N′-[(1E)-(5-Nitro­furan-2-yl)methyl­idene]thio­phene-2-carbohydrazide: crystal structure and Hirshfeld surface analysis

Cardoso, L.N.F.; Nogueira, T.C.M.; Wardell, J.L.; Wardell, S.M.S.V.; Souza, M.V.N. de; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989016009968

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ISSN: 2056-9890

Volume 72| Part 7| July 2016| Pages 1025-1031

https://doi.org/10.1107/S2056989016009968

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N′-[(1E)-(5-Nitrofuran-2-yl)methylidene]thiophene-2-carbohydrazide: crystal structure and Hirshfeld surface analysis

Laura N. F. Cardoso,^a Thais C. M. Nogueira,^a James L. Wardell,^a,^b ‡ Solange M. S. V. Wardell,^c Marcus V. N. de Souza,^a Mukesh M. Jotani ^d and Edward R. T. Tiekink ^e ^*

^aFundaçaö Oswaldo Cruz, Instituto de Tecnologia em Fármacos-Far Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil, ^bDepartment of Chemistry, University of Aberdeen, Old Aberdeen, AB24 3UE, Scotland, ^cCHEMSOL, 1 Harcourt Road, Aberdeen AB15 5NY, Scotland, ^dDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, and ^eResearch Centre for Crystalline Materials, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: edwardt@sunway.edu.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 16 June 2016; accepted 19 June 2016; online 24 June 2016)

In the title carbohydrazide, C₁₀H₇N₃O₄S, the dihedral angle between the terminal five-membered rings is 27.4 (2)°, with these lying to the same side of the plane through the central CN₂C(=O) atoms (r.m.s. deviation = 0.0403 Å), leading to a curved molecule. The conformation about the C=N imine bond [1.281 (5) Å] is E, and the carbonyl O and amide H atoms are anti. In the crystal, N—H⋯O hydrogen bonds lead to supramolecular chains, generated by a 4₁ screw-axis along the c direction. A three-dimensional architecture is consolidated by thienyl-C—H⋯O(nitro) and furanyl-C—H⋯O(nitro) interactions, as well as π–π interactions between the thienyl and furanyl rings [inter-centroid distance = 3.515 (2) Å]. These, and other, weak intermolecular interactions, e.g. nitro-N—O⋯π(thienyl), have been investigated by Hirshfeld surface analysis, which confirms the dominance of the conventional N—H⋯O hydrogen bonding to the overall molecular packing.

Keywords: crystal structure; carbohydrazide; hydrogen bonding; conformation; Hirshfeld surface analysis.

CCDC reference: 1486459

1. Chemical context

Thiophene and its derivatives have been well studied as materials, e.g. in applications in organic electronics and photonics (Perepichka & Perepichka, 2009 ) and in the medical area. In the latter context, the thiophene nucleus is present in many natural and synthetic products having a wide range of pharmacological activities, such as anti-viral (Chan et al., 2004 ), anti-cancer (Romagnoli et al., 2011 ), anti-bacterial (Sivadas et al., 2011 ; Jain et al., 2012 ), anti-fungal (Jain et al., 2012; Saeed et al., 2010 ), anti-inflammatory (Kumar et al., 2004 ) and anti-microbial and anti-tuberculosis (anti-TB) activities (Abdel-Aal et al., 2010 ). Our interests in the biological activities and structural chemistry of heterocyclic compounds have led us to investigate thiophene and its derivatives as tuberculostatic agents. Thus, some of us have reported the anti-TB activities of acetamido derivatives, 2-(RR′NCOCH₂)-thiophene (Lourenço et al., 2007 ; de Sousa, Ferreira et al., 2008 ; de Sousa, Lourenço et al., 2008 ), acetohydrazide derivatives 2-(ArCH=N–NRCOCH₂)-thiophene, 1 (Cardoso et al., 2014 ; Cardoso et al., 2016a ) and 2-(ArCH=N–NRCO)-thiophene, 2, R = H or Me (Cardoso et al., 2016a). Herein, we wish to report the crystal structure of the title compound, (E)-N′-(5-nitrofuran-2-ylmethylene)thiophene-2-carbohydrazide, (I), Scheme 1, as well as an analysis of its Hirshfeld surface. Crystal structures of 1: Ar = 5-nitrothien-2-yl; R = H, Me (Cardoso et al., 2016b ), 2: Ar = 5-nitrothien-2-yl; R = H Me (Cardoso et al., 2016b) and 1: Ar = 5-HOC₆H₄: R = H (Cardoso et al., 2014) have been previously published.

