	θ = 4.1–32.9°
α = 86.194 (1)°	µ = 0.56 mm⁻¹
β = 89.841 (1)°	T = 150 K
γ = 72.855 (1)°	Plate, colourless
V = 1509.50 (7) Å³	0.18 × 0.10 × 0.03 mm

Data collection top

Bruker SMART APEX2 CCD diffractometer	4311 reflections with I > 2σ(I)
Radiation source: Station 16.2SMX, Daresbury SRS	R_int = 0.018
Si111 monochromator	θ_max = 29.0°, θ_min = 4.0°
fine–slice ω scans	h = −8→8
10824 measured reflections	k = −10→10
4574 independent reflections	l = −26→27

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) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0721P)² + 1.2599P] where P = (F_o² + 2F_c²)/3
4574 reflections	(Δ/σ)_max = 0.001
441 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Special details top

Experimental. Collected at Daresbury SRS Station 16.2SMX, SADABS used to correct for beam decay (entered as _diffrn_standards_decay_% below).

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	0.16046 (7)	0.23586 (6)	0.40126 (3)	0.01755 (17)
Cl1A	0.30299 (9)	0.97445 (7)	0.09678 (3)	0.02518 (18)
S1	0.98182 (8)	−0.22413 (6)	0.42499 (2)	0.01265 (16)
S1A	1.02805 (8)	0.55067 (6)	0.22707 (2)	0.01389 (17)
S2	0.53889 (7)	0.36026 (6)	0.38526 (2)	0.01035 (16)
S2A	0.66913 (8)	1.10301 (6)	0.11975 (2)	0.01556 (17)
O1	1.0676 (2)	−0.19429 (19)	0.37273 (7)	0.0221 (4)
O1A	1.1984 (2)	0.5695 (2)	0.20171 (8)	0.0254 (4)
O2	1.0864 (2)	−0.22855 (19)	0.47642 (7)	0.0199 (4)
O2A	1.0034 (2)	0.5673 (2)	0.28664 (7)	0.0211 (4)
O3	0.7321 (2)	0.36121 (17)	0.37450 (7)	0.0142 (3)
O3A	0.8435 (2)	1.11607 (19)	0.14354 (8)	0.0223 (4)
O4	0.4310 (2)	0.45978 (17)	0.42562 (7)	0.0171 (4)
O4A	0.6407 (3)	1.1259 (2)	0.05959 (7)	0.0251 (4)
O5	0.5475 (3)	0.1246 (2)	0.26342 (7)	0.0291 (4)
O5A	0.1090 (3)	0.3633 (2)	0.09657 (7)	0.0239 (4)
N1	0.9323 (3)	−0.3863 (2)	0.42229 (9)	0.0156 (4)
N1A	1.0131 (3)	0.3819 (2)	0.21446 (9)	0.0176 (4)
N2	0.6067 (3)	−0.2923 (2)	0.45327 (9)	0.0159 (4)
