tert-Butyl 2-[2-(ethoxy­carbo­thio­yl­amino)-3-pyridyl­oxy]acetate and tert-butyl 2-(3-thio­xopyrido­[2,1-c][1,2,4]thia­diazol-8-yl­oxy)­acetate

Compounds (I), C₁₄H₂₀N₂O₄S, and (II), C₁₂H₁₄N₂O₃S₂, are two minor products of the same reaction. Both structures contain identical ester functionalities in similar orientations. Both independent mol­ecules of (I) contain an ethoxy­carbo­thio­yl­amine moiety, whilst (II) possesses a novel exocyclic thione system fused with a pyridine ring.

S1. Comment

An alternative approach to the resolution of racemates involves the development of enantioselective receptors capable of strongly binding substrates (Webb & Wilcox, 1993). The title compounds were synthesized during an on-going scheme of research investigating the preparation of thiourea derivatives as binding sites for the separation of racemic mixtures of carboxylic acid derivatives. Attempts to prepare substituted N,N'-bis(2-pyridyl) thioureas resulted in the formation of a mixture of products which were separated by column chromatography, concentrated and recrystallized. Two compounds were identified, i.e. (I) and (II), providing unexpected results.

Compound (I) crystallizes with two independent molecules in the asymmetric unit which are bound together via intermolecular hydrogen bonding [D···A separations of N1A—H1A···N2B and N1B—H1B···O3A = 2.920 (3) and 2.9737 (18) Å, respectively]. The two independent molecules possess expected geometries that are similar, but exhibit slight torsional differences in the pendant arms [N1—C1—O1—C2 = −175.15 (14) and −174.11 (13)°, whilst C9—C10—O4—C11 = −174.72 (14) and −179.23 (14)° for A and B, respectively]. The formation of the ethoxy group in (I) is attributed to the reaction between the isothiocyanate formed and the ethanol present in the chloroform (0.5–1.0% by volume as a stabilizing agent), which is more reactive than the free amine.

The second minor fraction produces the structure of (II), which contains a novel heteroatomic fused-ring system. Both (I) and (II) contain the same ester functionalities which are geometrically virtually identical, including their orientations with respect to the ring systems [O2—C8—C7—C6 = −179.25 (4) and −177.09 (4)° for A and B in (I), and O1—C4—C3—C2 = 178.28 (2)° in (II)]. The ring system is composed of a pyridine ring fused in the 3 and 4 positions to cyclic thiadiazolo and thione moieties. Inspection of the bond lengths shows a breakdown in the aromaticity of the pyridyl ring to alternating single and double bonds, apart from N1—C5 [1.394 (3) Å compared to 1.329 (3) and 1.330 (3) Å in (I)] which is disturbed by the electronic structure of the five-membered ring. The fused rings approximate planarity, exhibiting an angle from one ring plane normal to the other of 1.72 (5)°. The imine nature of N2 is confirmed by the lack of any peaks in the difference map corresponding to a proton. The five-membered ring system in (II) has not been observed in the solid state before and a search of the Cambridge Structural Database (Allen & Kennard, 1993) shows the structure of 2,4-dimethyl-1,2,4-thiazolidine-3,5-dithione (Raston et al., 1974) to be the closest for comparison, with similar bond lengths and angles for both compounds.

S2. Experimental

Thiophosgene (0.23 ml, 3.0 mmol) was added slowly to a mixture of tert-butyl 2-(2-amino-3-pyridyloxy)acetate (1.34 g, 6.0 mmol) in chloroform (40 ml) and 0.4 M aqueous potassium carbonate (15 ml, 6.0 mmol). The mixture was heated under reflux for 5 d. After allowing to cool to room temperature, the mixture was transferred into a separating funnel, the organic layer separated and the aqueous layer extracted with chloroform (30 ml). The organic layer was dried over magnesium sulfate and concentrated in vacuo to afford a brown oil. The crude product was purified by column chromatography on silica gel, eluting with ethyl acetate–petroleum ether (30:70, v/v), to produce three fractions. Two of these fractions were recrystallized from methanol where fraction 1 corresponds to compound (II) (60.4 mg, 5%), R_f = 0.28 and fraction 3 corresponds to compound (I) (208.4 mg, 16%), R_f = 0.1. The fractions were additionally characterized by ¹H NMR, ¹³C NMR and mass spectroscopy: (I) ¹ NMR (300 MHz, CDCl₃) δ 8.88 (1H, s, NH), 8.10 (1H, dd, J = 1.8, 4.4 Hz, H_pyr), 7.05 (2H, m, H_pyr), 4.63 (2H, q, J = 21.3 Hz, CH₂), 4.60 (2H, s, CH₂), 1.49 [9H, s, (CH₃)₃], 1.39 (3H, t, J = 14.3 Hz, CH₃). ¹³C NMR (300 MHz, CDCl₃) δ 189.0 (0), 167.2 (0), 144.5 (0), 141.6 (0), 140.9 (1), 120.9 (1), 120.4 (1), 83.4 (0), 68.1 (2), 66.9 (2), 28.1 (3), 14.1 (3). LRMS (ESIPOS) m/z 313 (M+H)⁺. (II) ¹ NMR (400 MHz, CDCl₃) δ 8.14 (1H, dd, J = 1, 7.2 Hz, H_pyr), 6.57 (1H, t, J = 14.5 Hz, H_pyr), 6.49 (1H, dd, J = 0.7, 7.5 Hz, H_pyr), 4.69 (2H, s, CH₂), 1.41 [9H, s, (CH₃)₃]. ¹³C NMR (400 MHz, CDCl₃) δ 192.4 (0), 165.1 (0), 148.4 (0), 147.1 (0), 119.1 (0), 112.1 (1), 106.9 (1), 82.3 (0), 65.9 (2), 27.9 (3). LRMS (ESIPOS) m/z 299 (M+H)⁺, 337 (M+K)⁺, 339 (M+CH₃CN)⁺.