2. Structural commentary

In (I), Fig. 1, the conformation about the C6=N2 bond [1.281 (5) Å] is E. A 5-nitrofuran-2-yl ring is connected at the C6 atom. The furanyl ring is almost planar [r.m.s deviation = 0.006 Å] and the nitro group is almost co-planar with its attached ring as seen in the O3—N3—C10—O2 torsion angle of −1.7 (5)°. The thienyl ring is also planar within experimental error [r.m.s. deviation = 0.005 Å] and orientated so that the sulfur atom is syn to the carbonyl-O1 atom. Overall, the molecule is curved with the rings lying to the same side of the plane through the bridging CN₂C(=O) atoms, r.m.s. deviation = 0.0403 Å, with twists noted in both the S1—C1—C5—O1 and N2—C6—C7—O2 torsion angles of −9.8 (5) and 5.4 (6)°, respectively; the dihedral angle between the five-membered rings is 27.4 (2)°.

Figure 1
The molecular structure of (I)

, showing displacement ellipsoids at the 70% probability level.

3. Supramolecular features

The anti relationship between the carbonyl-O and amide-H atoms enables the formation of directional N—H⋯O hydrogen bonds leading to supramolecular chains, generated by a 4₁ screw-axis propagating along the c-axis direction, Fig. 2a and Table 1. The chains are connected into a three-dimensional architecture by thienyl-C—H⋯O(nitro) and furanyl-C—H⋯O(nitro) interactions, involving the same nitro-O4 atom, Table 1. In addition, π–π interactions are formed between the two five-membered rings with the inter-centroid distance being 3.515 (2) Å, and the angle of inclination is 3.9 (2)° for symmetry operation: (i) 1 − y, $[{1\over 2}]$ − x, − $[{1\over 4}]$ + z. A view of the unit-cell contents is shown in Fig. 2b.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.87 (3)	2.05 (3)	2.882 (4)	159 (3)
C4—H4⋯O4ⁱⁱ	0.95	2.42	3.293 (6)	152
C8—H8⋯O4ⁱⁱⁱ	0.95	2.53	3.242 (5)	132
Symmetry codes: (i) $[-y+{\script{1\over 2}}, x, z-{\script{1\over 4}}]$ ; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+1, z-{\script{1\over 2}}]$ .

Figure 2
The molecular packing in (I)

, showing (a) a view of a supramolecular chain aligned along the c axis sustained by amide-N—H⋯O(carbonyl) hydrogen bonds and (b) a view in projection down the c axis of the unit-cell contents; one chain has been highlighted in space-filling mode. The N—H⋯O, C—H⋯O and π–π interactions are shown as orange, blue and purple dashed lines, respectively. Colour code: S yellow, O red, N blue, C grey and H green.

4. Hirshfeld surface analysis

Crystal Explorer 3.1 (Wolff et al., 2012 ) was used to generate Hirshfeld surfaces mapped over d_norm, d_e, shape-index, curvedness and electrostatic potential. The latter were calculated using TONTO (Spackman et al., 2008 ; Jayatilaka et al., 2005 ) integrated into Crystal Explorer, wherein the experimental structure was used as the input geometry. In addition, the electrostatic potentials were mapped on Hirshfeld surfaces using the STO-3G basis set at Hartree–Fock level of theory over a range ±0.12 au. The contact distances d_i and d_e from the Hirshfeld surface to the nearest atom inside and outside, respectively, enable the analysis of intermolecular interactions through the mapping of d_norm. The combination of d_e and d_i in the form of a two-dimensional fingerprint plot (McKinnon et al., 2004 ) provides a useful summary of intermolecular contacts in the crystal.