N2A	0.6726 (3)	0.4691 (2)	0.19691 (9)	0.0182 (5)
N3	0.4220 (3)	0.4054 (2)	0.32568 (9)	0.0174 (4)
N3A	0.4927 (3)	1.2259 (2)	0.14799 (10)	0.0186 (5)
N4	0.4364 (3)	−0.0809 (2)	0.28300 (8)	0.0204 (5)
N4A	0.0586 (3)	0.2989 (3)	0.00804 (9)	0.0258 (5)
C1	0.7916 (3)	−0.4047 (3)	0.46429 (10)	0.0158 (5)
H1A	0.7776	−0.5090	0.4636	0.019*
H1B	0.8384	−0.3937	0.5025	0.019*
C1A	0.8273 (3)	0.3648 (3)	0.23111 (10)	0.0177 (5)
H1A1	0.8272	0.2580	0.2268	0.021*
H1A2	0.8061	0.3857	0.2714	0.021*
C2	0.5902 (3)	−0.1436 (2)	0.43836 (9)	0.0104 (5)
C2A	0.6700 (3)	0.6140 (2)	0.17986 (9)	0.0118 (5)
C3	0.7519 (3)	−0.0915 (2)	0.42761 (9)	0.0098 (4)
C3A	0.8251 (3)	0.6725 (3)	0.19079 (9)	0.0126 (5)
C4	0.7321 (3)	0.0619 (2)	0.41259 (9)	0.0101 (4)
H4	0.8432	0.0944	0.4067	0.012*
C4A	0.8206 (3)	0.8199 (3)	0.17185 (9)	0.0128 (5)
H4A	0.9278	0.8552	0.1790	0.015*
C5	0.5525 (3)	0.1677 (2)	0.40615 (9)	0.0100 (4)
C5A	0.6629 (3)	0.9165 (3)	0.14273 (9)	0.0130 (5)
C6	0.3912 (3)	0.1149 (2)	0.41410 (9)	0.0114 (5)
C6A	0.5078 (3)	0.8593 (3)	0.13203 (9)	0.0144 (5)
C7	0.4086 (3)	−0.0352 (3)	0.43099 (9)	0.0121 (5)
H7	0.2967	−0.0660	0.4378	0.015*
C7A	0.5110 (3)	0.7131 (3)	0.14953 (10)	0.0151 (5)
H7A	0.4047	0.6779	0.1411	0.018*
C8	0.5705 (4)	−0.0106 (3)	0.28142 (10)	0.0226 (6)
C8A	0.0065 (4)	0.3334 (3)	0.06038 (11)	0.0229 (6)
C9	0.2396 (4)	−0.0010 (3)	0.26562 (13)	0.0324 (7)
H9A	0.2216	0.1097	0.2621	0.049*
H9B	0.1522	−0.0238	0.2940	0.049*
H9C	0.2122	−0.0350	0.2291	0.049*
C9A	−0.0677 (5)	0.2566 (4)	−0.03098 (13)	0.0444 (8)
H9D	−0.1918	0.2667	−0.0133	0.067*
H9E	−0.0101	0.1502	−0.0403	0.067*
H9F	−0.0861	0.3244	−0.0656	0.067*
C10	0.4762 (4)	−0.2415 (3)	0.30413 (11)	0.0234 (6)
H10A	0.6137	−0.2854	0.3122	0.035*
H10B	0.4368	−0.2992	0.2755	0.035*
H10C	0.4046	−0.2474	0.3388	0.035*
C10A	0.2476 (4)	0.2942 (4)	−0.01197 (12)	0.0354 (7)
H10D	0.3094	0.3439	0.0144	0.053*
H10E	0.2363	0.3483	−0.0495	0.053*
H10F	0.3250	0.1873	−0.0143	0.053*