S3. Refinement

H atoms were observed in the difference map, but were refined in calculated positions (C—H = 0.93–0.97 Å) using a riding model. No constraints or restraints were applied to the structural models, however, (I) was corrected for extinction effects using a refineable parameter where Fc is multiplied by a modified form of the overall scale factor.

Computing details

For both compounds, data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990).

(I)

Crystal data

C14H20N2O4S	Z = 4
Mr = 312.38	F(000) = 664
Triclinic, P1	Dx = 1.317 Mg m^−3
a = 10.661 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.852 (2) Å	Cell parameters from 20603 reflections
c = 13.501 (3) Å	θ = 1.8–26.0°
α = 76.85 (3)°	µ = 0.22 mm^−1
β = 81.35 (3)°	T = 150 K
γ = 72.12 (3)°	Block, colourless
V = 1575.1 (5) Å^3	0.2 × 0.1 × 0.1 mm

Data collection

KappaCCD diffractometer	4949 reflections with I > 2σ(I)
Radiation source: Nonius FR591 rotating anode	Rint = 0.047
ϕ and ω scans	θmax = 26°, θmin = 1.8°
Absorption correction: multi-scan (blessing, 1995) ?	h = −13→13
Tmin = 0.879, Tmax = 0.986	k = −14→14
20603 measured reflections	l = −16→16
6191 independent reflections

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.039	(Δ/σ)max = 0.001
wR(F^2) = 0.123	Δρmax = 0.39 e Å^−3
S = 0.88	Δρmin = −0.39 e Å^−3
6191 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
388 parameters	Extinction coefficient: 0.0076 (18)
0 restraints

Special details

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.

