Hydrogen-bonding synthons in lamotrigine salts: 3,5-di­amino-6-(2,3-di­chloro­phen­yl)-1,2,4-triazin-2-ium 2-[(2-carb­oxy­phen­yl)disulfan­yl]benzoate in its monohydrate and anhydrous forms

Lamotrigine is a drug used in the treatment of epilepsy and related convulsive diseases. The drug in its free form is rather inadequate for pharmacological use due to poor absorption by the patient, which limits its bioavailability. On the other hand, the lamotrigine mol­ecule is an excellent hydrogen-bonding agent and this has been exploited intensively in the search for better formulations. The formulation presently commercialized (under the brand name Lamictal) is rather complex and includes a number of anions in addition to the active pharmaceutical ingredient (API). The title salts of lamotrigine, namely 3,5-di­amino-6-(2,3-di­chloro­phen­yl)-1,2,4-triazin-2-ium 2-[(2-carb­oxy­phen­yl)di­sul­fan­yl]benzoate monohydrate, C₉H₈Cl₂N₅⁺·C₁₄H₉O₄S₂⁻·H₂O, (I), and the anhydrate, C₉H₈Cl₂N₅⁺·C₁₄H₉O₄S₂⁻, (II), contain a lamotriginium cation (L), a hydrogen di­thio­dibenzoate monoanion (D) and, in the case of (I), a disordered solvent water mol­ecule. Both L and D present their usual configurations severely twisted around their central C—C and S—S bonds, respectively. The supra­molecular structure generated by the many available donor and acceptor sites is characterized by a planar anti­symmetric motif of the form D–L–L–D, i.e. the structural building block. Although this characteristic motif is extremely similar in both structures, its conformation involves different donors and acceptors in its R₂²(8) central L–L homosynthon. The lateral R₂²(8) D–L hetero­synthons are, on the other hand, identical. These substructures are further connected by strong hydrogen bonds into broad two-dimensional structures, in turn weakly linked to each other. Even if the homo- and heterosynthons in (I) and (II) are rather frequent in lamotrigine structural chemistry, the composite tetra­meric synthon appears to be much less common. The occurrence of these motifs among lamotrigine salts and cocrystals is analyzed.

Computing details

For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008). Software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) andPLATON (Spek, 2009) for (I); SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009) for (II).

(I) 3,5-Diamino-6-(2,3-dichlorophenyl)-1,2,4-triazin-2-ium 2-[(2-carboxyphenyl)disulfanyl]benzoate monohydrate

Crystal data

C9H8Cl2N5^+·C14H9O4S2^−·H2O	Z = 2
Mr = 580.45	F(000) = 596
Triclinic, P1	Dx = 1.540 Mg m^−3
a = 8.0598 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.3474 (13) Å	Cell parameters from 1591 reflections
c = 13.4484 (10) Å	θ = 4.0–24.6°
α = 100.996 (7)°	µ = 0.47 mm^−1
β = 98.101 (7)°	T = 294 K
γ = 103.659 (8)°	Prism, pale_yellow
V = 1252.1 (2) Å^3	0.50 × 0.25 × 0.15 mm

Data collection

Oxford Diffraction Gemini CCD S Ultra diffractometer	3744 reflections with I > 2σ(I)
ω scans, thick slices	Rint = 0.035
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	θmax = 29.3°, θmin = 3.7°
Tmin = 0.84, Tmax = 0.95	h = −10→9
11193 measured reflections	k = −16→16
5794 independent reflections	l = −18→17

