Hydro­chloro­thia­zide N-methyl-2-pyrrolidone disolvate

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

doi:10.1107/S1600536806042838

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 11| November 2006| Pages o5169-o5171

https://doi.org/10.1107/S1600536806042838

Hydrochlorothiazide N-methyl-2-pyrrolidone disolvate

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

^aSolid State Research Group, Strathclyde Institute of Pharmacy and Biomedical 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 20 September 2006; accepted 15 October 2006; online 25 October 2006)

Hydrochlorothiazide forms a 1:2 solvate with N-methylpyrrolidone (systematic name: 6-chloro-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide 1,1-dioxide N-methyl-2-pyrrolidone disolvate), C₇H₈ClN₃O₄S₂·2C₅H₉NO. The compound crystallizes with one hydrochlorothiazide and two solvent molecules, one of which is disordered, in the asymmetric unit. The crystal structure is isostructural with the previously reported hydrochlorothiazide N,N-dimethylacetamide disolvate.

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 title compound of this report, (I), was produced during an automated parallel crystallization study of HCT (Johnston, Florence, Shankland et al., 2006 ). The sample was identified as a novel form using multi-sample foil transmission X-ray powder diffraction analysis (Florence et al., 2003 ). Subsequent manual recrystallization from a saturated N-methylpyrrolidone (NMP) solution by slow evaporation at 298 K yielded samples of (I) suitable for single-crystal diffraction (Fig. 1).

It is notable that the crystal structure of (I) is isostructural with that of the previously reported HCT N,N-dimethylacetamide (DMA) disolvate (Johnston, Florence & Kennedy, 2006 ), with the same space group and very similar unit-cell parameters and packing arrangements. Adjacent HCT chains pack as layers in the ab plane and form an alternating stacked arrangement with layers of solvent molecules in the direction of the c axis (Fig. 2). The structures differ slightly in the extent of solvent disorder, with both solvent molecules disordered in the HCT–DMA disolvate, compared with a single molecule in (I). The structure also contains four N—H⋯O hydrogen bonds, with N1, N2 and N3 of HCT donating contacts to adjacent O atoms of NMP (Table 1).

Figure 1
The asymmetric unit contents of (I)

, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Minor disorder components have been omitted for clarity.

Figure 2
The crystal packing in the structure of (I)

, viewed down the b axis, showing the alternating layers of HCT and NMP molecules.

Experimental

A single-crystal sample of the title compound was recrystallized from a saturated N-methylpyrrolidone solution by isothermal solvent evaporation at 298 K.

Crystal data

C₇H₈ClN₃O₄S₂·2C₅H₉NO
M_r = 496.00
Monoclinic, P 2₁ /c
a = 17.0756 (6) Å
b = 7.4819 (3) Å
c = 17.9978 (6) Å
β = 105.211 (2)°
V = 2218.81 (14) Å³
Z = 4
D_x = 1.485 Mg m⁻³
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 123 (2) K
Cut from prism, colourless
0.32 × 0.20 × 0.12 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: none
24804 measured reflections
4852 independent reflections
3673 reflections with I > 2σ(I)
R_int = 0.093
θ_max = 27.1°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.174
S = 1.08
4852 reflections
296 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.1041P)² + 0.892P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O6ⁱ	0.79 (5)	2.01 (5)	2.799 (4)	177 (5)
N2—H2N⋯O6ⁱⁱ	0.80 (4)	2.35 (4)	2.929 (4)	130 (3)
N3—H3N⋯O5	0.84 (3)	2.12 (4)	2.891 (4)	153 (4)
N3—H4N⋯O5ⁱⁱⁱ	0.86 (4)	2.04 (4)	2.884 (4)	169 (3)
C1—H1A⋯O6ⁱⁱ	0.99	2.58	3.075 (4)	111
C7—H7⋯O2^iv	0.95	2.33	3.249 (4)	164
C11—H11B⋯O3^v	0.99	2.52	3.423 (4)	152
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x, y+1, z; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Three C atoms (C14, C15 and C16) and the associated H atoms of one solvent molecule were treated as disordered over two sites. Isotropic refinement gave a refined occupancy of 0.52 (3):0.48 (3). All amine H atoms were found by difference synthesis and refined isotropically. All other H atoms were positioned geometrically at distances of 0.95 (CH), 0.98 (CH₃) or 0.99 Å (CH₂); a riding model was used during refinement, with U_iso(H) = 1.5U_eq(C) for methyl H atoms and U_iso(H) = 1.2U_eq(C) for all others.