Two views of Hirshfeld surfaces calculated for (I), mapped over d_norm in the −0.1 to 1.2 Å range are shown in Fig. 3. The bright-red spots near the amino-N—H and carbonyl-O atoms, labelled as `1' in Fig. 3, indicate their roles as respective donor and acceptor sites in the dominant N—H⋯O hydrogen bonding in the crystal. These also appear as blue and red regions, respectively, corresponding to positive and negative electrostatic potentials, respectively, on the Hirshfeld surface mapped over electrostatic potential in Fig. 4. The light-red spots labelled as `2' and `3' in Fig. 3, and light-blue and light-red regions in Fig. 4, represent the intermolecular thienyl-C—H⋯O(nitro) and furanyl-C—H⋯O(nitro) interactions involving the nitro-O4 atom as described above in Supramolecular features. The immediate environment about the molecule within d_norm mapped Hirshfeld surface mediated by the above interactions is illustrated in Fig. 5.

Figure 3
Two views of the Hirshfeld surface mapped over d_norm for (I)

, with labels 1, 2, 3 and 4 indicating specific intermolecular interactions discussed in the text.

Figure 4
A view of the Hirshfeld surface mapped over electrostatic potential for (I)

. The red and blue regions represent negative and positive electrostatic potentials, respectively.

Figure 5
A view of Hirshfeld surface mapped over d_norm for showing intermolecular interactions about a reference molecule of (I)

The presence of a short intermolecular C⋯C contact between thienyl-C2 and furanyl-C10 atoms, Table 2, which fall within π–π contact between the thienyl and furanyl rings can also be viewed as faint-red spots near these atoms, labelled as `4' in Fig. 3. In the crystal, a comparatively weak N—O⋯π interaction (Spek, 2009 ) between the nitro—O4 atom and a symmetry-related thienyl ring [N3⋯Cg(S1,C1–C4) = 3.506 (4) Å, O4⋯Cg(S1,C1–C4) = 3.639 (4) Å and N3—O4⋯Cg = 74.0 (2)°] is also evident from the light-blue and red regions corresponding to their respective potentials on the Hirshfeld surface mapped over electrostatic potential in Fig. 4.

Table 2
Summary of short interatomic contacts (Å) in the crystal of the title compound

Contact	Distance	Symmetry operation
C2⋯C10	3.361 (5)	$[{1\over 2}]$ − x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
C5⋯H2	2.89	$[{1\over 2}]$ − x, y, $[{1\over 4}]$ + z
N2⋯H6	2.72	$[{1\over 2}]$ − x, y, $[{1\over 4}]$ + z
N2⋯H1N	2.69 (4)	$[{1\over 2}]$ − x, y, $[{1\over 4}]$ + z
O1⋯H2	2.68	$[{1\over 2}]$ − x, y, $[{1\over 4}]$ + z
O1⋯H6	2.68	$[{1\over 2}]$ − x, y, $[{1\over 4}]$ + z

The overall two-dimensional fingerprint plot is shown in Fig. 6a and those delineated into O⋯H/H⋯O, H⋯H, N⋯H/H⋯N, C⋯H/H⋯C, C⋯C, C⋯O/O⋯C and S⋯H/H⋯S contacts (McKinnon et al., 2007 ) are illustrated in Fig. 6b–h, respectively; their relative contributions to the overall Hirshfeld surface are summarized in Table 3. In the fingerprint plot delineated into O⋯H/H⋯O contacts, which make the greatest contribution to the Hirshfeld surface, i.e. 36.4%, arises from the N—H⋯O hydrogen bond and is viewed as a pair of spikes with tips at d_e + d_i ∼2.1 Å in Fig. 6b. The C—H⋯O interactions, which are masked by the above interactions, appear as the groups of green points appearing in pairs in the plot. However, a forceps-like distribution of points in the fingerprint plot delineated into C⋯O/O⋯C contacts, Fig. 6g, with the tips at d_e + d_i ∼2.3 Å is indicative of C—H⋯O interactions. In the fingerprint plot corresponding to H⋯H contacts, which make the next most significant contribution to the surface, Fig. 6c, the points are scattered in the plot at (d_e, d_i) distances greater than their van der Waals separations with the comparatively low contribution, i.e. 13.6%, due to the relatively low hydrogen-atom content in the molecule. The absence of characteristic wings in the fingerprint plot delineated into C⋯H/H⋯C and the low contribution to the Hirshfeld surface, Fig. 6e and Table 3, clearly indicate the absence of C—H⋯π interactions in the crystal. However, a pair of thin edges with their ends at d_e + d_i ∼2.9 Å belong to short interatomic C⋯H contacts, Table 2. The lung-shaped distribution of points with the bending at at d_e + d_i ∼2.7 Å in the fingerprint plot corresponding to N⋯H/H⋯N contacts, Fig. 6e, with a 7.5% contribution to the Hirshfeld surface is the result of short interatomic N⋯H/H⋯N contacts, Table 2. The C⋯C contacts assigned to the short C2⋯C10 contact and π–π stacking interactions appear as the distribution of points around d_e = d_i ∼1.7 Å, Fig. 6f. The presence of π–π stacking interactions between the symmetry-related thienyl and furanyl rings is also indicated by the appearance of red and blue triangle pairs on the Hirshfeld surface mapped with the shape-index property identified with arrows in the images of Fig. 7, and in the flat region on the Hirshfeld surface mapped over curvedness in Fig. 8. Finally, although the S⋯H/H⋯S contacts in the structure of (I) make a 8.9% contribution to the surface, and also show a nearly symmetrical distribution of points in the corresponding fingerprint plot, Fig. 6h, they do not have a significant influence on the molecular packing as they are separated at distances greater than the sum of their van der Waals radii.