Refinement

Refinement on F^2	8 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.166	w = 1/[σ^2(Fo^2) + (0.0716P)^2 + 0.7292P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
5794 reflections	Δρmax = 0.78 e Å^−3
356 parameters	Δρmin = −0.42 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S11	0.77327 (12)	−0.07472 (7)	0.28054 (7)	0.0412 (2)
O11	0.8359 (3)	−0.2817 (2)	0.2858 (2)	0.0429 (6)
O21	0.7123 (3)	−0.4436 (2)	0.1645 (2)	0.0466 (6)
H21O	0.735 (5)	−0.483 (3)	0.207 (2)	0.056*
C11	0.6798 (4)	−0.1567 (3)	0.1521 (3)	0.0352 (7)
C21	0.6092 (4)	−0.1083 (3)	0.0785 (3)	0.0450 (9)
H21	0.6096	−0.0317	0.0964	0.054*
C31	0.5371 (5)	−0.1712 (3)	−0.0220 (3)	0.0487 (9)
H31	0.4906	−0.1369	−0.0710	0.058*
C41	0.5354 (5)	−0.2851 (3)	−0.0481 (3)	0.0467 (9)
H41	0.4862	−0.3283	−0.1148	0.056*
C51	0.6058 (4)	−0.3352 (3)	0.0239 (3)	0.0397 (8)
H51	0.6041	−0.4120	0.0051	0.048*
C61	0.6799 (4)	−0.2730 (3)	0.1249 (3)	0.0326 (7)
C71	0.7506 (4)	−0.3306 (3)	0.1995 (3)	0.0367 (8)
S12	0.69471 (11)	0.07312 (7)	0.29397 (7)	0.0398 (2)
O12	0.6162 (3)	0.2656 (2)	0.3413 (2)	0.0481 (6)
O22	0.7138 (3)	0.43096 (18)	0.29926 (17)	0.0362 (5)
C12	0.8473 (4)	0.1655 (3)	0.2412 (2)	0.0315 (7)
C22	0.9662 (4)	0.1253 (3)	0.1894 (3)	0.0391 (8)
H22	0.9681	0.0493	0.1833	0.047*
C32	1.0812 (4)	0.1955 (3)	0.1472 (3)	0.0433 (8)
H32	1.1613	0.1672	0.1142	0.052*
C42	1.0780 (5)	0.3079 (3)	0.1537 (3)	0.0465 (9)
H42	1.1560	0.3557	0.1255	0.056*
C52	0.9576 (4)	0.3485 (3)	0.2025 (3)	0.0370 (8)
H52	0.9534	0.4236	0.2055	0.044*
C62	0.8422 (4)	0.2791 (3)	0.2476 (2)	0.0309 (7)
C72	0.7146 (4)	0.3283 (3)	0.2994 (2)	0.0333 (7)
Cl1	0.16354 (15)	0.88548 (10)	0.09415 (8)	0.0631 (3)
Cl2	0.18343 (14)	0.64446 (9)	0.12805 (8)	0.0564 (3)
N1	0.4223 (4)	0.5934 (2)	0.3226 (2)	0.0399 (7)
N2	0.4335 (3)	0.4952 (2)	0.3473 (2)	0.0375 (7)
H2	0.519 (3)	0.469 (3)	0.334 (3)	0.045*
N3	0.3547 (4)	0.3462 (3)	0.4241 (2)	0.0470 (8)
H3A	0.287 (4)	0.300 (2)	0.449 (3)	0.056*
H3B	0.427 (4)	0.315 (3)	0.400 (3)	0.056*
N4	0.1980 (3)	0.4814 (2)	0.43416 (19)	0.0319 (6)
N5	0.0477 (4)	0.6160 (3)	0.4291 (3)	0.0423 (7)
H5A	−0.026 (3)	0.581 (3)	0.458 (3)	0.051*
H5B	0.008 (4)	0.657 (3)	0.395 (2)	0.051*
C1	0.3283 (4)	0.4407 (3)	0.4026 (2)	0.0349 (7)
C2	0.1771 (4)	0.5749 (3)	0.4059 (3)	0.0334 (7)
C3	0.2964 (4)	0.6347 (3)	0.3510 (3)	0.0379 (8)
C4	0.2864 (4)	0.7472 (3)	0.3306 (3)	0.0387 (8)
C5	0.2374 (4)	0.7607 (3)	0.2317 (3)	0.0438 (9)
C6	0.2278 (4)	0.8680 (3)	0.2161 (3)	0.0435 (9)
C7	0.2656 (4)	0.9625 (4)	0.3006 (3)	0.0513 (10)
H7	0.2608	1.0343	0.2906	0.062*
C8	0.3099 (5)	0.9469 (3)	0.3983 (3)	0.0512 (9)
H8	0.3308	1.0092	0.4540	0.061*
C9	0.3249 (4)	0.8428 (3)	0.4180 (3)	0.0364 (8)
H9	0.3583	0.8353	0.4849	0.044*
O1WA	0.0946 (5)	0.1640 (4)	0.4904 (3)	0.0521 (10)	0.686 (4)