Data collection: COLLECT (Nonius, 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: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806042838/kj2037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806042838/kj2037Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 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: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

6-chloro-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide 1,1-dioxide N-methyl-2-pyrrolidone disolvate top

Crystal data top

C₇H₈ClN₃O₄S₂·2C₅H₉NO	F(000) = 1040
M_r = 496.00	D_x = 1.485 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5023 reflections
a = 17.0756 (6) Å	θ = 1.0–27.1°
b = 7.4819 (3) Å	µ = 0.41 mm⁻¹
c = 17.9978 (6) Å	T = 123 K
β = 105.211 (2)°	Cut from prism, colourless
V = 2218.81 (14) Å³	0.32 × 0.20 × 0.12 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	3673 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.093
Graphite monochromator	θ_max = 27.1°, θ_min = 1.2°
φ and ω scans	h = −21→21
24804 measured reflections	k = −9→9
4852 independent reflections	l = −22→22

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.174	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.1041P)² + 0.892P] where P = (F_o² + 2F_c²)/3
4852 reflections	(Δ/σ)_max = 0.001
296 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.55 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	Occ. (<1)
Cl1	0.83783 (4)	0.43550 (10)	0.16447 (4)	0.0287 (2)
S1	0.65205 (4)	−0.18853 (10)	0.27397 (4)	0.0237 (2)
S2	0.89965 (4)	0.01810 (10)	0.15514 (4)	0.0210 (2)
O1	0.69144 (13)	−0.2471 (3)	0.35033 (12)	0.0372 (6)
O2	0.63256 (13)	−0.3193 (3)	0.21369 (13)	0.0310 (5)
O3	0.88310 (12)	0.0813 (3)	0.07722 (11)	0.0273 (5)
O4	0.90847 (11)	−0.1695 (3)	0.16923 (11)	0.0247 (5)
O5	0.98030 (12)	−0.0406 (3)	0.35009 (12)	0.0286 (5)
O6	0.54188 (14)	1.0488 (3)	−0.13077 (13)	0.0361 (6)
N1	0.56794 (15)	−0.0889 (3)	0.27559 (16)	0.0248 (5)
N2	0.62120 (16)	0.2066 (4)	0.28470 (16)	0.0304 (6)
N3	0.97927 (15)	0.1167 (4)	0.20314 (16)	0.0249 (5)
N4	0.90110 (15)	0.0930 (4)	0.41855 (14)	0.0288 (6)
N5	0.63002 (18)	0.9495 (4)	−0.02142 (15)	0.0378 (7)
C1	0.58148 (19)	0.0752 (4)	0.32033 (18)	0.0289 (7)
