Crystal structure of two N'-(1-phenyl-benzyl-idene)-2-(thio-phen-3-yl)acetohydrazides.

The synthesis, spectroscopic data, crystal and mol-ecular structures of two N'-(1-phenyl-benzyl-idene)-2-(thio-phen-3-yl)acetohydrazides, namely N'-[1-(4-hy-droxy-phen-yl)benzyl-idene]-2-(thio-phen-3-yl)acetohydrazide, C13H10N2O2S, (3a), and N'-[1-(4-meth-oxy-phen-yl)benzyl-idene]-2-(thio-phen-3-yl)acetohydrazide, C14H14N2O2S, (3b), are described. Both compounds differ in the substituent at the para position of the phenyl ring: -OH for (3a) and -OCH3 for (3b). In (3a), the thio-phene ring is disordered over two orientations with occupancies of 0.762 (3) and 0.238 (3). The configuration about the C=N bond is E. The thio-phene and phenyl rings are inclined by 84.0 (3) and 87.0 (9)° for the major- and minor-occupancy disorder components in (3a), and by 85.89 (12)° in (3b). Although these dihedral angles are similar, the conformation of the linker between the two rings is different [the C-C-C-N torsion angle is -ac for (3a) and -sc for (3b), while the C6-C7-N9-N10 torsion angle is +ap for (3a) and -sp for (3b)]. A common feature in the crystal packing of (3a) and (3b) is the presence of N-H⋯O hydrogen bonds, resulting in the formation of chains of mol-ecules running along the b-axis direction in the case of (3a), or inversion dimers for (3b). The most prominent contributions to the surface contacts are those in which H atoms are involved, as confirmed by an analysis of the Hirshfeld surface.

Chemical context

<span class="Chemical">Acetohydrazides are considered to be good candidates for different pharmaceutical applications, including their use as anti­bacterial, anti­fugal, anti­microbial and anti­convulsant agents (Yadav et al., 2015 ▸; Bharti et al., 2010 ▸; Loncle et al., 2004 ▸; Papakonstanti­nou-Garoufalias et al., 2002 ▸). Moreover, many of them have shown analgesic and anti­platelet properties (Wardakhan et al., 2013 ▸). Combinations of <class="Chemical">span class="Chemical">acetohydrazide with other heterocyclic rings have also been investigated, such as the hydrazide-based 2-oxonicotino­nitrile derivatives that are considered to be potential anti­microbial agents (El-Sayed et al., 2018 ▸).

As a continuation of our research (Nguyen et al., 2016 ▸; Vu et al., 2016 ▸, 2017 ▸) on the chemical and physical properties of novel polythio­phenes, a new thio­phene monomer-containing <span class="Chemical">acetohydrazide has been prepared. We have synthesized two N′-(1-(phenyl­benzyl­idene)-2-(thio­phen-3-yl)<class="Chemical">span class="Chemical">acetohydrazides and present here the spectroscopic data and crystal structures of the title compounds, together with the Hirshfeld surface analysis.

Structural commentary

The hy­droxy derivative (3a) crystallizes in the ortho­rhom­bic space group <span class="Chemical">Pbca. The thio­phene ring is <class="Chemical">span class="Disease">disordered over two sites (the major and minor components are labelled with the suffixes A and B, respectively), corresponding to a rotation about the C3—C6 bond of approximately 180° with population parameters 0.762 (3) for S1A/C1A–C5A and 0.238 (3) for S1B/C1B–C5B (Fig. 1 ▸). The configuration of the C11=N10 bond can be described as E [the N9—N10—C11—C12 torsion angle is 174.82 (16)°]. The torsion angle C7—N9—N10—C11 of 177.10 (18)° indicates that the conformation around the N9—N10 bond is +ap. The mol­ecule is twisted about the C6—C7 bond with a dihedral angle of 84.0 (3)° between the thio­phene and benzene rings [87.0 (9)° for S1B/C1B–C5B] .

Figure 1

A view of the mol­ecular structure of (3a), with atom labels and displacement ellipsoids drawn at the 50% probability level. The minor-disorder component is shown in light green.

The meth­oxy derivative (3b) (Fig. 2 ▸) crystallizes in the triclinic space group P . Compared to (3a), the central part of (3b) displays a similar +ap conformation around the N9—N10 bond and an E configuration of the C11=N10 bond, as illustrated by the torsion angles C7—N9—N10—C11 [177.8 (2)°] and N9—N10—C11—C12 [179.26 (19)°]. However, the conformation about the two other bonds, C6—C7 and especially C7—N9, in the linker between both rings is different. The torsion angle C3—C6—C7—N9 is −101.8 (2)° (or -ac) for (3a) and −85.4 (3)° (or -sc) for (3b). As a consequence, in (3b) a short C6—<span class="Chemical">H6⋯N10 inter­action occurs (Table 2 ▸). In (3a) we observe an +ap conformation [torsion angle C6—C7—N9—N10 is 167.45 (16)°], while this is <class="Chemical">span class="Chemical">-sp in (3b) [torsion angle C6—C7—N9—N10 is −5.8 (3)°]. The dihedral angle between the thio­phene and phenyl rings is 85.89 (12)°, in the same order as for (3a).

Figure 2

The mol­ecular structure of (3b) with atom labels and 50% probability displacement ellipsoids.