O1WB	0.2255 (12)	0.1963 (8)	0.5250 (7)	0.0521 (10)	0.314 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S11	0.0566 (5)	0.0269 (4)	0.0445 (5)	0.0196 (4)	0.0087 (4)	0.0093 (4)
O11	0.0468 (14)	0.0345 (13)	0.0537 (16)	0.0202 (11)	0.0079 (12)	0.0148 (12)
O21	0.0675 (16)	0.0252 (13)	0.0543 (16)	0.0198 (11)	0.0161 (13)	0.0142 (11)
C11	0.0354 (17)	0.0253 (16)	0.049 (2)	0.0136 (13)	0.0119 (15)	0.0095 (15)
C21	0.045 (2)	0.0317 (19)	0.062 (2)	0.0173 (15)	0.0090 (17)	0.0114 (18)
C31	0.054 (2)	0.042 (2)	0.054 (2)	0.0204 (17)	0.0032 (18)	0.0169 (19)
C41	0.050 (2)	0.041 (2)	0.045 (2)	0.0096 (16)	0.0078 (17)	0.0046 (17)
C51	0.0462 (19)	0.0267 (17)	0.052 (2)	0.0123 (14)	0.0203 (16)	0.0109 (16)
C61	0.0348 (16)	0.0235 (16)	0.0436 (19)	0.0103 (12)	0.0150 (14)	0.0097 (14)
C71	0.0359 (17)	0.0281 (17)	0.057 (2)	0.0174 (14)	0.0185 (16)	0.0169 (17)
S12	0.0536 (5)	0.0261 (4)	0.0491 (5)	0.0200 (4)	0.0215 (4)	0.0114 (4)
O12	0.0613 (16)	0.0322 (13)	0.0687 (18)	0.0268 (11)	0.0347 (14)	0.0203 (13)
O22	0.0475 (13)	0.0245 (11)	0.0441 (13)	0.0186 (10)	0.0174 (10)	0.0087 (10)
C12	0.0409 (17)	0.0258 (16)	0.0306 (16)	0.0149 (13)	0.0066 (13)	0.0059 (13)
C22	0.0474 (19)	0.0311 (18)	0.046 (2)	0.0230 (15)	0.0140 (16)	0.0078 (15)
C32	0.0443 (19)	0.043 (2)	0.050 (2)	0.0221 (16)	0.0208 (17)	0.0069 (17)
C42	0.054 (2)	0.042 (2)	0.049 (2)	0.0154 (17)	0.0221 (18)	0.0114 (17)
C52	0.0467 (19)	0.0267 (17)	0.0400 (19)	0.0135 (14)	0.0118 (15)	0.0064 (15)
C62	0.0393 (17)	0.0232 (15)	0.0319 (16)	0.0141 (13)	0.0047 (13)	0.0047 (13)
C72	0.0414 (18)	0.0271 (17)	0.0373 (18)	0.0181 (14)	0.0116 (14)	0.0074 (14)
Cl1	0.0787 (7)	0.0722 (7)	0.0600 (7)	0.0421 (6)	0.0246 (5)	0.0320 (6)
Cl2	0.0740 (7)	0.0533 (6)	0.0474 (6)	0.0274 (5)	0.0159 (5)	0.0090 (5)
N1	0.0438 (16)	0.0329 (15)	0.0527 (18)	0.0194 (12)	0.0203 (14)	0.0138 (14)
N2	0.0378 (15)	0.0361 (16)	0.0469 (17)	0.0196 (12)	0.0174 (13)	0.0111 (13)
N3	0.071 (2)	0.0416 (18)	0.0484 (19)	0.0381 (16)	0.0261 (16)	0.0192 (15)
N4	0.0430 (15)	0.0295 (14)	0.0315 (14)	0.0188 (12)	0.0136 (12)	0.0114 (12)
N5	0.0396 (16)	0.0386 (17)	0.065 (2)	0.0226 (13)	0.0246 (15)	0.0257 (15)
C1	0.0469 (19)	0.0323 (18)	0.0294 (16)	0.0172 (14)	0.0102 (14)	0.0061 (14)
C2	0.0338 (16)	0.0293 (17)	0.0401 (18)	0.0106 (13)	0.0103 (14)	0.0103 (14)
C3	0.0393 (18)	0.0360 (18)	0.046 (2)	0.0178 (14)	0.0124 (15)	0.0149 (16)
C4	0.0312 (17)	0.043 (2)	0.050 (2)	0.0160 (14)	0.0187 (15)	0.0159 (17)
C5	0.0370 (18)	0.049 (2)	0.051 (2)	0.0160 (16)	0.0222 (16)	0.0089 (18)
C6	0.0334 (18)	0.044 (2)	0.065 (2)	0.0185 (15)	0.0216 (17)	0.0238 (19)
C7	0.0342 (19)	0.055 (2)	0.070 (3)	0.0143 (16)	0.0125 (18)	0.024 (2)
C8	0.056 (2)	0.039 (2)	0.058 (2)	0.0161 (17)	0.0118 (19)	0.0065 (19)
C9	0.0331 (16)	0.0216 (15)	0.055 (2)	0.0095 (12)	0.0132 (15)	0.0048 (15)
O1WA	0.056 (2)	0.069 (3)	0.047 (2)	0.030 (2)	0.0202 (19)	0.0288 (19)
O1WB	0.056 (2)	0.069 (3)	0.047 (2)	0.030 (2)	0.0202 (19)	0.0288 (19)