Table 3
Percentage contribution of the different intermolecular interactions to the Hirshfeld surface of the title compound

Contact	%
H⋯H	13.8
O⋯H/H⋯O	36.4
C⋯H/H⋯C	7.4
N⋯H/H⋯N	7.5
C⋯C	6.6
C⋯O/O⋯C	8.3
S⋯H/H⋯S	8.9
N⋯O/O⋯N	3.1
S⋯O/O⋯S	2.6
C⋯N/N⋯C	2.1
O⋯O	1.5
N⋯S/S⋯N	0.6
S⋯S	0.6
C⋯S/S⋯C	0.5
N⋯N	0.1

Figure 6
The two-dimensional fingerprint plots for (I)

, showing (a) all interactions, and delineated into (b) O⋯H/H⋯O, (c) H⋯H, (d) N⋯H/H⋯N, (e) C⋯H/H⋯C, (f) C⋯C, (g) C⋯O/H⋯O and (h) S⋯H/H⋯S interactions.

Figure 7
Two views of Hirshfeld surface mapped with shape-index property for (I)

. The pairs of red and blue regions identified with arrows indicate π–π stacking interactions.

Figure 8
A view of Hirshfeld surface mapped over curvedness for (I)

. The flat regions highlight the involvement of rings in π–π stacking interactions.

The final analysis based on the Hirshfeld surfaces is an evaluation of enrichment ratios (ER) (Jelsch et al., 2014 ); a list of the ER values is given in Table 4. The low content of hydrogen in the molecular structure of (I) yields a very low ER, 0.72, indicating no propensity to form intermolecular H⋯H contacts. The ER value of 1.55 from O⋯H/H⋯O contacts is in the expected 1.2–1.6 range and confirm their involvement in the N—H⋯O and C—H⋯O interactions. The presence of intermolecular C—H⋯O interactions is also confirmed through the ER value near to unity i.e. 0.99, corresponding to the C⋯O/O⋯C contacts. The high propensity to form π–π stacking interactions between the thienyl and furanyl rings is reflected from the high enrichment ratio 2.66 for C⋯C contacts. The ER value of 1.26 resulting from 6.75% of the surface occupied by nitrogen atoms and a 7.5% contribution to the Hirshfeld surface from N⋯H/H⋯N contacts is due to the presence of short N⋯H contacts in the structure, Table 2. The ER values < 1 related to other contacts and low % contribution to the surface indicate their low significance in the crystal.

Table 4
Enrichment ratios (ER) for the title compound

Contact	ER
H⋯H	0.72
O⋯H/H⋯O	1.55
N⋯H/H⋯N	1.26
C⋯C	2.66
C⋯O/O⋯C	0.99
C⋯H/H⋯C	0.53
S⋯O/O⋯S	0.71
N⋯O/O⋯N	0.86
S⋯H/H⋯S	0.64

5. Database survey

A search of the crystallographic literature (Groom et al., 2016 ) reveals one closely related structure, namely the species with a methyl group rather than a nitro group, N′-[(5-methyl-2-furyl)methylene]thiophene-2-carbohydrazide [(II); Jiang, 2010 ].