H1A	0.5288	0.1229	0.3247	0.035*
H1B	0.6154	0.0494	0.3729	0.035*
C2	0.68438 (17)	0.1647 (4)	0.25432 (16)	0.0238 (6)
C3	0.70834 (16)	−0.0145 (4)	0.24753 (16)	0.0214 (6)
C4	0.77418 (16)	−0.0536 (4)	0.21818 (16)	0.0219 (6)
H4	0.7905	−0.1744	0.2158	0.026*
C5	0.81629 (16)	0.0808 (4)	0.19233 (16)	0.0210 (6)
C6	0.79023 (16)	0.2571 (4)	0.19616 (16)	0.0229 (6)
C7	0.72558 (17)	0.2987 (4)	0.22588 (17)	0.0256 (6)
H7	0.7090	0.4197	0.2270	0.031*
C8	0.93403 (18)	−0.0472 (4)	0.39273 (17)	0.0264 (7)
C9	0.90442 (19)	−0.2160 (4)	0.42372 (18)	0.0309 (7)
H9A	0.9502	−0.2975	0.4461	0.037*
H9B	0.8643	−0.2798	0.3826	0.037*
C10	0.8654 (2)	−0.1475 (5)	0.48563 (19)	0.0368 (8)
H10A	0.8162	−0.2174	0.4857	0.044*
H10B	0.9040	−0.1550	0.5373	0.044*
C11	0.84395 (19)	0.0454 (4)	0.46353 (18)	0.0314 (7)
H11A	0.7871	0.0562	0.4322	0.038*
H11B	0.8518	0.1220	0.5097	0.038*
C12	0.91140 (19)	0.2762 (4)	0.39683 (18)	0.0320 (7)
H12A	0.9503	0.2801	0.3654	0.048*
H12B	0.9317	0.3485	0.4433	0.048*
H12C	0.8591	0.3237	0.3671	0.048*
C13	0.56205 (19)	0.9407 (4)	−0.07679 (18)	0.0295 (7)
C14A	0.5044 (7)	0.7798 (12)	−0.0695 (6)	0.032 (3)*	0.52 (3)
H14A	0.4508	0.8221	−0.0653	0.039*	0.52 (3)
H14B	0.4969	0.6957	−0.1132	0.039*	0.52 (3)
C15A	0.5546 (8)	0.6956 (12)	0.0066 (5)	0.035 (2)*	0.52 (3)
H15A	0.5568	0.5641	0.0011	0.042*	0.52 (3)
H15B	0.5292	0.7227	0.0488	0.042*	0.52 (3)
C16A	0.6444 (5)	0.7776 (18)	0.0258 (6)	0.045 (3)*	0.52 (3)
H16A	0.6656	0.8027	0.0814	0.054*	0.52 (3)
H16B	0.6823	0.6969	0.0089	0.054*	0.52 (3)
C14B	0.5226 (8)	0.7851 (14)	−0.0571 (7)	0.033 (3)*	0.48 (3)
H14C	0.5107	0.6995	−0.1006	0.040*	0.48 (3)
H14D	0.4707	0.8193	−0.0461	0.040*	0.48 (3)
C15B	0.5793 (10)	0.6982 (14)	0.0145 (6)	0.045 (3)*	0.48 (3)
H15C	0.5501	0.6709	0.0539	0.055*	0.48 (3)
H15D	0.6037	0.5868	0.0008	0.055*	0.48 (3)
C16B	0.6381 (6)	0.829 (2)	0.0403 (7)	0.048 (3)*	0.48 (3)
H16C	0.6930	0.7750	0.0543	0.058*	0.48 (3)
H16D	0.6292	0.8906	0.0860	0.058*	0.48 (3)
C17	0.6911 (2)	1.0796 (6)	−0.0191 (2)	0.0549 (11)
H17A	0.7374	1.0236	−0.0326	0.082*
H17B	0.7089	1.1299	0.0329	0.082*
H17C	0.6692	1.1751	−0.0559	0.082*
H1N	0.538 (3)	−0.080 (6)	0.234 (3)	0.061 (14)*
H2N	0.613 (2)	0.310 (5)	0.290 (2)	0.035 (10)*
H3N	0.994 (2)	0.092 (5)	0.250 (2)	0.044 (11)*