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

	x	y	z	Uiso*/Ueq
S1A	0.26282 (4)	0.26435 (4)	0.36040 (3)	0.02799 (14)
S1B	0.58599 (4)	0.23713 (4)	0.77618 (3)	0.02847 (14)
O1A	0.32965 (10)	0.06801 (9)	0.50713 (8)	0.0239 (3)
O1B	0.38328 (10)	0.43746 (9)	0.76875 (9)	0.0234 (3)
O2A	0.04968 (10)	0.34599 (9)	0.62645 (9)	0.0244 (3)
O2B	0.33234 (10)	0.15085 (9)	1.00742 (8)	0.0228 (3)
O3A	0.03568 (10)	0.38645 (10)	0.82010 (9)	0.0278 (3)
O3B	0.08654 (11)	0.12373 (11)	1.06446 (9)	0.0325 (3)
O4A	−0.18703 (10)	0.46372 (10)	0.82076 (8)	0.0244 (3)
O4B	0.14651 (10)	0.02371 (10)	1.22213 (8)	0.0249 (3)
N1A	0.29680 (12)	0.23825 (11)	0.55713 (10)	0.0215 (3)
H1A	0.3213	0.1909	0.6136	0.026*
N1B	0.32589 (12)	0.26904 (11)	0.80962 (10)	0.0214 (3)
H1B	0.2467	0.3168	0.8106	0.026*
N2A	0.34798 (13)	0.42435 (12)	0.51756 (10)	0.0252 (3)
N2B	0.35819 (12)	0.08633 (12)	0.75662 (10)	0.0229 (3)
C1A	0.29712 (14)	0.18859 (13)	0.47771 (12)	0.0201 (3)
C1B	0.42800 (14)	0.31711 (13)	0.78493 (11)	0.0200 (3)
C2A	0.34673 (16)	−0.00644 (14)	0.43138 (13)	0.0253 (4)
H21A	0.4270	−0.0050	0.3870	0.03*
H22A	0.2723	0.0233	0.3898	0.03*
C2B	0.47752 (16)	0.50710 (14)	0.73142 (13)	0.0261 (4)
H21B	0.5104	0.5003	0.6614	0.031*
H22B	0.5520	0.4775	0.7730	0.031*
C3A	0.35520 (17)	−0.13199 (15)	0.48847 (14)	0.0306 (4)
H31A	0.4246	−0.1578	0.5334	0.046*
H32A	0.3739	−0.1854	0.4410	0.046*
H33A	0.2725	−0.1334	0.5277	0.046*
C3B	0.40651 (17)	0.63581 (15)	0.73757 (14)	0.0315 (4)
H31B	0.3327	0.6638	0.6967	0.047*
H32B	0.4659	0.6847	0.7127	0.047*
H33B	0.3753	0.6416	0.8073	0.047*
C4A	0.25820 (15)	0.36511 (14)	0.55357 (12)	0.0207 (3)
C4B	0.34395 (14)	0.14213 (13)	0.83424 (12)	0.0194 (3)
C5A	0.31143 (16)	0.54335 (15)	0.51687 (13)	0.0257 (4)
H5A	0.3730	0.5862	0.4913	0.031*
C5B	0.37458 (15)	−0.03340 (14)	0.77746 (13)	0.0248 (4)
H5B	0.3864	−0.0736	0.7236	0.03*
C6A	0.18694 (16)	0.60499 (15)	0.55228 (13)	0.0260 (4)
H6A	0.1655	0.6877	0.5499	0.031*
C6B	0.37442 (15)	−0.09857 (14)	0.87570 (13)	0.0254 (4)
H6B	0.3854	−0.1813	0.8875	0.03*
C7A	0.09403 (16)	0.54294 (14)	0.59144 (12)	0.0244 (4)
H7A	0.0098	0.5827	0.6167	0.029*
C7B	0.35788 (14)	−0.04091 (14)	0.95695 (13)	0.0229 (4)
H7B	0.3563	−0.0836	1.0238	0.027*
C8A	0.12956 (14)	0.42042 (14)	0.59205 (12)	0.0204 (3)
C8B	0.34375 (14)	0.08233 (14)	0.93614 (12)	0.0205 (3)
C9A	−0.07692 (14)	0.39695 (14)	0.67501 (12)	0.0233 (4)
H91A	−0.1324	0.3443	0.6797	0.028*
H92A	−0.1186	0.4744	0.6339	0.028*
C9B	0.30422 (15)	0.09750 (14)	1.11084 (12)	0.0223 (3)
H91B	0.3131	0.1475	1.1556	0.027*
H92B	0.3673	0.0186	1.1276	0.027*
C10A	−0.06643 (14)	0.41389 (13)	0.78027 (12)	0.0213 (3)
C10B	0.16483 (15)	0.08458 (14)	1.12756 (12)	0.0228 (3)
C11A	−0.20658 (16)	0.50094 (17)	0.92125 (13)	0.0293 (4)
C11B	0.01804 (15)	−0.00309 (16)	1.25824 (14)	0.0288 (4)
C12A	−0.17135 (19)	0.38823 (19)	1.00402 (14)	0.0400 (5)
H12A	−0.2242	0.3365	1.0014	0.06*
H12B	−0.1882	0.4110	1.0697	0.06*
H12C	−0.0794	0.3460	0.9932	0.06*
C12B	−0.00694 (17)	−0.07926 (17)	1.19122 (15)	0.0355 (4)
H12D	−0.0327	−0.0294	1.1267	0.053*
H12E	−0.0763	−0.1142	1.2241	0.053*
H12F	0.0724	−0.1425	1.1804	0.053*
C13A	−0.35321 (17)	0.5654 (2)	0.93023 (16)	0.0455 (5)
H13A	−0.3743	0.6296	0.8721	0.068*
H13B	−0.3757	0.5982	0.9915	0.068*
H13C	−0.4026	0.5092	0.9328	0.068*
C13B	−0.08973 (17)	0.11519 (18)	1.26010 (17)	0.0424 (5)
H13D	−0.0610	0.1655	1.2931	0.064*
H13E	−0.1687	0.0991	1.297	0.064*
H13F	−0.1077	0.1558	1.1914	0.064*
C14A	−0.12757 (17)	0.58830 (16)	0.91726 (15)	0.0337 (4)