Geometric parameters (Å, º)

S11—C11	1.783 (4)	C52—H52	0.9300
S11—S12	2.0538 (11)	C62—C72	1.499 (4)
O11—C71	1.223 (4)	Cl1—C6	1.718 (4)
O21—C71	1.330 (4)	Cl2—C5	1.721 (4)
O21—H21O	0.850 (10)	N1—C3	1.310 (4)
C11—C21	1.374 (5)	N1—N2	1.336 (4)
C11—C61	1.413 (4)	N2—C1	1.351 (4)
C21—C31	1.390 (5)	N2—H2	0.847 (10)
C21—H21	0.9300	N3—C1	1.311 (4)
C31—C41	1.380 (5)	N3—H3A	0.841 (10)
C31—H31	0.9300	N3—H3B	0.843 (10)
C41—C51	1.371 (5)	N4—C2	1.322 (4)
C41—H41	0.9300	N4—C1	1.353 (4)
C51—C61	1.395 (5)	N5—C2	1.313 (4)
C51—H51	0.9300	N5—H5A	0.837 (10)
C61—C71	1.463 (5)	N5—H5B	0.840 (10)
S12—C12	1.792 (3)	C2—C3	1.445 (4)
O12—C72	1.245 (4)	C3—C4	1.484 (5)
O22—C72	1.269 (4)	C4—C5	1.385 (5)
C12—C22	1.389 (4)	C4—C9	1.438 (5)
C12—C62	1.399 (4)	C5—C6	1.399 (5)
C22—C32	1.374 (5)	C6—C7	1.406 (5)
C22—H22	0.9300	C7—C8	1.373 (5)
C32—C42	1.380 (5)	C7—H7	0.9300
C32—H32	0.9300	C8—C9	1.390 (5)
C42—C52	1.382 (4)	C8—H8	0.9300
C42—H42	0.9300	C9—H9	0.9300
C52—C62	1.395 (4)
C11—S11—S12	105.99 (11)	O12—C72—O22	123.7 (3)
C71—O21—H21O	118 (3)	O12—C72—C62	117.5 (3)
C21—C11—C61	119.2 (3)	O22—C72—C62	118.8 (3)
C21—C11—S11	121.1 (3)	C3—N1—N2	116.7 (3)
C61—C11—S11	119.7 (3)	N1—N2—C1	123.8 (2)
C11—C21—C31	121.6 (3)	N1—N2—H2	119 (2)
C11—C21—H21	119.2	C1—N2—H2	117 (2)
C31—C21—H21	119.2	C1—N3—H3A	125 (2)
C41—C31—C21	119.0 (3)	C1—N3—H3B	123 (2)
C41—C31—H31	120.5	H3A—N3—H3B	110 (2)
C21—C31—H31	120.5	C2—N4—C1	116.5 (3)
C51—C41—C31	120.4 (4)	C2—N5—H5A	121 (2)
C51—C41—H41	119.8	C2—N5—H5B	121 (2)
C31—C41—H41	119.8	H5A—N5—H5B	112 (2)
C41—C51—C61	121.2 (3)	N3—C1—N2	118.1 (3)
C41—C51—H51	119.4	N3—C1—N4	120.7 (3)
C61—C51—H51	119.4	N2—C1—N4	121.2 (3)
C51—C61—C11	118.5 (3)	N5—C2—N4	119.9 (3)
C51—C61—C71	119.3 (3)	N5—C2—C3	118.9 (3)
C11—C61—C71	122.2 (3)	N4—C2—C3	121.2 (3)
O11—C71—O21	122.4 (3)	N1—C3—C2	120.5 (3)
O11—C71—C61	124.5 (3)	N1—C3—C4	118.2 (3)
O21—C71—C61	113.1 (3)	C2—C3—C4	121.3 (3)
C12—S12—S11	104.62 (10)	C5—C4—C9	120.3 (3)
C22—C12—C62	118.9 (3)	C5—C4—C3	122.0 (3)
C22—C12—S12	121.3 (2)	C9—C4—C3	117.6 (3)
C62—C12—S12	119.7 (2)	C4—C5—C6	120.2 (3)
C32—C22—C12	121.4 (3)	C4—C5—Cl2	120.0 (3)
C32—C22—H22	119.3	C6—C5—Cl2	119.8 (3)
C12—C22—H22	119.3	C5—C6—C7	120.3 (4)
C22—C32—C42	120.2 (3)	C5—C6—Cl1	120.7 (3)
C22—C32—H32	119.9	C7—C6—Cl1	119.0 (3)
C42—C32—H32	119.9	C8—C7—C6	118.7 (4)
C32—C42—C52	119.2 (3)	C8—C7—H7	120.6