H1N	0.905 (4)	−0.407 (4)	0.3917 (14)	0.030 (9)*
H2N	0.519 (4)	−0.316 (3)	0.4553 (12)	0.020 (8)*
H3N	0.464 (5)	0.331 (4)	0.3015 (14)	0.037 (9)*
H4N	0.301 (5)	0.433 (4)	0.3292 (13)	0.035 (9)*
H5N	1.036 (5)	0.364 (4)	0.1832 (15)	0.033 (9)*
H6N	0.594 (5)	0.438 (4)	0.1852 (13)	0.030 (9)*
H7N	0.486 (5)	1.202 (4)	0.1875 (16)	0.046 (9)*
H8	0.692 (4)	−0.071 (3)	0.2937 (12)	0.023 (7)*
H8A	−0.126 (5)	0.339 (3)	0.0660 (13)	0.034 (8)*
H8N	0.388 (4)	1.249 (3)	0.1287 (12)	0.021 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0063 (3)	0.0127 (3)	0.0325 (4)	−0.0006 (2)	0.0005 (2)	−0.0033 (2)
Cl1A	0.0177 (3)	0.0213 (3)	0.0350 (4)	−0.0046 (3)	−0.0123 (3)	0.0041 (3)
S1	0.0092 (3)	0.0083 (3)	0.0189 (3)	−0.0007 (2)	−0.0010 (2)	0.0013 (2)
S1A	0.0098 (3)	0.0154 (3)	0.0163 (3)	−0.0040 (2)	−0.0005 (2)	0.0013 (2)
S2	0.0088 (3)	0.0065 (3)	0.0156 (3)	−0.0023 (2)	0.0000 (2)	0.0002 (2)
S2A	0.0169 (3)	0.0123 (3)	0.0182 (3)	−0.0059 (2)	0.0027 (2)	0.0010 (2)
O1	0.0177 (9)	0.0180 (9)	0.0269 (10)	−0.0005 (7)	0.0089 (7)	0.0022 (7)
O1A	0.0110 (9)	0.0306 (10)	0.0340 (10)	−0.0071 (7)	−0.0001 (7)	0.0074 (8)
O2	0.0156 (8)	0.0176 (8)	0.0261 (9)	−0.0051 (7)	−0.0096 (7)	0.0023 (7)
O2A	0.0218 (9)	0.0253 (9)	0.0161 (9)	−0.0063 (7)	−0.0037 (7)	−0.0036 (7)
O3	0.0095 (8)	0.0105 (8)	0.0225 (9)	−0.0032 (6)	−0.0001 (6)	0.0021 (6)
O3A	0.0165 (9)	0.0176 (9)	0.0347 (10)	−0.0087 (7)	0.0014 (7)	0.0014 (7)
O4	0.0171 (9)	0.0101 (8)	0.0256 (9)	−0.0051 (7)	0.0042 (7)	−0.0070 (7)
O4A	0.0329 (10)	0.0239 (10)	0.0178 (9)	−0.0088 (8)	0.0045 (7)	0.0049 (7)
O5	0.0504 (12)	0.0222 (10)	0.0186 (9)	−0.0170 (9)	0.0040 (8)	−0.0018 (8)
O5A	0.0266 (10)	0.0251 (10)	0.0185 (9)	−0.0051 (8)	0.0023 (8)	−0.0032 (7)
N1	0.0173 (11)	0.0098 (10)	0.0191 (11)	−0.0029 (8)	−0.0030 (8)	−0.0021 (8)
N1A	0.0201 (11)	0.0156 (11)	0.0157 (11)	−0.0025 (8)	0.0027 (9)	−0.0026 (9)
N2	0.0123 (11)	0.0128 (10)	0.0247 (11)	−0.0081 (9)	−0.0021 (8)	0.0028 (8)