H4N	0.986 (2)	0.224 (5)	0.189 (2)	0.032 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0261 (4)	0.0232 (4)	0.0392 (4)	−0.0011 (3)	0.0127 (3)	0.0036 (3)
S1	0.0181 (4)	0.0252 (4)	0.0282 (4)	0.0008 (3)	0.0066 (3)	0.0044 (3)
S2	0.0179 (4)	0.0233 (4)	0.0224 (4)	0.0000 (3)	0.0066 (3)	−0.0006 (3)
O1	0.0254 (11)	0.0485 (14)	0.0340 (12)	−0.0007 (11)	0.0010 (9)	0.0174 (11)
O2	0.0282 (11)	0.0253 (11)	0.0422 (12)	−0.0012 (9)	0.0139 (10)	−0.0033 (9)
O3	0.0282 (11)	0.0337 (12)	0.0205 (10)	0.0016 (9)	0.0073 (9)	0.0022 (9)
O4	0.0213 (10)	0.0242 (11)	0.0303 (11)	0.0019 (8)	0.0097 (9)	−0.0018 (9)
O5	0.0278 (11)	0.0301 (11)	0.0312 (11)	0.0022 (9)	0.0133 (10)	0.0012 (9)
O6	0.0296 (12)	0.0368 (13)	0.0369 (13)	−0.0007 (10)	−0.0003 (10)	0.0083 (10)
N1	0.0177 (12)	0.0294 (14)	0.0269 (13)	0.0008 (10)	0.0053 (11)	0.0001 (11)
N2	0.0270 (14)	0.0262 (15)	0.0425 (16)	0.0012 (11)	0.0171 (12)	−0.0038 (12)
N3	0.0198 (12)	0.0260 (14)	0.0283 (14)	−0.0016 (11)	0.0054 (11)	0.0013 (12)
N4	0.0261 (13)	0.0316 (14)	0.0295 (14)	−0.0009 (11)	0.0086 (11)	0.0002 (11)
N5	0.0433 (17)	0.0437 (17)	0.0254 (14)	0.0050 (13)	0.0071 (13)	0.0052 (12)
C1	0.0277 (15)	0.0299 (16)	0.0321 (16)	−0.0015 (13)	0.0131 (13)	−0.0050 (13)
C2	0.0195 (14)	0.0259 (15)	0.0258 (14)	0.0014 (12)	0.0053 (11)	−0.0024 (12)
C7	0.0211 (14)	0.0210 (14)	0.0345 (16)	0.0022 (12)	0.0072 (12)	−0.0014 (12)
C6	0.0194 (13)	0.0222 (14)	0.0263 (14)	−0.0019 (12)	0.0049 (11)	0.0010 (12)
C5	0.0142 (13)	0.0253 (14)	0.0220 (14)	0.0015 (11)	0.0021 (11)	−0.0014 (11)
C4	0.0200 (14)	0.0214 (14)	0.0224 (14)	0.0023 (11)	0.0022 (11)	0.0009 (11)
C3	0.0162 (13)	0.0245 (14)	0.0224 (14)	0.0007 (11)	0.0032 (11)	0.0014 (11)
C8	0.0231 (15)	0.0296 (16)	0.0228 (14)	0.0004 (12)	−0.0004 (12)	−0.0029 (12)
C9	0.0304 (17)	0.0294 (16)	0.0312 (16)	−0.0015 (13)	0.0049 (13)	0.0010 (13)
C10	0.0380 (19)	0.0414 (19)	0.0326 (17)	−0.0058 (16)	0.0122 (15)	0.0032 (15)
C11	0.0298 (16)	0.0400 (18)	0.0276 (16)	0.0007 (14)	0.0134 (14)	−0.0020 (14)
C12	0.0336 (17)	0.0277 (16)	0.0326 (16)	−0.0013 (14)	0.0047 (14)	0.0022 (13)
C13	0.0286 (16)	0.0328 (17)	0.0278 (16)	0.0057 (13)	0.0086 (14)	−0.0026 (13)
C17	0.037 (2)	0.074 (3)	0.045 (2)	−0.010 (2)	−0.0049 (17)	0.009 (2)