Table 2

Hydrogen-bond geometry (Å, °) for (3b)

Cg1 is the centroid of the S1/C1–C5 thio­phene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯O8i	0.86	2.08	2.935 (3)	179
C6—H6A⋯N10	0.97	2.44	2.782 (3)	100
C13—H13⋯Cg1ii	0.93	2.68	3.611 (2)	179

Symmetry codes: (i) ; (ii) .

Supra­molecular features

In the crystal, mol­ecules of (3a) are connected by N9—H9⋯O8i [symmetry code: (i) −x + , y + , z] <span class="Chemical">hydrogen bonds, resulting in the formation of chains in the b-axis direction with a (4) graph-set motif (Fig. 3 ▸, Table 1 ▸). In addition, chains with a (11) graph-set motif running along the <class="Chemical">span class="Species">a-axis direction are formed by O18—H18⋯O8ii [symmetry code: (ii) x − , y, −z + ] hydrogen bonds (Fig. 4 ▸, Table 1 ▸). Two weaker inter­actions are present in the packing: a C—H⋯O and C—H⋯π(phen­yl) inter­action (for details see Table 1 ▸).

Figure 3

Part of the crystal structure of (3a), showing the chain formation through N—H⋯O inter­actions (red dashed lines) along the b-axis direction. The minor disorder component is not shown. Symmetry codes: (i) −x + , y + , z; (v) −x + , y − , z.

Table 1

Hydrogen-bond geometry (Å, °) for (3a)

Cg3 is the centroid of the C12–C17 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯O8i	0.86	2.12	2.953 (2)	162
O18—H18⋯O8ii	0.82	1.97	2.782 (2)	169
C2A—H2A⋯O8iii	0.93	2.57	3.439 (7)	155
C13—H13⋯Cg3iv	0.93	2.89	3.818 (3)	176

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Figure 4

Part of the crystal structure of (3a), illustrating the chain formation through O—H⋯O inter­actions (red dashed lines) along the a-axis direction. The minor disorder component is not shown. Symmetry codes: (i) x + , y, −z +  ; (ii) x − , y, −z + .

Replacing the –OH group in (3a) by an –OMe group in (3b) changes the <span class="Chemical">hydrogen-bonding pattern. The crystal packing of (3b) is now characterized by the presence of two different inversion dimers. The first type, with an (8) graph-set motif, is formed by N9—H9⋯O8i [symmetry code: (i) −x, −y + 2, −z + 1] <class="Chemical">span class="Chemical">hydrogen bonds (Fig. 5 ▸, Table 2 ▸). The second one involves C13—H13⋯π(thio­phene) inter­actions (Fig. 6 ▸, Table 2 ▸).

Figure 5

A partial packing diagram of (3b), showing dimer formation through N—H⋯O inter­actions (red dashed lines). Symmetry code: (i) −x, −y + 2, −z + 1.

Figure 6

A partial packing diagram of (3b), illustrating the dimer formation through C—H⋯π inter­actions (gray dashed lines). Cg1 is the centroid of the S1/C2–C5 thio­phene ring. Symmetry code: (ii) −x + 1, −y + 2, −z + 1.

No voids or π–π stackings are observed in the crystal packing of (3a) and (3b).

Database survey

A search of the Cambridge Structural Database (CSD, Version 5.40, update of May 2019; Groom et al., 2016 ▸) for the central linker between the two rings in the title compound, C—CH2—C(=O)—NH—N=CH—C (Fig. 7 ▸ a), resulted in 137 hits. Histograms of the distribution of the four torsion angles τ1 –τ4 along the linker backbone are shown in Fig. 7 ▸ b–e [the red and green lines depict the torsion angles for title compounds (3a) and (3b), respectively]. The histogram of τ1 reflects a wide spread with a preference for the −ap/+ap conformation, followed by the −sc/+sc conformation and only a few entries in the remaining regions. In the case of torsion angle τ2, two regions are preferred: −ap/+ap [for the majority of the entries and similar to (3a)] and −sp/+sp [similar to (3b)]. Torsion angles τ and τ4 show both a narrow spread in the region −ap/+ap.

Figure 7

(a) Fragment used for a search in the CSD. (b)–(e) Histograms of torsion angles τ1, τ2, τ3 and τ4, respectively. The vertical red and green lines show the torsion angles observed in title compounds (3a) and (3b), respectively.

Hirshfeld surface analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ▸) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ▸) were performed using CrystalExplorer (Turner et al., 2017 ▸). The Hirshfeld surfaces of compounds (3a) and (3b) mapped over d norm are given in Fig. 8 ▸.

Figure 8

The Hirshfeld surface mapped over d norm for (a) compound (3a) in the range −0.6166 to 1.1782 a.u., and (b) compound (3b) in the range −0.5274 to 1.2642 a.u.

The bright-red spots in Fig. 8 ▸ a near atoms O8 and N9 illustrate the N9—H9⋯O8 <span class="Chemical">hydrogen bond, and near atoms O8 and O18 the O18—H18⋯O8 <class="Chemical">span class="Chemical">hydrogen bond. The faint-red spots near atoms O8 and H2A, and C11 and H17 refer to short contacts in the crystal packing of (3a). The most significant contributions to the Hirshfeld surface are from H⋯H (30.5%), C⋯H/H⋯C (26.1%), O⋯H/H⋯O (18.6%) and S⋯H/H⋯S (10.7%) contacts.