The relative dispositions of the heteroatoms in the two structures are the same but, the twist in (II) is significantly less as seen in the dihedral angle of 10.2 (6)° between the five-membered rings. This is highlighted in the overlay diagram in Fig. 9. The molecular structure of the all thienyl analogue of (I) has been described recently (Cardoso et al., 2016b). There are two almost identical, near planar molecules in the asymmetric unit and each adopts the conformation indicated in Scheme 2, which might be described as having the thienyl-S atoms syn. The intramolecular S⋯S separations of 3.770 (4) and 3.879 (4) Å, are beyond the sum of their van der Waals radii. The conformational differences found for the thienyl molecules is consistent with our NMR studies that indicate multiple conformations exist in solution for these compounds.

Figure 9
Overlay diagram of molecules of (I)

(red image) and (II) (blue). The molecules have been overlapped so that the five-membered rings are coincident.

6. Synthesis and crystallization

The title compound was prepared following a procedure outlined in Fig. 10. Yellow rods of (I) were grown by slow evaporation of a methanol solution held at room temperature. Yellow solid; m.p.: 528–529 K. IR ν_max (cm⁻¹; KBr disc): 1629 (C=O); 3209 (N—H). ¹H NMR (400 MHz; DMSO) δ: 12.26 (1H; NH), 8.10–7.96 (3H; m; H-4′; H-8′ and H-9′), 7.81 (1H; d; J_HH = 3.9 Hz; H-5), 7.28 (1H; d; J_HH = 3.9 Hz; H-4), 7.26-7.24 (1H; m; H-3). ¹³C NMR (100 MHz DMSO) δ: 161.6 (C=O), 157.9 (C-2), 151.6 (C-4′), 137.5 (C-5′), 135.2 (C-3), 132.7 (C-2) 131.4 (C-7′), 129.7 (C-8′), 128.2 (C-9′), 127.1 (C-9′). HRMS m/z: 288.0082 [M + Na]⁺; (calculated for [C₁₀H₇N₃O₄S+Na]⁺: 288.0055.

Figure 10
Preparation of the title compound. Reagents: i = SO₂Cl₂, MeOH; ii = N₂H₂·H₂O, EtOH; iii = 5-nitrofurancarbaldehyde, EtOH.

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 5. The C-bound H atoms were geometrically placed (C—H = 0.95 Å) and refined as riding with U_iso(H) = 1.2U_eq(C). The N-bound H atom was located from a difference map and refined with (N—H = 0.88±0.01 Å), and with U_iso(H) = 1.2U_eq(C). The slightly elongated displacement ellipsoid for the C2 atom in the thienyl ring is likely due to unresolved disorder in the ring where the second, co-planar orientation related by 180° to that modelled is present. However, this was not modelled as the maximum residual electron density peak was only 0.46 e Å⁻³, 0.61 Å from the C2 atom. It is also noted that the relevant S—C and C—C bond lengths show the expected values.

Table 5
Experimental details

Crystal data
Chemical formula	C₁₀H₇N₃O₄S
M_r	265.25
Crystal system, space group	Tetragonal, I4₁cd
Temperature (K)	100
a, c (Å)	17.4072 (16), 14.4881 (10)
V (Å³)	4390.0 (9)
Z	16
Radiation type	Mo Kα
μ (mm⁻¹)	0.31
Crystal size (mm)	0.13 × 0.03 × 0.02

Data collection
Diffractometer	Rigaku Saturn724+ (2x2 bin mode)
Absorption correction	Multi-scan (CrystalClear-SM Expert; Rigaku, 2011 )
T_min, T_max	0.543, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10325, 2292, 2081
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.113, 1.05
No. of reflections	2292
No. of parameters	166
No. of restraints	2
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.31
Absolute structure	Flack x determined using 766 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al. 2013 )
Absolute structure parameter	−0.06 (6)
Computer programs: CrystalClear-SM Expert (Rigaku, 2011), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), QMol (Gans & Shalloway, 2001 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1486459

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989016009968/hb7593sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016009968/hb7593Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016009968/hb7593Isup3.cml

checkCIF report

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell refinement: CrystalClear-SM Expert (Rigaku, 2011); data reduction: CrystalClear-SM Expert (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