H14A	−0.0349	0.5462	0.9137	0.051*
H14B	−0.1515	0.6230	0.9775	0.051*
H14C	−0.1461	0.6513	0.8580	0.051*
C14B	0.04239 (19)	−0.07507 (19)	1.36487 (15)	0.0428 (5)
H14D	0.1209	−0.1416	1.3622	0.064*
H14E	−0.0318	−0.1053	1.3933	0.064*
H14F	0.0535	−0.0240	1.4068	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1A	0.0367 (3)	0.0227 (2)	0.0210 (2)	−0.00307 (18)	−0.00597 (17)	−0.00228 (17)
S1B	0.0206 (2)	0.0217 (2)	0.0384 (3)	−0.00324 (16)	−0.00142 (17)	−0.00098 (18)
O1A	0.0302 (6)	0.0181 (6)	0.0217 (6)	−0.0040 (4)	−0.0024 (5)	−0.0044 (4)
O1B	0.0226 (5)	0.0165 (6)	0.0294 (6)	−0.0053 (4)	0.0007 (4)	−0.0030 (4)
O2A	0.0248 (6)	0.0201 (6)	0.0276 (6)	−0.0070 (4)	0.0057 (4)	−0.0075 (5)
O2B	0.0296 (6)	0.0203 (6)	0.0187 (6)	−0.0088 (4)	0.0009 (4)	−0.0035 (4)
O3A	0.0211 (6)	0.0315 (7)	0.0283 (7)	−0.0041 (5)	−0.0039 (5)	−0.0042 (5)
O3B	0.0266 (6)	0.0370 (7)	0.0298 (7)	−0.0062 (5)	−0.0082 (5)	0.0017 (5)
O4A	0.0196 (5)	0.0312 (6)	0.0225 (6)	−0.0048 (5)	−0.0010 (4)	−0.0091 (5)
O4B	0.0222 (6)	0.0292 (6)	0.0228 (6)	−0.0094 (5)	0.0004 (4)	−0.0023 (5)
N1A	0.0256 (7)	0.0179 (7)	0.0175 (7)	−0.0025 (5)	−0.0021 (5)	−0.0013 (5)
N1B	0.0189 (6)	0.0164 (7)	0.0245 (7)	−0.0024 (5)	−0.0005 (5)	0.0000 (5)
N2A	0.0283 (7)	0.0233 (7)	0.0233 (7)	−0.0074 (6)	−0.0003 (5)	−0.0043 (6)
N2B	0.0226 (7)	0.0239 (7)	0.0219 (7)	−0.0073 (5)	−0.0014 (5)	−0.0035 (6)
C1A	0.0167 (7)	0.0192 (8)	0.0228 (8)	−0.0034 (6)	0.0003 (6)	−0.0045 (6)
C1B	0.0248 (8)	0.0186 (8)	0.0159 (8)	−0.0057 (6)	−0.0029 (6)	−0.0017 (6)
C2A	0.0316 (9)	0.0235 (9)	0.0234 (9)	−0.0099 (7)	0.0019 (6)	−0.0097 (7)
C2B	0.0287 (8)	0.0233 (9)	0.0288 (9)	−0.0131 (7)	0.0001 (7)	−0.0035 (7)
C3A	0.0367 (9)	0.0222 (9)	0.0327 (10)	−0.0079 (7)	−0.0004 (7)	−0.0072 (7)
C3B	0.0351 (9)	0.0232 (9)	0.0377 (11)	−0.0112 (7)	−0.0041 (7)	−0.0039 (7)
C4A	0.0244 (8)	0.0194 (8)	0.0172 (8)	−0.0044 (6)	−0.0030 (6)	−0.0032 (6)
C4B	0.0156 (7)	0.0190 (8)	0.0223 (8)	−0.0046 (6)	−0.0002 (6)	−0.0027 (6)
C5A	0.0298 (9)	0.0253 (9)	0.0242 (9)	−0.0123 (7)	−0.0001 (7)	−0.0042 (7)
C5B	0.0245 (8)	0.0245 (9)	0.0276 (9)	−0.0084 (7)	−0.0007 (6)	−0.0085 (7)
C6A	0.0349 (9)	0.0179 (8)	0.0250 (9)	−0.0061 (7)	−0.0054 (7)	−0.0038 (6)
C6B	0.0251 (8)	0.0176 (8)	0.0331 (10)	−0.0069 (6)	−0.0020 (7)	−0.0032 (7)
C7A	0.0255 (8)	0.0231 (8)	0.0222 (9)	−0.0044 (6)	−0.0003 (6)	−0.0044 (6)
C7B	0.0222 (8)	0.0212 (8)	0.0235 (9)	−0.0066 (6)	−0.0021 (6)	0.0000 (6)
C8A	0.0243 (8)	0.0200 (8)	0.0170 (8)	−0.0066 (6)	−0.0019 (6)	−0.0031 (6)
C8B	0.0170 (7)	0.0212 (8)	0.0224 (8)	−0.0050 (6)	−0.0002 (6)	−0.0044 (6)
C9A	0.0189 (7)	0.0236 (8)	0.0269 (9)	−0.0059 (6)	0.0024 (6)	−0.0067 (7)
C9B	0.0246 (8)	0.0227 (8)	0.0181 (8)	−0.0058 (6)	−0.0015 (6)	−0.0026 (6)
C10A	0.0195 (8)	0.0178 (8)	0.0249 (9)	−0.0054 (6)	−0.0001 (6)	−0.0020 (6)
C10B	0.0250 (8)	0.0192 (8)	0.0227 (9)	−0.0039 (6)	−0.0012 (6)	−0.0045 (6)
C11A	0.0244 (8)	0.0412 (10)	0.0214 (9)	−0.0049 (7)	−0.0015 (6)	−0.0108 (7)
C11B	0.0213 (8)	0.0357 (10)	0.0313 (10)	−0.0141 (7)	0.0034 (7)	−0.0059 (7)
C12A	0.0414 (10)	0.0550 (13)	0.0253 (10)	−0.0216 (9)	−0.0015 (8)	−0.0010 (9)
C12B	0.0337 (9)	0.0368 (11)	0.0400 (11)	−0.0159 (8)	−0.0028 (8)	−0.0076 (8)
C13A	0.0258 (9)	0.0738 (15)	0.0356 (11)	−0.0018 (9)	0.0016 (8)	−0.0278 (10)
C13B	0.0270 (9)	0.0491 (12)	0.0525 (13)	−0.0097 (8)	0.0087 (8)	−0.0219 (10)
C14A	0.0355 (9)	0.0317 (10)	0.0340 (10)	−0.0017 (8)	−0.0099 (8)	−0.0124 (8)
C14B	0.0436 (11)	0.0595 (14)	0.0299 (11)	−0.0291 (10)	0.0036 (8)	−0.0019 (9)