For compound (3b), the N9—H9⋯O8 dimer formation is viewed as the bright-red spots near atoms O8 and N9 in Fig. 8 ▸ b. The faint-red spots near atoms H19C and H13 are indicative for a short H19C⋯H19C contact and the C13—H13⋯π(thio­phene) inter­action. The most significant contributions to the Hirshfeld surface are from H⋯H (40.6%), C⋯H/H⋯C (22.2%), O⋯H/H⋯O (15.1%) and S⋯H/H⋯S (12.5%) contacts.

Synthesis and crystallization

The reaction scheme to synthesize the title compounds, (3a) and (3b), is given in Fig. 9 ▸.

Figure 9

Reaction scheme for the title compounds (3a) and (3b).

Methyl 2-(thio­phen-3-yl)acetate (1) and 2-(thio­phen-3-yl)<span class="Chemical">acetohydrazide (2) were synthesized according to our previous research (Vu et al., 2017 ▸).

′

Compound (2) (3 mmol) and the appropriate <span class="Chemical">benzaldehyde derivatives (6 mmol) with <class="Chemical">span class="Chemical">acetic acid (1.5 mL) in ethanol (20 mL) were refluxed for 5 h. The reaction mixture was cooled down and the solid product was separated by filtration and purified by recrystallization in ethanol to give the compounds (3a) and (3b).

′

White crystals; m.p. 443 K; yield 63%. IR (KBr, cm−1): 3289, 3207 (NH), 3050, 2874 (C—H), 1621 (C=O), 1606 (CH=N), 1511 (C=C). 1H NMR [Bruker XL-500, 500 MHz, d 6-CDCl3, δ (ppm), J (Hz)]: 7.19 (m, 1H, H2), 7.11 (d, 1H, 5 J = 5.0, H4), 7.25 (dd, 1H, 2 J = 3.0, 4 J = 5.0, H5), 4.07 (s, 2H, <span class="Chemical">H6), 9.17 (s, 1H, H8), 7.79 (s, 1H, H9), 7.52 (d, 2H, J = 8.5 H11, H15), 6.87 (d, 2H, J = 8.5 H12, H14), 10.10/10.04 (s, 1H, H16). 13C NMR [Bruker XL-500, 125 MHz, d 6-CDCl3, δ (ppm)]: 122.3/122.4 (C2), 135.3/135.4 (C3), 128.7/128.8 (C4), 125.4/125.8 (C5), 33.6/35.9 (C6), 165.7/171.4 (C7), 146.7 (C9), 143.5 (C10), 128.3/128.6 (C11, C15), 115.6/116.6 (C12,C14), 159.6/159.2 (C13). Calculation for C13<class="Chemical">span class="Species">H12N2O2S: M [+H] = 260.9 au.

′

White crystals, m.p. 431 K, yield 53%. IR (KBr, cm−1): 3442, 3112 (NH), 3014, 2950 (C—H), 1706 (C=O), 1617 (CH=N), 1558, 1503 (C=C). 1H NMR [Bruker XL-500, 500 MHz, d 6-CDCl3, δ (ppm), J (Hz)]: 7.22 (m, 1H, H2); 7.12 (m, 1H, H4); 7.26 (dd, 1H, 2 J = 3.0, 5 J = 5.0, H5); 4.11 (s, 2H, <span class="Chemical">H6); 8.97 (s, 1H, H8); 7.69 (s, 1H, H9); 7.61 (d, 2H, J = 8.5, H11, H15); 6.94 (d, 2H, J = 8.5, H12, H14); 3.85 (m, 3H, H16). 13C NMR [Bruker XL-500, 125 MHz, d 6-CDCl3, δ (ppm)]: 122.8 (C2), 134.4 (C3), 129.3 (C4), 125.4 (C5), 34.3 (C6), 172.9 (C7), 143.6 (C9), 126.4 (C10), 128.8 (C11, C15), 114.3 (C12, C14), 161.3 (C13), 55.4 (C16). Calculation for C14<class="Chemical">span class="Species">H14N2O2S: M [+H] = 274.9 au.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All <span class="Disease">H atoms were placed in idealized positions and refined in riding mode, with U iso(H) values assigned as 1.2U eq of the parent atoms (1.5 times for methyl groups), with C—H distances of 0.93 (aromatic), 0.96 (CH3) and 0.97 Å (CH2), N—H distances of 0.86 Å and O—H distances of 0.82 Å (rotating OH). In (3a), the thio­phene ring is <class="Chemical">span class="Disease">disordered over two positions [population parameters 0.762 (3) and 0.238 (3)] and was refined with restraints for the bond lengths and angles in the ring. The anisotropic temperature factors for atoms S1, C2, C4 and C5 in both orientations were constrained to be equal. In the final cycles of refinement, four and two outliers were omitted for (3a) and (3b), respectively.