Geometric parameters (Å, º) top

Cl1—C6	1.735 (3)	C4—H4	0.9500
S1—O1	1.431 (2)	C8—C9	1.520 (4)
S1—O2	1.434 (2)	C9—C10	1.529 (4)
S1—N1	1.625 (3)	C9—H9A	0.9900
S1—C3	1.756 (3)	C9—H9B	0.9900
S2—O4	1.427 (2)	C10—C11	1.516 (5)
S2—O3	1.436 (2)	C10—H10A	0.9900
S2—N3	1.588 (3)	C10—H10B	0.9900
S2—C5	1.787 (3)	C11—H11A	0.9900
O5—C8	1.239 (4)	C11—H11B	0.9900
O6—C13	1.241 (4)	C12—H12A	0.9800
N1—C1	1.453 (4)	C12—H12B	0.9800
N1—H1N	0.79 (4)	C12—H12C	0.9800
N2—C2	1.368 (4)	C13—C14B	1.435 (11)
N2—C1	1.437 (4)	C13—C14A	1.582 (11)
N2—H2N	0.79 (4)	C14A—C15A	1.547 (12)
N3—H3N	0.84 (4)	C14A—H14A	0.9900
N3—H4N	0.86 (4)	C14A—H14B	0.9900
N4—C8	1.330 (4)	C15A—C16A	1.602 (14)
N4—C12	1.448 (4)	C15A—H15A	0.9900
N4—C11	1.466 (4)	C15A—H15B	0.9900
N5—C13	1.318 (4)	C16A—H16A	0.9900
N5—C16B	1.411 (10)	C16A—H16B	0.9900
N5—C17	1.419 (5)	C14B—C15B	1.538 (14)
N5—C16A	1.525 (10)	C14B—H14C	0.9900
C1—H1A	0.9900	C14B—H14D	0.9900
C1—H1B	0.9900	C15B—C16B	1.390 (14)
C2—C7	1.397 (4)	C15B—H15C	0.9900
C2—C3	1.416 (4)	C15B—H15D	0.9900
C7—C6	1.382 (4)	C16B—H16C	0.9900
C7—H7	0.9500	C16B—H16D	0.9900
C6—C5	1.400 (4)	C17—H17A	0.9800
C5—C4	1.386 (4)	C17—H17B	0.9800
C4—C3	1.393 (4)	C17—H17C	0.9800