C32—C42—H42	120.4	C6—C7—H7	120.6
C52—C42—H42	120.4	C7—C8—C9	123.3 (4)
C42—C52—C62	121.4 (3)	C7—C8—H8	118.3
C42—C52—H52	119.3	C9—C8—H8	118.3
C62—C52—H52	119.3	C8—C9—C4	117.1 (3)
C52—C62—C12	118.9 (3)	C8—C9—H9	121.4
C52—C62—C72	118.8 (3)	C4—C9—H9	121.4
C12—C62—C72	122.3 (3)
S12—S11—C11—C21	13.6 (3)	C12—C62—C72—O22	−177.7 (3)
S12—S11—C11—C61	−167.2 (2)	C3—N1—N2—C1	−2.9 (5)
C61—C11—C21—C31	0.3 (5)	N1—N2—C1—N3	−178.4 (3)
S11—C11—C21—C31	179.5 (3)	N1—N2—C1—N4	2.4 (5)
C11—C21—C31—C41	0.5 (5)	C2—N4—C1—N3	−177.7 (3)
C21—C31—C41—C51	−0.8 (5)	C2—N4—C1—N2	1.5 (5)
C31—C41—C51—C61	0.3 (5)	C1—N4—C2—N5	176.5 (3)
C41—C51—C61—C11	0.5 (5)	C1—N4—C2—C3	−4.5 (5)
C41—C51—C61—C71	178.9 (3)	N2—N1—C3—C2	−0.2 (5)
C21—C11—C61—C51	−0.8 (4)	N2—N1—C3—C4	176.3 (3)
S11—C11—C61—C51	179.9 (2)	N5—C2—C3—N1	−177.0 (3)
C21—C11—C61—C71	−179.1 (3)	N4—C2—C3—N1	4.1 (5)
S11—C11—C61—C71	1.6 (4)	N5—C2—C3—C4	6.6 (5)
C51—C61—C71—O11	171.1 (3)	N4—C2—C3—C4	−172.3 (3)
C11—C61—C71—O11	−10.6 (5)	N1—C3—C4—C5	71.0 (4)
C51—C61—C71—O21	−9.3 (4)	C2—C3—C4—C5	−112.5 (4)
C11—C61—C71—O21	169.1 (3)	N1—C3—C4—C9	−110.8 (4)
S11—S12—C12—C22	9.4 (3)	C2—C3—C4—C9	65.7 (4)
S11—S12—C12—C62	−173.6 (2)	C9—C4—C5—C6	1.1 (5)
C62—C12—C22—C32	1.8 (5)	C3—C4—C5—C6	179.3 (3)
S12—C12—C22—C32	178.8 (3)	C9—C4—C5—Cl2	−177.5 (2)
C12—C22—C32—C42	−1.4 (6)	C3—C4—C5—Cl2	0.7 (4)
C22—C32—C42—C52	−0.3 (6)	C4—C5—C6—C7	−0.8 (5)
C32—C42—C52—C62	1.6 (5)	Cl2—C5—C6—C7	177.7 (2)
C42—C52—C62—C12	−1.1 (5)	C4—C5—C6—Cl1	−178.9 (2)
C42—C52—C62—C72	−180.0 (3)	Cl2—C5—C6—Cl1	−0.3 (4)
C22—C12—C62—C52	−0.5 (5)	C5—C6—C7—C8	−0.7 (5)
S12—C12—C62—C52	−177.6 (2)	Cl1—C6—C7—C8	177.3 (3)
C22—C12—C62—C72	178.3 (3)	C6—C7—C8—C9	2.2 (5)
S12—C12—C62—C72	1.2 (4)	C7—C8—C9—C4	−1.9 (5)
C52—C62—C72—O12	−178.1 (3)	C5—C4—C9—C8	0.2 (4)
C12—C62—C72—O12	3.1 (5)	C3—C4—C9—C8	−178.0 (3)
C52—C62—C72—O22	1.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O21—H21O···O22^i	0.85 (1)	1.78 (2)	2.599 (3)	162 (4)
C21—H21···S12	0.93	2.64	3.181 (4)	118
C22—H22···S11	0.93	2.59	3.146 (4)	119
N2—H2···O22	0.85 (1)	1.84 (1)	2.686 (3)	172 (4)
N3—H3A···O1WA	0.84 (1)	2.22 (1)	3.052 (5)	172 (4)
N3—H3A···O1WB	0.84 (1)	1.81 (2)	2.607 (9)	157 (4)
N3—H3B···O12	0.84 (1)	1.98 (1)	2.811 (4)	171 (3)
N5—H5A···N4^ii	0.84 (1)	2.26 (1)	3.080 (4)	168 (4)
N5—H5B···O11^iii	0.84 (1)	2.23 (2)	3.041 (4)	163 (3)