N2A	0.0175 (11)	0.0171 (11)	0.0237 (11)	−0.0111 (9)	−0.0023 (9)	−0.0008 (8)
N3	0.0156 (11)	0.0147 (11)	0.0196 (11)	−0.0020 (9)	−0.0054 (9)	0.0035 (9)
N3A	0.0181 (12)	0.0135 (10)	0.0232 (12)	−0.0031 (9)	−0.0004 (9)	−0.0010 (9)
N4	0.0252 (11)	0.0162 (10)	0.0175 (11)	−0.0030 (9)	0.0038 (9)	0.0007 (8)
N4A	0.0355 (13)	0.0252 (12)	0.0186 (11)	−0.0121 (10)	0.0005 (9)	0.0001 (9)
C1	0.0188 (12)	0.0098 (11)	0.0194 (12)	−0.0062 (9)	−0.0046 (10)	0.0036 (9)
C1A	0.0222 (13)	0.0135 (12)	0.0191 (12)	−0.0083 (10)	0.0007 (10)	0.0010 (9)
C2	0.0136 (11)	0.0103 (11)	0.0089 (10)	−0.0059 (9)	−0.0007 (8)	0.0000 (8)
C2A	0.0137 (11)	0.0136 (11)	0.0102 (11)	−0.0067 (9)	0.0041 (9)	−0.0037 (9)
C3	0.0092 (11)	0.0091 (11)	0.0099 (10)	−0.0010 (9)	−0.0007 (8)	−0.0006 (8)
C3A	0.0108 (11)	0.0156 (12)	0.0111 (11)	−0.0036 (9)	0.0010 (9)	−0.0012 (9)
C4	0.0092 (11)	0.0110 (11)	0.0111 (10)	−0.0044 (9)	0.0007 (8)	−0.0010 (8)
C4A	0.0111 (11)	0.0149 (12)	0.0142 (11)	−0.0064 (9)	0.0020 (9)	−0.0030 (9)
C5	0.0107 (11)	0.0079 (10)	0.0119 (11)	−0.0036 (9)	0.0009 (8)	−0.0006 (8)
C5A	0.0159 (12)	0.0116 (11)	0.0125 (11)	−0.0054 (9)	0.0022 (9)	−0.0020 (9)
C6	0.0086 (11)	0.0111 (11)	0.0135 (11)	−0.0012 (9)	0.0013 (8)	−0.0035 (9)
C6A	0.0111 (11)	0.0184 (12)	0.0131 (11)	−0.0036 (9)	0.0000 (9)	−0.0010 (9)
C7	0.0099 (11)	0.0139 (11)	0.0148 (11)	−0.0070 (9)	0.0018 (9)	−0.0013 (9)
C7A	0.0130 (11)	0.0184 (12)	0.0169 (12)	−0.0089 (10)	0.0009 (9)	−0.0026 (9)
C8	0.0322 (15)	0.0249 (15)	0.0110 (12)	−0.0083 (12)	0.0036 (10)	−0.0046 (10)
C8A	0.0290 (15)	0.0186 (13)	0.0218 (14)	−0.0094 (11)	0.0008 (11)	0.0052 (10)
C9	0.0257 (15)	0.0276 (15)	0.0387 (17)	−0.0019 (12)	0.0025 (12)	0.0070 (12)
C9A	0.062 (2)	0.061 (2)	0.0252 (15)	−0.0406 (18)	0.0013 (14)	−0.0061 (14)
C10	0.0296 (14)	0.0159 (12)	0.0213 (13)	−0.0022 (11)	0.0081 (11)	0.0003 (10)
C10A	0.0318 (16)	0.0441 (18)	0.0236 (14)	−0.0013 (13)	0.0058 (12)	−0.0008 (13)