Table 3

Experimental details

	(3a)	(3b)
Crystal data
Chemical formula	C13H12N2O2S	C14H14N2O2S
M r	260.31	274.33
Crystal system, space group	Orthorhombic, P b c a	Triclinic, P
Temperature (K)	293	293
a, b, c (Å)	13.0820 (8), 8.0287 (4), 24.0442 (12)	6.5185 (2), 9.7447 (5), 10.9291 (6)
α, β, γ (°)	90, 90, 90	78.327 (4), 83.070 (4), 87.013 (4)
V (Å3)	2525.4 (2)	674.63 (6)
Z	8	2
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	0.25	0.24
Crystal size (mm)	0.35 × 0.2 × 0.05	0.5 × 0.15 × 0.05
Data collection
Diffractometer	Rigaku Oxford Diffraction SuperNova, Single source at offset/far, Eos	Rigaku Oxford Diffraction SuperNova, Single source at offset/far, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 ▸)	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 ▸)
T min, T max	0.453, 1.000	0.687, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13596, 2571, 1759	13795, 2752, 2238
R int	0.039	0.027
(sin θ/λ)max (Å−1)	0.625	0.625
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.046, 0.109, 1.07	0.051, 0.145, 1.06
No. of reflections	2571	2752
No. of parameters	178	173
No. of restraints	80	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.19, −0.18	0.33, −0.38

Computer programs: CrysAlis PRO (Rigaku OD, 2018 ▸), SHELXT (Sheldrick, 2015 ▸ a ▸), SHELXL (Sheldrick, 2015 ▸b) and OLEX2 (Dolomanov et al., 2009 ▸).

Crystal structure: contains datablock(s) 3a, 3b. DOI: 10.1107/S2056989019008892/rz5260sup1.cif

Structure factors: contains datablock(s) 3a. DOI: 10.1107/S2056989019008892/rz52603asup2.hkl

Structure factors: contains datablock(s) 3b. DOI: 10.1107/S2056989019008892/rz52603bsup3.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019008892/rz52603asup4.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019008892/rz52603bsup5.cml

CCDC references: 1935593, 1935592

Additional supporting information: crystallographic information; 3D view; checkCIF report

C13H12N2O2S	Dx = 1.369 Mg m−3
Mr = 260.31	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3446 reflections
a = 13.0820 (8) Å	θ = 3.1–23.7°
b = 8.0287 (4) Å	µ = 0.25 mm−1
c = 24.0442 (12) Å	T = 293 K
V = 2525.4 (2) Å3	Plate, white
Z = 8	0.35 × 0.2 × 0.05 mm
F(000) = 1088

Rigaku Oxford Diffraction SuperNova, Single source at offset/far, Eos diffractometer	2571 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	1759 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.039
Detector resolution: 15.9631 pixels mm-1	θmax = 26.4°, θmin = 3.1°
ω scans	h = −16→15
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	k = −9→10
Tmin = 0.453, Tmax = 1.000	l = −28→30
13596 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.046	w = 1/[σ2(Fo2) + (0.0334P)2 + 0.6755P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.109	(Δ/σ)max < 0.001
S = 1.07	Δρmax = 0.19 e Å−3
2571 reflections	Δρmin = −0.18 e Å−3
178 parameters	Extinction correction: SHELXL (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
80 restraints	Extinction coefficient: 0.0022 (6)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1A	0.67164 (8)	0.8283 (2)	0.43607 (8)	0.0718 (4)	0.762 (3)
S1B	0.6152 (4)	0.9867 (10)	0.3990 (3)	0.0718 (4)	0.238 (3)
C2A	0.5667 (3)	0.7484 (7)	0.4673 (3)	0.0542 (12)	0.762 (3)
H2A	0.568185	0.659897	0.492216	0.065*	0.762 (3)
C2B	0.4941 (11)	0.970 (3)	0.4213 (16)	0.0542 (12)	0.238 (3)
H2B	0.443026	1.047111	0.413833	0.065*	0.238 (3)
C3	0.47998 (16)	0.8287 (2)	0.45167 (8)	0.0449 (5)
C4A	0.5018 (5)	0.9582 (10)	0.4141 (5)	0.062 (2)	0.762 (3)
H4A	0.451169	1.026238	0.399205	0.074*	0.762 (3)
C4B	0.5719 (9)	0.741 (3)	0.4587 (11)	0.062 (2)	0.238 (3)
H4B	0.575924	0.640913	0.478166	0.074*	0.238 (3)
C5A	0.6056 (6)	0.9770 (11)	0.4008 (4)	0.100 (3)	0.762 (3)
H5A	0.633233	1.056338	0.376954	0.120*	0.762 (3)
C5B	0.6580 (10)	0.818 (2)	0.4337 (11)	0.100 (3)	0.238 (3)
H5B	0.725438	0.781636	0.435909	0.120*	0.238 (3)
C6	0.37396 (16)	0.7786 (3)	0.47035 (8)	0.0506 (6)
H6A	0.377254	0.726825	0.506761	0.061*
H6B	0.330528	0.876200	0.472922	0.061*
C7	0.33041 (15)	0.6577 (3)	0.42864 (8)	0.0419 (5)
O8	0.36037 (11)	0.51138 (17)	0.42613 (5)	0.0476 (4)
N9	0.26256 (13)	0.7198 (2)	0.39247 (6)	0.0455 (4)
H9	0.236595	0.816955	0.397669	0.055*
N10	0.23452 (13)	0.6255 (2)	0.34641 (6)	0.0441 (4)
C11	0.16622 (15)	0.6908 (2)	0.31536 (8)	0.0444 (5)
H11	0.135667	0.790093	0.326364	0.053*
C12	0.13478 (16)	0.6139 (2)	0.26302 (8)	0.0428 (5)
C13	0.04946 (18)	0.6712 (3)	0.23499 (9)	0.0553 (6)
H13	0.012178	0.759047	0.249952	0.066*
C14	0.01803 (18)	0.6010 (3)	0.18517 (9)	0.0561 (6)
H14	−0.040209	0.640454	0.167331	0.067*
C15	0.07373 (17)	0.4720 (2)	0.16220 (8)	0.0462 (5)
C16	0.16018 (17)	0.4149 (3)	0.18911 (9)	0.0562 (6)
H16	0.198233	0.328679	0.173641	0.067*
C17	0.19021 (17)	0.4850 (3)	0.23870 (9)	0.0538 (6)
H17	0.248657	0.445441	0.256329	0.065*
O18	0.04708 (13)	0.39577 (19)	0.11361 (6)	0.0620 (5)
H18	−0.003809	0.441085	0.100663	0.093*