Geometric parameters (Å, º)

S1A—C1A	1.6656 (17)	C5A—H5A	0.93
S1B—C1B	1.6614 (16)	C5B—C6B	1.375 (2)
O1A—C1A	1.3414 (19)	C5B—H5B	0.93
O1A—C2A	1.454 (2)	C6A—C7A	1.384 (2)
O1B—C1B	1.3347 (19)	C6A—H6A	0.93
O1B—C2B	1.4535 (19)	C6B—C7B	1.382 (2)
O2A—C8A	1.3693 (19)	C6B—H6B	0.93
O2A—C9A	1.4247 (19)	C7A—C8A	1.382 (2)
O2B—C8B	1.3640 (19)	C7A—H7A	0.93
O2B—C9B	1.4242 (19)	C7B—C8B	1.388 (2)
O3A—C10A	1.2079 (19)	C7B—H7B	0.93
O3B—C10B	1.1975 (19)	C9A—C10A	1.505 (2)
O4A—C10A	1.3304 (19)	C9A—H91A	0.97
O4A—C11A	1.487 (2)	C9A—H92A	0.97
O4B—C10B	1.335 (2)	C9B—C10B	1.519 (2)
O4B—C11B	1.4868 (19)	C9B—H91B	0.97
N1A—C1A	1.335 (2)	C9B—H92B	0.97
N1A—C4A	1.423 (2)	C11A—C14A	1.510 (3)
N1A—H1A	0.86	C11A—C13A	1.515 (2)
N1B—C1B	1.344 (2)	C11A—C12A	1.521 (3)
N1B—C4B	1.423 (2)	C11B—C14B	1.512 (3)
N1B—H1B	0.86	C11B—C12B	1.515 (3)
N2A—C4A	1.328 (2)	C11B—C13B	1.518 (3)
N2A—C5A	1.341 (2)	C12A—H12A	0.96
N2B—C4B	1.328 (2)	C12A—H12B	0.96
N2B—C5B	1.343 (2)	C12A—H12C	0.96
C2A—C3A	1.494 (2)	C12B—H12D	0.96
C2A—H21A	0.97	C12B—H12E	0.96
C2A—H22A	0.97	C12B—H12F	0.96
C2B—C3B	1.496 (2)	C13A—H13A	0.96
C2B—H21B	0.97	C13A—H13B	0.96
C2B—H22B	0.97	C13A—H13C	0.96
C3A—H31A	0.96	C13B—H13D	0.96
C3A—H32A	0.96	C13B—H13E	0.96
C3A—H33A	0.96	C13B—H13F	0.96
C3B—H31B	0.96	C14A—H14A	0.96
C3B—H32B	0.96	C14A—H14B	0.96
C3B—H33B	0.96	C14A—H14C	0.96
C4A—C8A	1.403 (2)	C14B—H14D	0.96
C4B—C8B	1.397 (2)	C14B—H14E	0.96
C5A—C6A	1.377 (2)	C14B—H14F	0.96
C1A—O1A—C2A	119.30 (12)	C7A—C8A—C4A	118.38 (14)
C1B—O1B—C2B	118.52 (12)	O2B—C8B—C7B	125.28 (14)
C8A—O2A—C9A	116.91 (12)	O2B—C8B—C4B	116.43 (14)
C8B—O2B—C9B	116.49 (12)	C7B—C8B—C4B	118.28 (15)
C10A—O4A—C11A	120.91 (12)	O2A—C9A—C10A	111.55 (13)
C10B—O4B—C11B	120.00 (12)	O2A—C9A—H91A	109.3
C1A—N1A—C4A	123.66 (13)	C10A—C9A—H91A	109.3
C1A—N1A—H1A	118.2	O2A—C9A—H92A	109.3
C4A—N1A—H1A	118.2	C10A—C9A—H92A	109.3
C1B—N1B—C4B	122.44 (12)	H91A—C9A—H92A	108
C1B—N1B—H1B	118.8	O2B—C9B—C10B	110.48 (13)
C4B—N1B—H1B	118.8	O2B—C9B—H91B	109.6
C4A—N2A—C5A	117.49 (14)	C10B—C9B—H91B	109.6
C4B—N2B—C5B	118.20 (14)	O2B—C9B—H92B	109.6
N1A—C1A—O1A	109.31 (13)	C10B—C9B—H92B	109.6
N1A—C1A—S1A	125.37 (12)	H91B—C9B—H92B	108.1
O1A—C1A—S1A	125.32 (12)	O3A—C10A—O4A	126.45 (15)
O1B—C1B—N1B	109.94 (12)	O3A—C10A—C9A	124.82 (14)
O1B—C1B—S1B	125.60 (12)	O4A—C10A—C9A	108.74 (13)
N1B—C1B—S1B	124.46 (12)	O3B—C10B—O4B	127.06 (15)