O1—S1—O2	118.35 (14)	C9—C10—H10A	110.9
O1—S1—N1	108.55 (14)	C11—C10—H10B	110.9
O2—S1—N1	107.21 (13)	C9—C10—H10B	110.9
O1—S1—C3	109.54 (14)	H10A—C10—H10B	108.9
O2—S1—C3	109.62 (13)	N4—C11—C10	103.1 (2)
N1—S1—C3	102.34 (13)	N4—C11—H11A	111.2
O4—S2—O3	118.80 (12)	C10—C11—H11A	111.2
O4—S2—N3	108.95 (14)	N4—C11—H11B	111.2
O3—S2—N3	107.43 (14)	C10—C11—H11B	111.2
O4—S2—C5	104.41 (12)	H11A—C11—H11B	109.1
O3—S2—C5	107.89 (13)	N4—C12—H12A	109.5
N3—S2—C5	109.06 (13)	N4—C12—H12B	109.5
C1—N1—S1	112.6 (2)	H12A—C12—H12B	109.5
C1—N1—H1N	115 (3)	N4—C12—H12C	109.5
S1—N1—H1N	112 (3)	H12A—C12—H12C	109.5
C2—N2—C1	122.4 (3)	H12B—C12—H12C	109.5
C2—N2—H2N	116 (3)	O6—C13—N5	124.6 (3)
C1—N2—H2N	120 (3)	O6—C13—C14B	132.1 (6)
S2—N3—H3N	115 (3)	N5—C13—C14B	103.4 (6)
S2—N3—H4N	116 (2)	O6—C13—C14A	120.7 (5)
H3N—N3—H4N	118 (4)	N5—C13—C14A	114.8 (5)
C8—N4—C12	124.0 (3)	C15A—C14A—C13	99.9 (7)
C8—N4—C11	113.9 (3)	C15A—C14A—H14A	111.8
C12—N4—C11	121.6 (3)	C13—C14A—H14A	111.8
C13—N5—C16B	116.6 (5)	C15A—C14A—H14B	111.8
C13—N5—C17	123.5 (3)	C13—C14A—H14B	111.8
C16B—N5—C17	119.8 (5)	H14A—C14A—H14B	109.5
C13—N5—C16A	111.1 (4)	C14A—C15A—C16A	108.1 (7)
C17—N5—C16A	123.5 (4)	C14A—C15A—H15A	110.1
N2—C1—N1	110.8 (2)	C16A—C15A—H15A	110.1
N2—C1—H1A	109.5	C14A—C15A—H15B	110.1
N1—C1—H1A	109.5	C16A—C15A—H15B	110.1
N2—C1—H1B	109.5	H15A—C15A—H15B	108.4
N1—C1—H1B	109.5	N5—C16A—C15A	101.5 (6)
H1A—C1—H1B	108.1	N5—C16A—H16A	111.5
N2—C2—C7	120.5 (3)	C15A—C16A—H16A	111.5
N2—C2—C3	121.8 (3)	N5—C16A—H16B	111.5
C7—C2—C3	117.6 (2)	C15A—C16A—H16B	111.5
C6—C7—C2	120.7 (3)	H16A—C16A—H16B	109.3
C6—C7—H7	119.7	C13—C14B—C15B	108.5 (8)
C2—C7—H7	119.7	C13—C14B—H14C	110.0
C7—C6—C5	121.8 (3)	C15B—C14B—H14C	110.0
C7—C6—Cl1	116.4 (2)	C13—C14B—H14D	110.0
C5—C6—Cl1	121.8 (2)	C15B—C14B—H14D	110.0
C4—C5—C6	117.9 (2)	H14C—C14B—H14D	108.4
C4—C5—S2	118.0 (2)	C16B—C15B—C14B	102.9 (9)
C6—C5—S2	124.1 (2)	C16B—C15B—H15C	111.2
C5—C4—C3	121.1 (3)	C14B—C15B—H15C	111.2
C5—C4—H4	119.4	C16B—C15B—H15D	111.2
C3—C4—H4	119.4	C14B—C15B—H15D	111.2
C4—C3—C2	120.7 (3)	H15C—C15B—H15D	109.1
C4—C3—S1	120.1 (2)	C15B—C16B—N5	105.9 (8)
C2—C3—S1	119.2 (2)	C15B—C16B—H16C	110.6
O5—C8—N4	125.6 (3)	N5—C16B—H16C	110.6
O5—C8—C9	126.0 (3)	C15B—C16B—H16D	110.6
N4—C8—C9	108.4 (3)	N5—C16B—H16D	110.6
C8—C9—C10	103.8 (3)	H16C—C16B—H16D	108.7
C8—C9—H9A	111.0	N5—C17—H17A	109.5
C10—C9—H9A	111.0	N5—C17—H17B	109.5
C8—C9—H9B	111.0	H17A—C17—H17B	109.5
C10—C9—H9B	111.0	N5—C17—H17C	109.5
H9A—C9—H9B	109.0	H17A—C17—H17C	109.5
C11—C10—C9	104.5 (2)	H17B—C17—H17C	109.5
C11—C10—H10A	110.9