	U11	U22	U33	U12	U13	U23
S1A	0.0493 (6)	0.0807 (8)	0.0853 (7)	0.0003 (5)	−0.0078 (5)	−0.0050 (6)
S1B	0.0493 (6)	0.0807 (8)	0.0853 (7)	0.0003 (5)	−0.0078 (5)	−0.0050 (6)
C2A	0.065 (2)	0.051 (2)	0.047 (3)	0.0092 (16)	−0.0120 (16)	0.0016 (17)
C2B	0.065 (2)	0.051 (2)	0.047 (3)	0.0092 (16)	−0.0120 (16)	0.0016 (17)
C3	0.0513 (14)	0.0403 (11)	0.0430 (11)	−0.0013 (10)	−0.0106 (10)	−0.0057 (9)
C4A	0.060 (3)	0.053 (3)	0.072 (6)	−0.0011 (18)	−0.008 (2)	0.015 (3)
C4B	0.060 (3)	0.053 (3)	0.072 (6)	−0.0011 (18)	−0.008 (2)	0.015 (3)
C5A	0.132 (6)	0.063 (3)	0.103 (4)	−0.025 (3)	−0.011 (3)	0.021 (2)
C5B	0.132 (6)	0.063 (3)	0.103 (4)	−0.025 (3)	−0.011 (3)	0.021 (2)
C6	0.0551 (15)	0.0539 (13)	0.0427 (11)	0.0014 (11)	−0.0020 (10)	−0.0088 (10)
C7	0.0408 (13)	0.0444 (12)	0.0405 (11)	−0.0017 (9)	0.0056 (9)	−0.0002 (9)
O8	0.0533 (10)	0.0400 (8)	0.0495 (8)	0.0012 (7)	−0.0023 (7)	0.0005 (6)
N9	0.0489 (11)	0.0370 (9)	0.0506 (10)	0.0033 (8)	−0.0043 (8)	−0.0084 (8)
N10	0.0471 (11)	0.0408 (10)	0.0444 (9)	−0.0029 (8)	−0.0030 (8)	−0.0029 (8)
C11	0.0451 (13)	0.0420 (11)	0.0461 (11)	0.0020 (9)	0.0006 (10)	0.0014 (9)
C12	0.0458 (13)	0.0404 (11)	0.0424 (11)	−0.0007 (9)	−0.0002 (9)	0.0024 (9)
C13	0.0611 (16)	0.0527 (14)	0.0520 (13)	0.0196 (11)	−0.0082 (11)	−0.0087 (10)
C14	0.0600 (15)	0.0569 (14)	0.0515 (13)	0.0146 (11)	−0.0136 (11)	−0.0038 (11)
C15	0.0553 (14)	0.0429 (12)	0.0405 (11)	0.0003 (10)	−0.0008 (10)	0.0007 (9)
C16	0.0616 (16)	0.0536 (13)	0.0535 (13)	0.0137 (11)	−0.0009 (12)	−0.0088 (11)
C17	0.0516 (15)	0.0545 (13)	0.0553 (13)	0.0117 (11)	−0.0082 (11)	−0.0018 (11)
O18	0.0748 (13)	0.0574 (10)	0.0539 (9)	0.0122 (8)	−0.0116 (8)	−0.0129 (8)