O1A—C2A—C3A	106.91 (13)	O3B—C10B—C9B	124.12 (15)
O1A—C2A—H21A	110.3	O4B—C10B—C9B	108.82 (13)
C3A—C2A—H21A	110.3	O4A—C11A—C14A	109.35 (14)
O1A—C2A—H22A	110.3	O4A—C11A—C13A	102.61 (13)
C3A—C2A—H22A	110.3	C14A—C11A—C13A	110.07 (16)
H21A—C2A—H22A	108.6	O4A—C11A—C12A	108.74 (15)
O1B—C2B—C3B	107.29 (13)	C14A—C11A—C12A	114.02 (15)
O1B—C2B—H21B	110.3	C13A—C11A—C12A	111.42 (16)
C3B—C2B—H21B	110.3	O4B—C11B—C14B	102.19 (13)
O1B—C2B—H22B	110.3	O4B—C11B—C12B	109.39 (14)
C3B—C2B—H22B	110.3	C14B—C11B—C12B	110.89 (16)
H21B—C2B—H22B	108.5	O4B—C11B—C13B	108.80 (14)
C2A—C3A—H31A	109.5	C14B—C11B—C13B	111.44 (17)
C2A—C3A—H32A	109.5	C12B—C11B—C13B	113.49 (15)
H31A—C3A—H32A	109.5	C11A—C12A—H12A	109.5
C2A—C3A—H33A	109.5	C11A—C12A—H12B	109.5
H31A—C3A—H33A	109.5	H12A—C12A—H12B	109.5
H32A—C3A—H33A	109.5	C11A—C12A—H12C	109.5
C2B—C3B—H31B	109.5	H12A—C12A—H12C	109.5
C2B—C3B—H32B	109.5	H12B—C12A—H12C	109.5
H31B—C3B—H32B	109.5	C11B—C12B—H12D	109.5
C2B—C3B—H33B	109.5	C11B—C12B—H12E	109.5
H31B—C3B—H33B	109.5	H12D—C12B—H12E	109.5
H32B—C3B—H33B	109.5	C11B—C12B—H12F	109.5
N2A—C4A—C8A	123.29 (14)	H12D—C12B—H12F	109.5
N2A—C4A—N1A	118.01 (13)	H12E—C12B—H12F	109.5
C8A—C4A—N1A	118.64 (14)	C11A—C13A—H13A	109.5
N2B—C4B—C8B	123.06 (14)	C11A—C13A—H13B	109.5
N2B—C4B—N1B	116.81 (14)	H13A—C13A—H13B	109.5
C8B—C4B—N1B	120.13 (15)	C11A—C13A—H13C	109.5
N2A—C5A—C6A	123.03 (16)	H13A—C13A—H13C	109.5
N2A—C5A—H5A	118.5	H13B—C13A—H13C	109.5
C6A—C5A—H5A	118.5	C11B—C13B—H13D	109.5
N2B—C5B—C6B	122.26 (16)	C11B—C13B—H13E	109.5
N2B—C5B—H5B	118.9	H13D—C13B—H13E	109.5
C6B—C5B—H5B	118.9	C11B—C13B—H13F	109.5
C5A—C6A—C7A	119.52 (15)	H13D—C13B—H13F	109.5
C5A—C6A—H6A	120.2	H13E—C13B—H13F	109.5
C7A—C6A—H6A	120.2	C11A—C14A—H14A	109.5
C5B—C6B—C7B	119.89 (15)	C11A—C14A—H14B	109.5
C5B—C6B—H6B	120.1	H14A—C14A—H14B	109.5
C7B—C6B—H6B	120.1	C11A—C14A—H14C	109.5
C8A—C7A—C6A	118.29 (15)	H14A—C14A—H14C	109.5
C8A—C7A—H7A	120.9	H14B—C14A—H14C	109.5
C6A—C7A—H7A	120.9	C11B—C14B—H14D	109.5
C6B—C7B—C8B	118.29 (15)	C11B—C14B—H14E	109.5
C6B—C7B—H7B	120.9	H14D—C14B—H14E	109.5
C8B—C7B—H7B	120.9	C11B—C14B—H14F	109.5
O2A—C8A—C7A	125.90 (14)	H14D—C14B—H14F	109.5
O2A—C8A—C4A	115.71 (13)	H14E—C14B—H14F	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···N2B	0.86	2.06	2.920 (2)	173
N1B—H1B···O3A	0.86	2.14	2.9737 (18)	163