Geometric parameters (Å, º) top

Cl1—C6	1.736 (2)	N4A—C8A	1.327 (3)
Cl1A—C6A	1.734 (2)	N4A—C10A	1.448 (4)
S1—O2	1.4321 (17)	N4A—C9A	1.455 (4)
S1—O1	1.4328 (18)	C1—H1A	0.9900
S1—N1	1.633 (2)	C1—H1B	0.9900
S1—C3	1.762 (2)	C1A—H1A1	0.9900
S1A—O1A	1.4305 (18)	C1A—H1A2	0.9900
S1A—O2A	1.4354 (17)	C2—C7	1.406 (3)
S1A—N1A	1.626 (2)	C2—C3	1.414 (3)
S1A—C3A	1.756 (2)	C2A—C7A	1.409 (3)
S2—O4	1.4330 (16)	C2A—C3A	1.419 (3)
S2—O3	1.4355 (16)	C3—C4	1.389 (3)
S2—N3	1.617 (2)	C3A—C4A	1.384 (3)
S2—C5	1.772 (2)	C4—C5	1.384 (3)
S2A—O3A	1.4337 (18)	C4—H4	0.9500
S2A—O4A	1.4339 (18)	C4A—C5A	1.381 (3)
S2A—N3A	1.617 (2)	C4A—H4A	0.9500
S2A—C5A	1.770 (2)	C5—C6	1.407 (3)
O5—C8	1.244 (3)	C5A—C6A	1.410 (3)
O5A—C8A	1.236 (3)	C6—C7	1.373 (3)
N1—C1	1.466 (3)	C6A—C7A	1.368 (3)
N1—H1N	0.80 (3)	C7—H7	0.9500
N1A—C1A	1.461 (3)	C7A—H7A	0.9500
N1A—H5N	0.78 (3)	C8—H8	0.93 (3)
N2—C2	1.353 (3)	C8A—H8A	0.96 (3)
N2—C1	1.448 (3)	C9—H9A	0.9800
N2—H2N	0.74 (3)	C9—H9B	0.9800
N2A—C2A	1.354 (3)	C9—H9C	0.9800
N2A—C1A	1.453 (3)	C9A—H9D	0.9800
N2A—H6N	0.77 (3)	C9A—H9E	0.9800
N3—H3N	0.90 (3)	C9A—H9F	0.9800
N3—H4N	0.85 (3)	C10—H10A	0.9800
N3A—H7N	0.95 (4)	C10—H10B	0.9800
N3A—H8N	0.85 (3)	C10—H10C	0.9800
N4—C8	1.320 (3)	C10A—H10D	0.9800
N4—C9	1.454 (3)	C10A—H10E	0.9800
N4—C10	1.465 (3)	C10A—H10F	0.9800