S1A—C2A	1.691 (4)	C7—O8	1.240 (2)
C2A—H2A	0.9300	C7—N9	1.339 (2)
S1B—C2B	1.677 (9)	N9—H9	0.8600
C2B—H2B	0.9300	N9—N10	1.391 (2)
C2A—C3	1.357 (4)	N10—C11	1.277 (2)
C2B—C3	1.360 (9)	C11—H11	0.9300
C4A—H4A	0.9300	C11—C12	1.461 (3)
C4B—H4B	0.9300	C12—C13	1.382 (3)
S1A—C5A	1.700 (7)	C12—C17	1.393 (3)
C4A—C5A	1.404 (6)	C13—H13	0.9300
C5A—H5A	0.9300	C13—C14	1.386 (3)
S1B—C5B	1.688 (9)	C14—H14	0.9300
C4B—C5B	1.419 (9)	C14—C15	1.381 (3)
C5B—H5B	0.9300	C15—C16	1.381 (3)
C3—C4A	1.407 (4)	C15—O18	1.364 (2)
C3—C4B	1.404 (9)	C16—H16	0.9300
C3—C6	1.512 (3)	C16—C17	1.376 (3)
C6—H6A	0.9700	C17—H17	0.9300
C6—H6B	0.9700	O18—H18	0.8200
C6—C7	1.508 (3)
C4A—C5A—S1A	107.6 (5)	C3—C4B—C5B	114.2 (9)
C4B—C5B—S1B	107.2 (8)	O8—C7—C6	121.54 (19)
S1A—C2A—H2A	124.0	O8—C7—N9	122.07 (18)
S1B—C2B—H2B	124.2	N9—C7—C6	116.27 (18)
C5A—C4A—C3	115.0 (5)	C7—N9—H9	120.4
C5A—C4A—H4A	122.5	C7—N9—N10	119.29 (16)
C5B—C4B—H4B	122.9	N10—N9—H9	120.4
C2A—S1A—C5A	94.3 (3)	C11—N10—N9	115.25 (17)
S1A—C5A—H5A	126.2	N10—C11—H11	119.1
C4A—C5A—H5A	126.2	N10—C11—C12	121.81 (19)
C2B—S1B—C5B	95.2 (6)	C12—C11—H11	119.1
S1B—C5B—H5B	126.4	C13—C12—C11	120.45 (18)
C4B—C5B—H5B	126.4	C13—C12—C17	117.57 (19)
C2A—C3—C4A	111.1 (3)	C17—C12—C11	121.95 (19)
C2B—C3—C4B	111.5 (7)	C12—C13—H13	119.1
C4A—C3—C6	125.0 (3)	C12—C13—C14	121.7 (2)
C2A—C3—C6	123.9 (3)	C14—C13—H13	119.1
C4B—C3—C6	128.0 (6)	C13—C14—H14	120.2
C2B—C3—C6	120.4 (5)	C15—C14—C13	119.6 (2)
C3—C6—H6A	110.0	C15—C14—H14	120.2
C3—C2A—S1A	112.1 (3)	C14—C15—C16	119.6 (2)
C3—C2B—S1B	111.6 (7)	O18—C15—C14	123.0 (2)
C3—C6—H6B	110.0	O18—C15—C16	117.47 (19)
H6A—C6—H6B	108.3	C15—C16—H16	119.9
C3—C2A—H2A	124.0	C17—C16—C15	120.3 (2)
C3—C2B—H2B	124.2	C17—C16—H16	119.9
C7—C6—C3	108.68 (16)	C12—C17—H17	119.4
C7—C6—H6A	110.0	C16—C17—C12	121.3 (2)
C3—C4A—H4A	122.5	C16—C17—H17	119.4
C3—C4B—H4B	122.9	C15—O18—H18	109.5
C7—C6—H6B	110.0
C2A—S1A—C5A—C4A	−0.7 (11)	C6—C3—C4B—C5B	176.8 (17)
C2B—S1B—C5B—C4B	5 (3)	C6—C3—C4A—C5A	−177.0 (8)
C5B—S1B—C2B—C3	−5 (3)	C6—C7—N9—N10	167.45 (16)
C5A—S1A—C2A—C3	0.8 (7)	C7—N9—N10—C11	177.10 (18)
S1B—C2B—C3—C4B	3 (3)	O8—C7—N9—N10	−8.6 (3)
S1A—C2A—C3—C4A	−0.7 (5)	N9—N10—C11—C12	174.82 (16)
S1A—C2A—C3—C6	176.5 (3)	N10—C11—C12—C13	169.1 (2)
S1B—C2B—C3—C6	−173.1 (14)	N10—C11—C12—C17	−12.8 (3)
C2B—C3—C6—C7	95 (2)	C11—C12—C13—C14	179.8 (2)
C2A—C3—C6—C7	−91.1 (5)	C11—C12—C17—C16	−179.4 (2)
C4A—C3—C6—C7	85.7 (7)	C12—C13—C14—C15	−0.9 (4)
C4B—C3—C6—C7	−81.0 (17)	C13—C12—C17—C16	−1.2 (3)
C2A—C3—C4A—C5A	0.1 (11)	C13—C14—C15—C16	−0.1 (3)
C2B—C3—C4B—C5B	1 (3)	C13—C14—C15—O18	179.4 (2)
C3—C4A—C5A—S1A	0.5 (14)	C14—C15—C16—C17	0.5 (3)
C3—C4B—C5B—S1B	−4 (3)	C15—C16—C17—C12	0.1 (3)
C3—C6—C7—O8	74.2 (2)	C17—C12—C13—C14	1.6 (3)
C3—C6—C7—N9	−101.8 (2)	O18—C15—C16—C17	−179.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O8i	0.86	2.12	2.953 (2)	162
O18—H18···O8ii	0.82	1.97	2.782 (2)	169
C2A—H2A···O8iii	0.93	2.57	3.439 (7)	155
C13—H13···Cg3iv	0.93	2.89	3.818 (3)	176

C14H14N2O2S	Z = 2
Mr = 274.33	F(000) = 288
Triclinic, P1	Dx = 1.350 Mg m−3
a = 6.5185 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7447 (5) Å	Cell parameters from 5534 reflections
c = 10.9291 (6) Å	θ = 3.1–27.2°
α = 78.327 (4)°	µ = 0.24 mm−1
β = 83.070 (4)°	T = 293 K
γ = 87.013 (4)°	Needle, white
V = 674.63 (6) Å3	0.5 × 0.15 × 0.05 mm