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

(II) 3,5-Diamino-6-(2,3-dichlorophenyl)-1,2,4-triazin-2-ium 2-[(2-carboxyphenyl)disulfanyl]benzoate

Crystal data

C9H8Cl2N5^+·C14H9O4S2^−	Z = 2
Mr = 562.44	F(000) = 576
Triclinic, P1	Dx = 1.560 Mg m^−3
a = 8.5368 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.3100 (8) Å	Cell parameters from 2580 reflections
c = 12.9348 (8) Å	θ = 3.9–28.3°
α = 64.689 (6)°	µ = 0.49 mm^−1
β = 86.474 (5)°	T = 294 K
γ = 77.230 (5)°	Prism, colourless
V = 1197.56 (14) Å^3	0.44 × 0.26 × 0.16 mm

Data collection

Oxford Diffraction Gemini CCD S Ultra diffractometer	3784 reflections with I > 2σ(I)
ω scans, thick slices	Rint = 0.028
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	θmax = 28.8°, θmin = 3.4°
Tmin = 0.82, Tmax = 0.90	h = −11→10
10448 measured reflections	k = −16→16
5165 independent reflections	l = −16→15

Refinement

Refinement on F^2	8 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0463P)^2 + 0.5271P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
5165 reflections	Δρmax = 0.69 e Å^−3
343 parameters	Δρmin = −0.40 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S11	0.73570 (9)	1.26649 (6)	0.70633 (6)	0.04003 (18)
O11	0.7797 (2)	1.47988 (16)	0.70498 (17)	0.0447 (5)
O21	0.6634 (3)	1.56226 (16)	0.82134 (18)	0.0480 (5)
H21O	0.687 (4)	1.627 (2)	0.770 (2)	0.072*
C11	0.6616 (3)	1.2586 (2)	0.8408 (2)	0.0319 (5)
C21	0.6106 (3)	1.1548 (2)	0.9203 (2)	0.0410 (6)
H21	0.6180	1.0873	0.9039	0.049*
C31	0.5496 (3)	1.1506 (3)	1.0225 (3)	0.0478 (7)
H31	0.5163	1.0804	1.0743	0.057*
C41	0.5373 (4)	1.2488 (3)	1.0488 (3)	0.0504 (7)
H41	0.4942	1.2460	1.1175	0.061*
C51	0.5891 (3)	1.3514 (2)	0.9729 (2)	0.0421 (6)
H51	0.5824	1.4174	0.9915	0.050*
C61	0.6516 (3)	1.3585 (2)	0.8688 (2)	0.0317 (5)
C71	0.7057 (3)	1.4711 (2)	0.7898 (2)	0.0341 (6)
S12	0.65073 (8)	1.13349 (6)	0.68552 (6)	0.03733 (18)
O12	0.5271 (2)	0.97209 (15)	0.65169 (16)	0.0404 (4)
O22	0.65550 (19)	0.79103 (14)	0.65987 (15)	0.0341 (4)
C12	0.8020 (3)	0.9961 (2)	0.7504 (2)	0.0305 (5)
C22	0.9368 (3)	0.9932 (3)	0.8073 (3)	0.0438 (7)
H22	0.9500	1.0646	0.8107	0.053*
C32	1.0506 (3)	0.8864 (3)	0.8584 (3)	0.0525 (8)
H32	1.1406	0.8865	0.8953	0.063*
C42	1.0333 (3)	0.7795 (3)	0.8559 (3)	0.0497 (7)
H42	1.1099	0.7070	0.8919	0.060*
C52	0.9007 (3)	0.7810 (2)	0.7991 (2)	0.0388 (6)
H52	0.8890	0.7085	0.7972	0.047*
C62	0.7838 (3)	0.8881 (2)	0.7445 (2)	0.0277 (5)
C72	0.6447 (3)	0.8848 (2)	0.6814 (2)	0.0281 (5)
Cl1	0.13956 (11)	0.45741 (7)	0.85919 (7)	0.0587 (2)
Cl2	0.14555 (11)	0.18571 (7)	0.90091 (8)	0.0671 (3)
N1	0.3716 (2)	0.65097 (18)	0.63653 (19)	0.0358 (5)
N2	0.3601 (2)	0.76963 (19)	0.61448 (19)	0.0345 (5)
H2	0.4487 (19)	0.782 (2)	0.628 (2)	0.041*
N3	0.2263 (3)	0.96928 (19)	0.5602 (2)	0.0396 (5)
H3A	0.1440 (19)	1.0264 (18)	0.541 (2)	0.048*
H3B	0.3078 (19)	0.990 (2)	0.573 (2)	0.048*
N4	0.0856 (2)	0.82868 (17)	0.56417 (18)	0.0309 (5)
N5	−0.0450 (2)	0.6778 (2)	0.5876 (2)	0.0414 (6)
H5A	−0.1348 (19)	0.7259 (18)	0.581 (2)	0.050*
H5B	−0.050 (3)	0.6039 (10)	0.614 (2)	0.050*
C1	0.2237 (3)	0.8559 (2)	0.5791 (2)	0.0293 (5)
C2	0.0902 (3)	0.7111 (2)	0.5919 (2)	0.0308 (5)
C3	0.2401 (3)	0.6199 (2)	0.6266 (2)	0.0320 (5)