(II)

Crystal data

C12H14N2O3S2	F(000) = 624
Mr = 298.37	Dx = 1.399 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.521 (3) Å	Cell parameters from 12963 reflections
b = 6.827 (1) Å	θ = 2.7–27.4°
c = 13.574 (3) Å	µ = 0.38 mm^−1
β = 100.06 (3)°	T = 150 K
V = 1416.2 (5) Å^3	Plate, light brown
Z = 4	0.18 × 0.15 × 0.03 mm

Data collection

KappaCCD diffractometer	2304 reflections with I > 2σ(I)
ϕ and ω scans	Rint = 0.058
Absorption correction: multi-scan (blessing, 1995) ?	θmax = 27.4°, θmin = 2.7°
Tmin = 0.888, Tmax = 0.998	h = −19→19
12963 measured reflections	k = −8→8
3159 independent reflections	l = −17→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.122	(Δ/σ)max = 0.005
S = 0.81	Δρmax = 0.28 e Å^−3
3159 reflections	Δρmin = −0.29 e Å^−3
175 parameters

Special details

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.

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

	x	y	z	Uiso*/Ueq
S1	0.17975 (3)	0.16465 (7)	0.38132 (4)	0.02727 (17)
S2	0.26781 (3)	0.21694 (8)	0.59705 (4)	0.03121 (18)
O1	−0.10406 (9)	0.23694 (19)	0.33327 (10)	0.0245 (3)
O2	−0.20851 (9)	0.1316 (2)	0.16325 (11)	0.0328 (4)
O3	−0.32551 (9)	0.2608 (2)	0.21808 (12)	0.0332 (4)
N1	0.09447 (10)	0.2276 (2)	0.51582 (12)	0.0191 (4)
N2	0.07236 (11)	0.1847 (2)	0.34494 (12)	0.0239 (4)
C1	0.06582 (13)	0.2565 (3)	0.60604 (15)	0.0228 (4)
H1	0.1054	0.2567	0.666	0.0270*
C2	−0.01982 (13)	0.2841 (3)	0.60526 (14)	0.0232 (4)
H2A	−0.0396	0.3048	0.6653	0.028*
C3	−0.08142 (13)	0.2824 (3)	0.51326 (15)	0.0227 (4)
H3	−0.1404	0.3049	0.5139	0.027*
C4	−0.05394 (13)	0.2480 (3)	0.42546 (14)	0.0206 (4)
C5	0.03748 (13)	0.2175 (2)	0.42444 (14)	0.0195 (4)
C6	−0.19561 (13)	0.2667 (3)	0.32871 (15)	0.0245 (4)
H6A	−0.2071	0.4030	0.3419	0.029*
H6B	−0.2165	0.1868	0.3787	0.029*
C7	−0.24207 (13)	0.2105 (3)	0.22550 (15)	0.0241 (5)
C8	−0.39160 (14)	0.2016 (3)	0.13089 (17)	0.0338 (5)
C9	−0.39432 (14)	−0.0180 (3)	0.12423 (19)	0.0449 (6)
H9A	−0.3415	−0.0649	0.1046	0.067*
H9B	−0.4438	−0.0576	0.0755	0.067*
H9C	−0.3994	−0.0718	0.1883	0.067*
C10	−0.47550 (17)	0.2806 (5)	0.1576 (3)	0.0649 (9)
H10A	−0.4851	0.2225	0.2192	0.097*
H10B	−0.5236	0.2492	0.1053	0.097*
H10C	−0.4711	0.4202	0.1654	0.097*
C11	−0.37139 (18)	0.2968 (5)	0.0371 (2)	0.0693 (10)
H11A	−0.3626	0.4348	0.0483	0.104*
H11B	−0.4194	0.2764	−0.0169	0.104*
H11C	−0.3193	0.2397	0.0203	0.104*
C12	0.18184 (13)	0.2046 (3)	0.50625 (15)	0.0230 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0207 (3)	0.0381 (3)	0.0234 (3)	0.0016 (2)	0.0049 (2)	−0.0009 (2)
S2	0.0223 (3)	0.0384 (3)	0.0300 (3)	0.0012 (2)	−0.0035 (2)	−0.0020 (2)
O1	0.0160 (7)	0.0381 (8)	0.0185 (7)	−0.0013 (6)	0.0008 (6)	−0.0021 (6)
O2	0.0209 (8)	0.0512 (9)	0.0269 (8)	−0.0050 (7)	0.0058 (6)	−0.0082 (7)
O3	0.0180 (8)	0.0437 (9)	0.0348 (9)	0.0037 (6)	−0.0034 (7)	−0.0087 (7)
N1	0.0178 (9)	0.0203 (7)	0.0184 (8)	−0.0013 (6)	0.0010 (6)	−0.0004 (6)
N2	0.0210 (9)	0.0320 (9)	0.0187 (8)	0.0004 (7)	0.0038 (7)	−0.0003 (7)
C1	0.0268 (12)	0.0244 (10)	0.0166 (10)	−0.0012 (8)	0.0018 (8)	0.0003 (8)
C2	0.0297 (12)	0.0246 (9)	0.0159 (10)	−0.0020 (8)	0.0055 (8)	−0.0013 (7)
C3	0.0194 (10)	0.0250 (9)	0.0240 (11)	−0.0015 (8)	0.0045 (8)	0.0004 (8)
C4	0.0212 (10)	0.0202 (9)	0.0193 (10)	−0.0021 (7)	0.0006 (8)	0.0019 (7)
C5	0.0218 (10)	0.0182 (8)	0.0174 (10)	−0.0012 (7)	0.0004 (8)	0.0012 (7)
C6	0.0186 (11)	0.0303 (10)	0.0244 (11)	0.0002 (8)	0.0038 (8)	−0.0004 (8)
C7	0.0182 (10)	0.0266 (10)	0.0269 (11)	−0.0043 (8)	0.0020 (9)	0.0032 (8)
C8	0.0151 (11)	0.0488 (13)	0.0341 (13)	−0.0034 (9)	−0.0049 (9)	−0.0015 (10)
C9	0.0260 (12)	0.0529 (15)	0.0518 (15)	−0.0067 (11)	−0.0041 (11)	−0.0058 (12)
C10	0.0259 (15)	0.085 (2)	0.077 (2)	0.0144 (13)	−0.0101 (14)	−0.0205 (17)
C11	0.0430 (17)	0.106 (2)	0.0497 (18)	−0.0268 (16)	−0.0176 (14)	0.0365 (17)
C12	0.0215 (11)	0.0215 (9)	0.0258 (11)	0.0005 (7)	0.0037 (8)	0.0016 (8)