Rigaku Oxford Diffraction SuperNova, Single source at offset/far, Eos diffractometer	2752 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	2238 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.027
Detector resolution: 15.9631 pixels mm-1	θmax = 26.4°, θmin = 2.6°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	k = −12→12
Tmin = 0.687, Tmax = 1.000	l = −13→13
13795 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051	H-atom parameters constrained
wR(F2) = 0.145	w = 1/[σ2(Fo2) + (0.0537P)2 + 0.5294P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
2752 reflections	Δρmax = 0.33 e Å−3
173 parameters	Δρmin = −0.38 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.68895 (12)	0.78924 (10)	0.16957 (9)	0.0734 (3)
C2	0.5595 (4)	0.7356 (3)	0.3147 (3)	0.0534 (6)
H2	0.619153	0.726965	0.389168	0.064*
C3	0.3579 (4)	0.7066 (2)	0.3100 (2)	0.0436 (5)
C4	0.3123 (4)	0.7275 (3)	0.1841 (2)	0.0512 (6)
H4	0.182310	0.712513	0.163071	0.061*
C5	0.4790 (4)	0.7727 (3)	0.0935 (2)	0.0497 (6)
H5	0.476097	0.790729	0.006852	0.060*
C6	0.2002 (4)	0.6708 (3)	0.4234 (2)	0.0479 (6)
H6A	0.265853	0.615910	0.493142	0.057*
H6B	0.093072	0.615347	0.404620	0.057*
C7	0.1056 (3)	0.8042 (3)	0.4589 (2)	0.0418 (5)
O8	−0.0513 (2)	0.86009 (19)	0.41630 (16)	0.0508 (4)
N9	0.2051 (3)	0.8658 (2)	0.53376 (18)	0.0417 (5)
H9	0.160089	0.945717	0.549350	0.050*
N10	0.3778 (3)	0.8031 (2)	0.58594 (17)	0.0412 (5)
C11	0.4621 (3)	0.8739 (2)	0.6517 (2)	0.0411 (5)
H11	0.406000	0.961642	0.660165	0.049*
C12	0.6438 (3)	0.8207 (2)	0.7139 (2)	0.0372 (5)
C13	0.7354 (4)	0.9057 (2)	0.7794 (2)	0.0423 (5)
H13	0.679005	0.994741	0.782354	0.051*
C14	0.9070 (4)	0.8605 (2)	0.8396 (2)	0.0444 (5)
H14	0.966061	0.919004	0.882266	0.053*
C15	0.9921 (3)	0.7276 (2)	0.8368 (2)	0.0409 (5)
C16	0.9037 (4)	0.6415 (2)	0.7722 (2)	0.0442 (5)
H16	0.960075	0.552276	0.769944	0.053*
C17	0.7322 (4)	0.6880 (2)	0.7113 (2)	0.0435 (5)
H17	0.674636	0.629647	0.667808	0.052*
O18	1.1602 (3)	0.69079 (19)	0.90073 (17)	0.0565 (5)
C19	1.2603 (4)	0.5592 (3)	0.8926 (3)	0.0634 (8)
H19A	1.307244	0.557208	0.806228	0.095*
H19B	1.164788	0.485433	0.925510	0.095*
H19C	1.376398	0.546115	0.940466	0.095*

	U11	U22	U33	U12	U13	U23
S1	0.0554 (5)	0.0848 (6)	0.0861 (6)	−0.0076 (4)	0.0084 (4)	−0.0394 (5)
C2	0.0441 (13)	0.0592 (16)	0.0640 (16)	0.0019 (11)	−0.0103 (12)	−0.0270 (13)
C3	0.0445 (13)	0.0376 (12)	0.0529 (14)	−0.0006 (9)	−0.0085 (10)	−0.0175 (10)
C4	0.0541 (15)	0.0493 (14)	0.0568 (15)	−0.0023 (11)	−0.0156 (12)	−0.0207 (12)
C5	0.0528 (14)	0.0505 (14)	0.0506 (14)	−0.0044 (11)	0.0003 (11)	−0.0238 (11)
C6	0.0503 (14)	0.0436 (13)	0.0526 (14)	−0.0098 (10)	−0.0110 (11)	−0.0108 (11)
C7	0.0368 (12)	0.0511 (13)	0.0368 (11)	−0.0088 (10)	−0.0037 (9)	−0.0056 (10)
O8	0.0366 (9)	0.0680 (12)	0.0511 (10)	−0.0008 (8)	−0.0129 (7)	−0.0152 (8)
N9	0.0364 (10)	0.0489 (11)	0.0424 (10)	0.0032 (8)	−0.0114 (8)	−0.0121 (8)
N10	0.0381 (10)	0.0472 (11)	0.0386 (10)	0.0011 (8)	−0.0096 (8)	−0.0069 (8)
C11	0.0421 (12)	0.0422 (12)	0.0396 (12)	0.0021 (9)	−0.0073 (9)	−0.0087 (9)
C12	0.0370 (11)	0.0399 (12)	0.0343 (11)	−0.0020 (9)	−0.0055 (9)	−0.0052 (9)
C13	0.0485 (13)	0.0361 (12)	0.0436 (12)	0.0034 (10)	−0.0101 (10)	−0.0098 (9)
C14	0.0498 (13)	0.0439 (13)	0.0444 (13)	−0.0029 (10)	−0.0149 (10)	−0.0143 (10)
C15	0.0393 (12)	0.0467 (13)	0.0356 (11)	−0.0006 (10)	−0.0088 (9)	−0.0034 (9)
C16	0.0482 (13)	0.0365 (12)	0.0491 (13)	0.0036 (10)	−0.0117 (11)	−0.0094 (10)
C17	0.0470 (13)	0.0408 (12)	0.0465 (13)	−0.0032 (10)	−0.0113 (10)	−0.0135 (10)
O18	0.0538 (10)	0.0595 (11)	0.0613 (11)	0.0109 (8)	−0.0284 (9)	−0.0142 (9)
C19	0.0560 (16)	0.0645 (18)	0.0690 (18)	0.0175 (13)	−0.0214 (14)	−0.0085 (14)