C4	0.2482 (3)	0.4890 (2)	0.6501 (2)	0.0354 (6)
C5	0.2010 (3)	0.4083 (2)	0.7538 (2)	0.0383 (6)
C6	0.2043 (3)	0.2872 (2)	0.7723 (3)	0.0427 (7)
C7	0.2552 (3)	0.2480 (3)	0.6893 (3)	0.0488 (7)
H7	0.2567	0.1675	0.7021	0.059*
C8	0.3044 (3)	0.3279 (3)	0.5863 (3)	0.0478 (7)
H8	0.3410	0.3003	0.5307	0.057*
C9	0.2996 (3)	0.4478 (2)	0.5655 (2)	0.0411 (6)
H9	0.3305	0.5016	0.4954	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S11	0.0611 (4)	0.0278 (3)	0.0380 (4)	−0.0185 (3)	0.0065 (3)	−0.0166 (3)
O11	0.0587 (12)	0.0332 (10)	0.0514 (12)	−0.0235 (9)	0.0149 (10)	−0.0216 (9)
O21	0.0724 (14)	0.0251 (9)	0.0529 (13)	−0.0144 (9)	0.0075 (10)	−0.0213 (9)
C11	0.0319 (13)	0.0269 (12)	0.0376 (14)	−0.0085 (10)	−0.0014 (10)	−0.0131 (11)
C21	0.0517 (16)	0.0305 (13)	0.0452 (17)	−0.0177 (12)	0.0016 (13)	−0.0161 (12)
C31	0.0542 (17)	0.0415 (16)	0.0474 (18)	−0.0243 (14)	0.0107 (14)	−0.0131 (14)
C41	0.0549 (18)	0.0504 (17)	0.0465 (18)	−0.0147 (14)	0.0197 (14)	−0.0219 (14)
C51	0.0468 (16)	0.0316 (13)	0.0503 (18)	−0.0046 (12)	0.0056 (13)	−0.0221 (13)
C61	0.0310 (13)	0.0231 (12)	0.0411 (15)	−0.0039 (10)	−0.0018 (11)	−0.0142 (11)
C71	0.0355 (13)	0.0277 (12)	0.0428 (16)	−0.0060 (11)	−0.0040 (11)	−0.0182 (11)
S12	0.0473 (4)	0.0266 (3)	0.0427 (4)	−0.0061 (3)	−0.0077 (3)	−0.0187 (3)
O12	0.0336 (10)	0.0332 (9)	0.0603 (13)	−0.0015 (8)	−0.0101 (8)	−0.0266 (9)
O22	0.0345 (9)	0.0251 (8)	0.0494 (11)	−0.0093 (7)	−0.0026 (8)	−0.0201 (8)
C12	0.0364 (13)	0.0277 (12)	0.0309 (13)	−0.0095 (10)	0.0022 (10)	−0.0147 (10)
C22	0.0452 (16)	0.0408 (15)	0.0570 (18)	−0.0130 (13)	−0.0063 (13)	−0.0290 (14)
C32	0.0419 (16)	0.0614 (19)	0.063 (2)	−0.0055 (15)	−0.0169 (14)	−0.0345 (17)
C42	0.0446 (16)	0.0472 (16)	0.0564 (19)	0.0050 (13)	−0.0179 (14)	−0.0256 (15)
C52	0.0450 (15)	0.0320 (13)	0.0434 (16)	−0.0056 (12)	−0.0068 (12)	−0.0200 (12)
C62	0.0290 (12)	0.0268 (12)	0.0302 (13)	−0.0092 (10)	0.0030 (10)	−0.0135 (10)
C72	0.0297 (12)	0.0257 (12)	0.0319 (13)	−0.0116 (10)	0.0043 (10)	−0.0126 (10)
Cl1	0.0803 (6)	0.0491 (4)	0.0488 (5)	−0.0151 (4)	0.0096 (4)	−0.0232 (4)
Cl2	0.0863 (6)	0.0453 (4)	0.0607 (5)	−0.0300 (4)	0.0017 (4)	−0.0066 (4)
N1	0.0291 (11)	0.0292 (11)	0.0498 (14)	−0.0056 (9)	−0.0029 (9)	−0.0172 (10)
N2	0.0249 (11)	0.0309 (11)	0.0507 (14)	−0.0093 (9)	−0.0037 (9)	−0.0178 (10)
N3	0.0329 (12)	0.0264 (11)	0.0597 (15)	−0.0123 (9)	−0.0014 (11)	−0.0152 (11)
N4	0.0248 (10)	0.0252 (10)	0.0409 (12)	−0.0085 (8)	0.0008 (8)	−0.0108 (9)
N5	0.0275 (11)	0.0285 (11)	0.0656 (16)	−0.0095 (9)	−0.0035 (11)	−0.0153 (12)
C1	0.0258 (12)	0.0307 (12)	0.0313 (13)	−0.0088 (10)	0.0039 (10)	−0.0124 (10)
C2	0.0273 (12)	0.0298 (12)	0.0354 (14)	−0.0090 (10)	0.0010 (10)	−0.0126 (11)
C3	0.0287 (12)	0.0261 (12)	0.0399 (15)	−0.0060 (10)	−0.0012 (10)	−0.0124 (11)
C4	0.0278 (13)	0.0278 (12)	0.0487 (16)	−0.0040 (10)	−0.0046 (11)	−0.0146 (12)
C5	0.0331 (13)	0.0354 (14)	0.0450 (16)	−0.0057 (11)	−0.0017 (11)	−0.0163 (12)
C6	0.0377 (14)	0.0283 (13)	0.0555 (18)	−0.0089 (11)	−0.0067 (13)	−0.0096 (13)
C7	0.0481 (17)	0.0341 (15)	0.067 (2)	−0.0054 (13)	−0.0061 (15)	−0.0248 (15)
C8	0.0462 (16)	0.0458 (16)	0.059 (2)	−0.0044 (13)	−0.0020 (14)	−0.0312 (15)
C9	0.0389 (15)	0.0336 (14)	0.0475 (17)	−0.0066 (11)	0.0056 (12)	−0.0152 (12)