Geometric parameters (Å, º)

S1—N2	1.6593 (17)	C3—H3	0.93
S1—C12	1.712 (2)	C4—C5	1.437 (3)
S2—C12	1.653 (2)	C6—C7	1.509 (3)
O1—C4	1.355 (2)	C6—H6A	0.97
O1—C6	1.426 (2)	C6—H6B	0.97
O2—C7	1.196 (2)	C8—C9	1.502 (3)
O3—C7	1.326 (3)	C8—C11	1.510 (4)
O3—C8	1.481 (3)	C8—C10	1.511 (4)
N1—C1	1.388 (3)	C9—H9A	0.96
N1—C5	1.394 (3)	C9—H9B	0.96
N1—C12	1.393 (3)	C9—H9C	0.96
N2—C5	1.308 (3)	C10—H10A	0.96
C1—C2	1.341 (3)	C10—H10B	0.96
C1—H1	0.93	C10—H10C	0.96
C2—C3	1.434 (3)	C11—H11A	0.96
C2—H2A	0.93	C11—H11B	0.96
C3—C4	1.355 (3)	C11—H11C	0.96
N2—S1—C12	97.23 (9)	O2—C7—C6	125.05 (19)
C4—O1—C6	116.05 (15)	O3—C7—C6	107.85 (17)
C7—O3—C8	121.40 (17)	O3—C8—C9	109.19 (18)
C1—N1—C5	122.74 (17)	O3—C8—C11	109.85 (19)
C1—N1—C12	124.42 (17)	C9—C8—C11	112.7 (2)
C5—N1—C12	112.84 (16)	O3—C8—C10	102.50 (19)
C5—N2—S1	107.91 (14)	C9—C8—C10	110.7 (2)
C2—C1—N1	118.88 (18)	C11—C8—C10	111.3 (2)
C2—C1—H1	120.6	C8—C9—H9A	109.5
N1—C1—H1	120.6	C8—C9—H9B	109.5
C1—C2—C3	120.99 (19)	H9A—C9—H9B	109.5
C1—C2—H2A	119.5	C8—C9—H9C	109.5
C3—C2—H2A	119.5	H9A—C9—H9C	109.5
C4—C3—C2	120.21 (19)	H9B—C9—H9C	109.5
C4—C3—H3	119.9	C8—C10—H10A	109.5
C2—C3—H3	119.9	C8—C10—H10B	109.5
C3—C4—O1	127.14 (18)	H10A—C10—H10B	109.5
C3—C4—C5	119.79 (18)	C8—C10—H10C	109.5
O1—C4—C5	113.06 (17)	H10A—C10—H10C	109.5
N2—C5—N1	116.92 (17)	H10B—C10—H10C	109.5
N2—C5—C4	125.76 (18)	C8—C11—H11A	109.5
N1—C5—C4	117.30 (17)	C8—C11—H11B	109.5
O1—C6—C7	108.36 (16)	H11A—C11—H11B	109.5
O1—C6—H6A	110	C8—C11—H11C	109.5
C7—C6—H6A	110	H11A—C11—H11C	109.5
O1—C6—H6B	110	H11B—C11—H11C	109.5
C7—C6—H6B	110	N1—C12—S2	126.63 (16)
H6A—C6—H6B	108.4	N1—C12—S1	105.06 (14)
O2—C7—O3	127.09 (19)	S2—C12—S1	128.30 (13)