O2—S1—O1	118.00 (11)	N2A—C2A—C7A	120.5 (2)
O2—S1—N1	108.58 (10)	N2A—C2A—C3A	122.4 (2)
O1—S1—N1	108.28 (11)	C7A—C2A—C3A	117.1 (2)
O2—S1—C3	110.17 (10)	C4—C3—C2	121.31 (19)
O1—S1—C3	108.51 (10)	C4—C3—S1	118.17 (16)
N1—S1—C3	102.12 (10)	C2—C3—S1	120.11 (16)
O1A—S1A—O2A	118.65 (11)	C4A—C3A—C2A	121.3 (2)
O1A—S1A—N1A	108.46 (11)	C4A—C3A—S1A	120.39 (17)
O2A—S1A—N1A	107.67 (11)	C2A—C3A—S1A	118.29 (17)
O1A—S1A—C3A	109.92 (10)	C5—C4—C3	120.7 (2)
O2A—S1A—C3A	108.80 (10)	C5—C4—H4	119.6
N1A—S1A—C3A	102.04 (11)	C3—C4—H4	119.6
O4—S2—O3	118.49 (9)	C5A—C4A—C3A	121.1 (2)
O4—S2—N3	107.21 (11)	C5A—C4A—H4A	119.5
O3—S2—N3	107.14 (11)	C3A—C4A—H4A	119.5
O4—S2—C5	109.69 (10)	C4—C5—C6	118.10 (19)
O3—S2—C5	106.03 (9)	C4—C5—S2	118.06 (16)
N3—S2—C5	107.87 (10)	C6—C5—S2	123.78 (16)
O3A—S2A—O4A	118.50 (11)	C4A—C5A—C6A	117.9 (2)
O3A—S2A—N3A	107.69 (11)	C4A—C5A—S2A	118.19 (17)
O4A—S2A—N3A	107.36 (12)	C6A—C5A—S2A	123.85 (17)
O3A—S2A—C5A	104.96 (10)	C7—C6—C5	121.7 (2)
O4A—S2A—C5A	109.65 (10)	C7—C6—Cl1	116.86 (17)
N3A—S2A—C5A	108.34 (11)	C5—C6—Cl1	121.38 (17)
C1—N1—S1	112.79 (16)	C7A—C6A—C5A	121.9 (2)
C1—N1—H1N	111 (2)	C7A—C6A—Cl1A	117.40 (17)
S1—N1—H1N	116 (2)	C5A—C6A—Cl1A	120.73 (18)
C1A—N1A—S1A	111.16 (16)	C6—C7—C2	120.7 (2)
C1A—N1A—H5N	112 (2)	C6—C7—H7	119.7
S1A—N1A—H5N	111 (2)	C2—C7—H7	119.7
C2—N2—C1	121.7 (2)	C6A—C7A—C2A	120.8 (2)
C2—N2—H2N	119 (2)	C6A—C7A—H7A	119.6
C1—N2—H2N	120 (2)	C2A—C7A—H7A	119.6
C2A—N2A—C1A	123.0 (2)	O5—C8—N4	125.3 (3)
C2A—N2A—H6N	118 (2)	O5—C8—H8	119.4 (17)
C1A—N2A—H6N	118 (2)	N4—C8—H8	115.2 (17)
S2—N3—H3N	111 (2)	O5A—C8A—N4A	125.3 (3)
S2—N3—H4N	114 (2)	O5A—C8A—H8A	123.6 (18)
H3N—N3—H4N	113 (3)	N4A—C8A—H8A	111.0 (18)
S2A—N3A—H7N	111 (2)	N4—C9—H9A	109.5
S2A—N3A—H8N	113.8 (19)	N4—C9—H9B	109.5
H7N—N3A—H8N	117 (3)	H9A—C9—H9B	109.5
C8—N4—C9	121.6 (2)	N4—C9—H9C	109.5
C8—N4—C10	121.9 (2)	H9A—C9—H9C	109.5
C9—N4—C10	116.5 (2)	H9B—C9—H9C	109.5
C8A—N4A—C10A	121.4 (2)	N4A—C9A—H9D	109.5
C8A—N4A—C9A	121.7 (2)	N4A—C9A—H9E	109.5
C10A—N4A—C9A	116.8 (2)	H9D—C9A—H9E	109.5
N2—C1—N1	111.50 (18)	N4A—C9A—H9F	109.5
N2—C1—H1A	109.3	H9D—C9A—H9F	109.5
N1—C1—H1A	109.3	H9E—C9A—H9F	109.5
N2—C1—H1B	109.3	N4—C10—H10A	109.5
N1—C1—H1B	109.3	N4—C10—H10B	109.5
H1A—C1—H1B	108.0	H10A—C10—H10B	109.5
N2A—C1A—N1A	111.24 (19)	N4—C10—H10C	109.5
N2A—C1A—H1A1	109.4	H10A—C10—H10C	109.5
N1A—C1A—H1A1	109.4	H10B—C10—H10C	109.5
N2A—C1A—H1A2	109.4	N4A—C10A—H10D	109.5
N1A—C1A—H1A2	109.4	N4A—C10A—H10E	109.5
H1A1—C1A—H1A2	108.0	H10D—C10A—H10E	109.5
N2—C2—C7	120.5 (2)	N4A—C10A—H10F	109.5
N2—C2—C3	122.1 (2)	H10D—C10A—H10F	109.5
C7—C2—C3	117.30 (19)	H10E—C10A—H10F	109.5