Geometric parameters (Å, º)

S11—C11	1.784 (3)	C52—H52	0.9300
S11—S12	2.0506 (9)	C62—C72	1.498 (3)
O11—C71	1.207 (3)	Cl1—C5	1.725 (3)
O21—C71	1.323 (3)	Cl2—C6	1.726 (3)
O21—H21O	0.849 (10)	N1—C3	1.294 (3)
C11—C21	1.396 (3)	N1—N2	1.345 (3)
C11—C61	1.407 (3)	N2—C1	1.341 (3)
C21—C31	1.375 (4)	N2—H2	0.847 (10)
C21—H21	0.9300	N3—C1	1.315 (3)
C31—C41	1.371 (4)	N3—H3A	0.838 (9)
C31—H31	0.9300	N3—H3B	0.839 (10)
C41—C51	1.374 (4)	N4—C2	1.326 (3)
C41—H41	0.9300	N4—C1	1.341 (3)
C51—C61	1.392 (4)	N5—C2	1.319 (3)
C51—H51	0.9300	N5—H5A	0.841 (10)
C61—C71	1.481 (3)	N5—H5B	0.833 (9)
S12—C12	1.785 (2)	C2—C3	1.450 (3)
O12—C72	1.236 (3)	C3—C4	1.492 (3)
O22—C72	1.283 (3)	C4—C5	1.387 (4)
C12—C22	1.389 (3)	C4—C9	1.401 (4)
C12—C62	1.407 (3)	C5—C6	1.399 (4)
C22—C32	1.371 (4)	C6—C7	1.366 (4)
C22—H22	0.9300	C7—C8	1.383 (4)
C32—C42	1.369 (4)	C7—H7	0.9300
C32—H32	0.9300	C8—C9	1.374 (4)
C42—C52	1.380 (4)	C8—H8	0.9300
C42—H42	0.9300	C9—H9	0.9300
C52—C62	1.393 (3)
C11—S11—S12	103.92 (8)	O12—C72—O22	123.3 (2)
C71—O21—H21O	109 (2)	O12—C72—C62	119.1 (2)
C21—C11—C61	118.2 (2)	O22—C72—C62	117.6 (2)
C21—C11—S11	121.4 (2)	C3—N1—N2	116.6 (2)
C61—C11—S11	120.40 (18)	C1—N2—N1	123.87 (19)
C31—C21—C11	121.1 (3)	C1—N2—H2	124.3 (19)
C31—C21—H21	119.5	N1—N2—H2	111.8 (19)
C11—C21—H21	119.5	C1—N3—H3A	123.2 (17)
C41—C31—C21	120.6 (3)	C1—N3—H3B	123.4 (17)
C41—C31—H31	119.7	H3A—N3—H3B	113 (2)
C21—C31—H31	119.7	C2—N4—C1	116.2 (2)
C31—C41—C51	119.5 (3)	C2—N5—H5A	121.3 (18)
C31—C41—H41	120.3	C2—N5—H5B	121.4 (18)
C51—C41—H41	120.3	H5A—N5—H5B	114 (2)
C41—C51—C61	121.3 (3)	N3—C1—N4	119.7 (2)
C41—C51—H51	119.4	N3—C1—N2	118.7 (2)
C61—C51—H51	119.4	N4—C1—N2	121.5 (2)
C51—C61—C11	119.3 (2)	N5—C2—N4	118.6 (2)
C51—C61—C71	119.2 (2)	N5—C2—C3	120.1 (2)
C11—C61—C71	121.5 (2)	N4—C2—C3	121.2 (2)
O11—C71—O21	123.2 (2)	N1—C3—C2	120.3 (2)
O11—C71—C61	123.9 (2)	N1—C3—C4	118.2 (2)
O21—C71—C61	112.9 (2)	C2—C3—C4	121.5 (2)
C12—S12—S11	105.17 (8)	C5—C4—C9	119.4 (2)
C22—C12—C62	119.2 (2)	C5—C4—C3	120.6 (2)
C22—C12—S12	121.56 (19)	C9—C4—C3	119.9 (2)
C62—C12—S12	119.25 (18)	C4—C5—C6	119.6 (3)
C32—C22—C12	120.9 (2)	C4—C5—Cl1	119.9 (2)
C32—C22—H22	119.6	C6—C5—Cl1	120.6 (2)
C12—C22—H22	119.6	C7—C6—C5	120.4 (3)
C42—C32—C22	120.9 (3)	C7—C6—Cl2	119.5 (2)
C42—C32—H32	119.6	C5—C6—Cl2	120.1 (2)
C22—C32—H32	119.6	C6—C7—C8	120.1 (3)
C32—C42—C52	119.0 (3)	C6—C7—H7	119.9
C32—C42—H42	120.5	C8—C7—H7	119.9
C52—C42—H42	120.5	C9—C8—C7	120.4 (3)
C42—C52—C62	121.8 (2)	C9—C8—H8	119.8
C42—C52—H52	119.1	C7—C8—H8	119.8
C62—C52—H52	119.1	C8—C9—C4	120.0 (3)
C52—C62—C12	118.2 (2)	C8—C9—H9	120.0
C52—C62—C72	119.4 (2)	C4—C9—H9	120.0
C12—C62—C72	122.4 (2)
S12—S11—C11—C21	19.1 (2)	C12—C62—C72—O22	165.4 (2)
S12—S11—C11—C61	−160.19 (18)	C3—N1—N2—C1	−2.8 (4)
C61—C11—C21—C31	1.1 (4)	C2—N4—C1—N3	−175.8 (2)
S11—C11—C21—C31	−178.2 (2)	C2—N4—C1—N2	3.3 (4)
C11—C21—C31—C41	0.0 (4)	N1—N2—C1—N3	179.9 (2)
C21—C31—C41—C51	−1.1 (5)	N1—N2—C1—N4	0.8 (4)
C31—C41—C51—C61	1.1 (4)	C1—N4—C2—N5	174.6 (2)
C41—C51—C61—C11	0.1 (4)	C1—N4—C2—C3	−5.2 (4)
C41—C51—C61—C71	179.9 (2)	N2—N1—C3—C2	0.8 (4)
C21—C11—C61—C51	−1.1 (4)	N2—N1—C3—C4	179.8 (2)
S11—C11—C61—C51	178.21 (19)	N5—C2—C3—N1	−176.5 (3)
C21—C11—C61—C71	179.0 (2)	N4—C2—C3—N1	3.4 (4)
S11—C11—C61—C71	−1.7 (3)	N5—C2—C3—C4	4.5 (4)
C51—C61—C71—O11	170.2 (3)	N4—C2—C3—C4	−175.7 (2)
C11—C61—C71—O11	−9.9 (4)	N1—C3—C4—C5	100.9 (3)
C51—C61—C71—O21	−10.3 (3)	C2—C3—C4—C5	−80.1 (3)
C11—C61—C71—O21	169.6 (2)	N1—C3—C4—C9	−81.0 (3)
S11—S12—C12—C22	4.2 (2)	C2—C3—C4—C9	98.1 (3)
S11—S12—C12—C62	−176.30 (17)	C9—C4—C5—C6	−0.4 (4)
C62—C12—C22—C32	−0.7 (4)	C3—C4—C5—C6	177.8 (2)
S12—C12—C22—C32	178.8 (2)	C9—C4—C5—Cl1	179.27 (19)
C12—C22—C32—C42	−0.8 (5)	C3—C4—C5—Cl1	−2.6 (3)
C22—C32—C42—C52	1.2 (5)	C4—C5—C6—C7	0.6 (4)
C32—C42—C52—C62	−0.1 (5)	Cl1—C5—C6—C7	−179.1 (2)
C42—C52—C62—C12	−1.3 (4)	C4—C5—C6—Cl2	−179.89 (19)
C42—C52—C62—C72	178.4 (3)	Cl1—C5—C6—Cl2	0.4 (3)
C22—C12—C62—C52	1.7 (4)	C5—C6—C7—C8	0.2 (4)
S12—C12—C62—C52	−177.84 (19)	Cl2—C6—C7—C8	−179.3 (2)
C22—C12—C62—C72	−178.0 (2)	C6—C7—C8—C9	−1.3 (4)
S12—C12—C62—C72	2.5 (3)	C7—C8—C9—C4	1.5 (4)
C52—C62—C72—O12	166.6 (2)	C5—C4—C9—C8	−0.6 (4)
C12—C62—C72—O12	−13.8 (3)	C3—C4—C9—C8	−178.8 (2)
C52—C62—C72—O22	−14.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O21—H21O···O22^i	0.85 (1)	1.88 (2)	2.683 (2)	158 (3)
C21—H21···S12	0.93	2.64	3.150 (3)	115
C22—H22···S11	0.93	2.60	3.152 (3)	118
N2—H2···O22	0.85 (1)	1.87 (1)	2.717 (2)	173 (3)
N3—H3A···N4^ii	0.84 (1)	2.36 (1)	3.168 (3)	161 (3)
N3—H3B···O12	0.84 (1)	2.11 (1)	2.906 (3)	158 (2)
N5—H5A···O22^iii	0.84 (1)	2.18 (2)	2.932 (3)	149 (3)
N5—H5B···O11^iv	0.83 (1)	2.25 (2)	2.941 (3)	140 (2)

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