S1—C2	1.700 (3)	C11—H11	0.9300
S1—C5	1.715 (3)	C11—C12	1.456 (3)
C2—H2	0.9300	C12—C13	1.396 (3)
C2—C3	1.368 (3)	C12—C17	1.393 (3)
C3—C4	1.415 (3)	C13—H13	0.9300
C3—C6	1.507 (3)	C13—C14	1.374 (3)
C4—H4	0.9300	C14—H14	0.9300
C4—C5	1.403 (4)	C14—C15	1.387 (3)
C5—H5	0.9300	C15—C16	1.387 (3)
C6—H6A	0.9700	C15—O18	1.363 (3)
C6—H6B	0.9700	C16—H16	0.9300
C6—C7	1.511 (3)	C16—C17	1.379 (3)
C7—O8	1.230 (3)	C17—H17	0.9300
C7—N9	1.348 (3)	O18—C19	1.422 (3)
N9—H9	0.8600	C19—H19A	0.9600
N9—N10	1.382 (2)	C19—H19B	0.9600
N10—C11	1.277 (3)	C19—H19C	0.9600
C2—S1—C5	93.48 (13)	N10—C11—C12	121.7 (2)
S1—C2—H2	123.7	C12—C11—H11	119.2
C3—C2—S1	112.5 (2)	C13—C12—C11	119.1 (2)
C3—C2—H2	123.7	C17—C12—C11	123.1 (2)
C2—C3—C4	111.0 (2)	C17—C12—C13	117.8 (2)
C2—C3—C6	124.5 (2)	C12—C13—H13	119.3
C4—C3—C6	124.3 (2)	C14—C13—C12	121.4 (2)
C3—C4—H4	122.7	C14—C13—H13	119.3
C5—C4—C3	114.5 (2)	C13—C14—H14	120.0
C5—C4—H4	122.7	C13—C14—C15	120.0 (2)
S1—C5—H5	125.7	C15—C14—H14	120.0
C4—C5—S1	108.50 (19)	C14—C15—C16	119.5 (2)
C4—C5—H5	125.7	O18—C15—C14	116.0 (2)
C3—C6—H6A	109.8	O18—C15—C16	124.5 (2)
C3—C6—H6B	109.8	C15—C16—H16	119.9
C3—C6—C7	109.57 (19)	C17—C16—C15	120.1 (2)
H6A—C6—H6B	108.2	C17—C16—H16	119.9
C7—C6—H6A	109.8	C12—C17—H17	119.4
C7—C6—H6B	109.8	C16—C17—C12	121.2 (2)
O8—C7—C6	121.7 (2)	C16—C17—H17	119.4
O8—C7—N9	120.2 (2)	C15—O18—C19	117.5 (2)
N9—C7—C6	117.9 (2)	O18—C19—H19A	109.5
C7—N9—H9	119.3	O18—C19—H19B	109.5
C7—N9—N10	121.3 (2)	O18—C19—H19C	109.5
N10—N9—H9	119.3	H19A—C19—H19B	109.5
C11—N10—N9	115.4 (2)	H19A—C19—H19C	109.5
N10—C11—H11	119.2	H19B—C19—H19C	109.5
S1—C2—C3—C4	0.8 (3)	N10—C11—C12—C13	176.9 (2)
S1—C2—C3—C6	−173.66 (19)	N10—C11—C12—C17	−3.1 (4)
C2—S1—C5—C4	0.8 (2)	C11—C12—C13—C14	180.0 (2)
C2—C3—C4—C5	−0.2 (3)	C11—C12—C17—C16	−179.6 (2)
C2—C3—C6—C7	84.9 (3)	C12—C13—C14—C15	−0.4 (4)
C3—C4—C5—S1	−0.5 (3)	C13—C12—C17—C16	0.4 (3)
C3—C6—C7—O8	90.8 (3)	C13—C14—C15—C16	0.4 (4)
C3—C6—C7—N9	−85.4 (3)	C13—C14—C15—O18	−179.0 (2)
C4—C3—C6—C7	−88.8 (3)	C14—C15—C16—C17	0.0 (4)
C5—S1—C2—C3	−1.0 (2)	C14—C15—O18—C19	−175.7 (2)
C6—C3—C4—C5	174.3 (2)	C15—C16—C17—C12	−0.4 (4)
C6—C7—N9—N10	−5.8 (3)	C16—C15—O18—C19	4.9 (4)
C7—N9—N10—C11	177.8 (2)	C17—C12—C13—C14	0.0 (3)
O8—C7—N9—N10	177.97 (19)	O18—C15—C16—C17	179.4 (2)
N9—N10—C11—C12	179.26 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O8i	0.86	2.08	2.935 (3)	179
C6—H6A···N10	0.97	2.44	2.782 (3)	100
C13—H13···Cg1ii	0.93	2.68	3.611 (2)	179