O2—S1—N1—C1	69.22 (18)	S1A—C3A—C4A—C5A	179.31 (17)
O1—S1—N1—C1	−161.54 (15)	C3—C4—C5—C6	−1.3 (3)
C3—S1—N1—C1	−47.16 (18)	C3—C4—C5—S2	−178.50 (16)
O1A—S1A—N1A—C1A	−170.70 (16)	O4—S2—C5—C4	−124.24 (17)
O2A—S1A—N1A—C1A	59.74 (18)	O3—S2—C5—C4	4.8 (2)
C3A—S1A—N1A—C1A	−54.69 (18)	N3—S2—C5—C4	119.31 (19)
C2—N2—C1—N1	−42.9 (3)	O4—S2—C5—C6	58.7 (2)
S1—N1—C1—N2	65.1 (2)	O3—S2—C5—C6	−172.23 (18)
C2A—N2A—C1A—N1A	−37.9 (3)	N3—S2—C5—C6	−57.7 (2)
S1A—N1A—C1A—N2A	65.0 (2)	C3A—C4A—C5A—C6A	−1.1 (3)
C1—N2—C2—C7	−176.4 (2)	C3A—C4A—C5A—S2A	−179.77 (16)
C1—N2—C2—C3	5.9 (3)	O3A—S2A—C5A—C4A	−5.9 (2)
C1A—N2A—C2A—C7A	−176.3 (2)	O4A—S2A—C5A—C4A	122.37 (18)
C1A—N2A—C2A—C3A	4.5 (3)	N3A—S2A—C5A—C4A	−120.75 (19)
N2—C2—C3—C4	−179.7 (2)	O3A—S2A—C5A—C6A	175.47 (19)
C7—C2—C3—C4	2.5 (3)	O4A—S2A—C5A—C6A	−56.2 (2)
N2—C2—C3—S1	7.7 (3)	N3A—S2A—C5A—C6A	60.7 (2)
C7—C2—C3—S1	−170.05 (16)	C4—C5—C6—C7	3.8 (3)
O2—S1—C3—C4	84.64 (19)	S2—C5—C6—C7	−179.20 (17)
O1—S1—C3—C4	−45.9 (2)	C4—C5—C6—Cl1	−174.61 (16)
N1—S1—C3—C4	−160.14 (17)	S2—C5—C6—Cl1	2.4 (3)
O2—S1—C3—C2	−102.56 (18)	C4A—C5A—C6A—C7A	−0.1 (3)
O1—S1—C3—C2	126.87 (18)	S2A—C5A—C6A—C7A	178.50 (18)
N1—S1—C3—C2	12.7 (2)	C4A—C5A—C6A—Cl1A	178.92 (17)
N2A—C2A—C3A—C4A	178.6 (2)	S2A—C5A—C6A—Cl1A	−2.5 (3)
C7A—C2A—C3A—C4A	−0.7 (3)	C5—C6—C7—C2	−3.1 (3)
N2A—C2A—C3A—S1A	0.8 (3)	Cl1—C6—C7—C2	175.37 (17)
C7A—C2A—C3A—S1A	−178.55 (16)	N2—C2—C7—C6	−177.9 (2)
O1A—S1A—C3A—C4A	−39.7 (2)	C3—C2—C7—C6	−0.1 (3)
O2A—S1A—C3A—C4A	91.75 (19)	C5A—C6A—C7A—C2A	0.9 (3)
N1A—S1A—C3A—C4A	−154.64 (18)	Cl1A—C6A—C7A—C2A	−178.17 (17)
O1A—S1A—C3A—C2A	138.16 (17)	N2A—C2A—C7A—C6A	−179.8 (2)
O2A—S1A—C3A—C2A	−90.39 (19)	C3A—C2A—C7A—C6A	−0.5 (3)
N1A—S1A—C3A—C2A	23.2 (2)	C9—N4—C8—O5	−3.1 (4)
C2—C3—C4—C5	−1.8 (3)	C10—N4—C8—O5	179.1 (2)
S1—C3—C4—C5	170.89 (17)	C10A—N4A—C8A—O5A	−0.4 (4)
C2A—C3A—C4A—C5A	1.5 (3)	C9A—N4A—C8A—O5A	176.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2Aⁱ	0.80 (3)	2.60 (3)	3.290 (3)	146 (3)
N2—H2N···O4ⁱ	0.74 (3)	2.47 (3)	3.023 (3)	134 (3)
N3—H3N···O5	0.90 (3)	2.07 (3)	2.954 (3)	165 (3)
N3—H4N···O2Aⁱⁱ	0.85 (4)	2.35 (4)	3.092 (3)	146 (3)
N1A—H5N···O5Aⁱⁱⁱ	0.78 (4)	2.12 (4)	2.882 (3)	167 (3)
N2A—H6N···N3Aⁱ	0.77 (4)	2.48 (4)	3.177 (3)	150 (3)
N3A—H7N···O5^iv	0.95 (4)	1.89 (4)	2.820 (3)	164 (3)
N3A—H8N···O5A^iv	0.86 (3)	2.12 (3)	2.942 (3)	163 (2)
C1A—H1A1···O3Aⁱ	0.99	2.42	3.157 (3)	131
C1—H1A···O3ⁱ	0.99	2.56	3.235 (3)	125
C1A—H1A2···O3	0.99	2.51	3.467 (3)	162
C7—H7···O2ⁱⁱ	0.95	2.56	3.466 (3)	159
C7A—H7A···O1Aⁱⁱ	0.95	2.45	3.163 (3)	132
C9—H9B···O1ⁱⁱ	0.98	2.54	3.442 (3)	152
C10—H10C···O1ⁱⁱ	0.98	2.51	3.323 (3)	141

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

Acknowledgements

The authors 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: https://www.cposs.org.uk). Thanks are also due to the CCLRC for provision of a beamtime grant at Daresbury SRS.

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