O1—S1—N1—C1	65.6 (2)	C12—N4—C8—O5	3.5 (5)
O2—S1—N1—C1	−165.5 (2)	C11—N4—C8—O5	175.8 (3)
C3—S1—N1—C1	−50.2 (2)	C12—N4—C8—C9	−175.9 (3)
C2—N2—C1—N1	−42.9 (4)	C11—N4—C8—C9	−3.6 (3)
S1—N1—C1—N2	65.8 (3)	O5—C8—C9—C10	168.1 (3)
C1—N2—C2—C7	−174.7 (3)	N4—C8—C9—C10	−12.6 (3)
C1—N2—C2—C3	7.9 (5)	C8—C9—C10—C11	22.9 (3)
N2—C2—C7—C6	179.0 (3)	C8—N4—C11—C10	18.3 (3)
C3—C2—C7—C6	−3.4 (4)	C12—N4—C11—C10	−169.2 (3)
C2—C7—C6—C5	0.9 (4)	C9—C10—C11—N4	−24.6 (3)
C2—C7—C6—Cl1	−178.7 (2)	C16B—N5—C13—O6	172.2 (9)
C7—C6—C5—C4	1.1 (4)	C17—N5—C13—O6	−3.6 (5)
Cl1—C6—C5—C4	−179.3 (2)	C16A—N5—C13—O6	−168.2 (6)
C7—C6—C5—S2	−179.6 (2)	C16B—N5—C13—C14B	−7.4 (10)
Cl1—C6—C5—S2	−0.1 (4)	C17—N5—C13—C14B	176.8 (5)
O4—S2—C5—C4	−6.0 (2)	C16A—N5—C13—C14B	12.2 (8)
O3—S2—C5—C4	121.3 (2)	C16B—N5—C13—C14A	−6.7 (10)
N3—S2—C5—C4	−122.4 (2)	C17—N5—C13—C14A	177.5 (5)
O4—S2—C5—C6	174.8 (2)	C16A—N5—C13—C14A	12.9 (8)
O3—S2—C5—C6	−58.0 (3)	O6—C13—C14A—C15A	−177.5 (5)
N3—S2—C5—C6	58.4 (3)	N5—C13—C14A—C15A	1.4 (7)
C6—C5—C4—C3	−0.4 (4)	C14B—C13—C14A—C15A	5 (3)
S2—C5—C4—C3	−179.7 (2)	C13—C14A—C15A—C16A	−14.2 (10)
C5—C4—C3—C2	−2.3 (4)	C13—N5—C16A—C15A	−20.6 (10)
C5—C4—C3—S1	175.8 (2)	C17—N5—C16A—C15A	174.8 (5)
N2—C2—C3—C4	−178.4 (3)	C14A—C15A—C16A—N5	21.0 (11)
C7—C2—C3—C4	4.2 (4)	O6—C13—C14B—C15B	177.0 (6)
N2—C2—C3—S1	3.5 (4)	N5—C13—C14B—C15B	−3.5 (8)
C7—C2—C3—S1	−173.9 (2)	C14A—C13—C14B—C15B	180 (4)
O1—S1—C3—C4	83.6 (3)	C13—C14B—C15B—C16B	12.5 (14)
O2—S1—C3—C4	−47.8 (3)	C14B—C15B—C16B—N5	−15.9 (16)
N1—S1—C3—C4	−161.3 (2)	C13—N5—C16B—C15B	16.2 (17)
O1—S1—C3—C2	−98.2 (3)	C17—N5—C16B—C15B	−167.9 (10)
O2—S1—C3—C2	130.4 (2)	C16A—N5—C16B—C15B	−61 (2)
N1—S1—C3—C2	16.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O6ⁱ	0.79 (5)	2.01 (5)	2.799 (4)	177 (5)
N2—H2N···O6ⁱⁱ	0.80 (4)	2.35 (4)	2.929 (4)	130 (3)
N3—H3N···O5	0.84 (3)	2.12 (4)	2.891 (4)	153 (4)
N3—H4N···O5ⁱⁱⁱ	0.86 (4)	2.04 (4)	2.884 (4)	169 (3)
C1—H1A···O6ⁱⁱ	0.99	2.58	3.075 (4)	111
C7—H7···O2^iv	0.95	2.33	3.249 (4)	164
C11—H11B···O3^v	0.99	2.52	3.423 (4)	152

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, −y+3/2, z+1/2; (iii) −x+2, y+1/2, −z+1/2; (iv) x, y+1, z; (v) x, −y+1/2, z+1/2.

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

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