N'-[(1E)-(5-Nitrofuran-2-yl)methylidene]thiophene-2-carbohydrazide top

Crystal data top

C₁₀H₇N₃O₄S	D_x = 1.605 Mg m⁻³
M_r = 265.25	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁cd	Cell parameters from 9311 reflections
a = 17.4072 (16) Å	θ = 3.3–27.5°
c = 14.4881 (10) Å	µ = 0.31 mm⁻¹
V = 4390.0 (9) Å³	T = 100 K
Z = 16	Rod, yellow
F(000) = 2176	0.13 × 0.03 × 0.02 mm

Data collection top

Rigaku Saturn724+ (2x2 bin mode) diffractometer	2292 independent reflections
Radiation source: Rotating Anode	2081 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.061
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
profile data from ω–scans	h = −22→22
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011)	k = −22→13
T_min = 0.543, T_max = 1.000	l = −15→18
10325 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters not defined?
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.066P)² + 2.8065P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.113	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.46 e Å⁻³
2292 reflections	Δρ_min = −0.31 e Å⁻³
166 parameters	Absolute structure: Flack x determined using 766 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al. 2013)
2 restraints	Absolute structure parameter: −0.06 (6)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.48085 (6)	0.10242 (6)	0.44233 (8)	0.0259 (3)
O1	0.36361 (17)	0.16769 (16)	0.56218 (18)	0.0200 (6)
O2	0.22698 (16)	0.39128 (15)	0.66600 (18)	0.0161 (6)
O3	0.25495 (19)	0.40880 (19)	0.8415 (2)	0.0265 (7)
O4	0.18400 (18)	0.51202 (19)	0.8477 (2)	0.0266 (7)
N1	0.31555 (19)	0.25578 (19)	0.4618 (2)	0.0165 (7)
H1N	0.319 (3)	0.278 (2)	0.4082 (17)	0.020*
N2	0.28004 (19)	0.29467 (19)	0.5325 (2)	0.0171 (7)
N3	0.2125 (2)	0.4568 (2)	0.8067 (2)	0.0196 (7)
C1	0.4111 (2)	0.1666 (2)	0.4094 (3)	0.0162 (8)
C2	0.4137 (2)	0.1857 (2)	0.3137 (3)	0.0206 (9)
H2	0.3797	0.2195	0.2824	0.025*
C3	0.4770 (2)	0.1443 (2)	0.2728 (3)	0.0221 (9)
H3	0.4901	0.1482	0.2093	0.027*
C4	0.5164 (3)	0.0990 (2)	0.3336 (3)	0.0251 (10)
H4	0.5595	0.0686	0.3166	0.030*
C5	0.3616 (2)	0.1960 (2)	0.4838 (3)	0.0158 (8)
C6	0.2361 (2)	0.3499 (2)	0.5074 (3)	0.0170 (8)
H6	0.2247	0.3576	0.4439	0.020*
C7	0.2040 (2)	0.4004 (2)	0.5764 (3)	0.0166 (8)
C8	0.1580 (2)	0.4633 (2)	0.5673 (3)	0.0183 (8)
H8	0.1351	0.4815	0.5120	0.022*
C9	0.1511 (2)	0.4962 (2)	0.6561 (3)	0.0181 (8)
H9	0.1228	0.5406	0.6731	0.022*
C10	0.1940 (2)	0.4502 (2)	0.7116 (3)	0.0160 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0246 (6)	0.0270 (6)	0.0260 (5)	0.0060 (4)	0.0037 (5)	0.0022 (4)
O1	0.0246 (16)	0.0207 (15)	0.0146 (14)	0.0052 (11)	0.0020 (11)	0.0039 (11)
O2	0.0182 (14)	0.0169 (14)	0.0132 (13)	0.0042 (10)	−0.0002 (11)	−0.0039 (11)
O3	0.0289 (17)	0.0334 (18)	0.0174 (15)	0.0083 (13)	−0.0045 (13)	−0.0010 (13)
O4	0.0333 (18)	0.0288 (18)	0.0179 (15)	0.0057 (14)	0.0017 (13)	−0.0096 (13)
N1	0.0219 (17)	0.0185 (17)	0.0093 (15)	0.0042 (13)	0.0034 (13)	0.0006 (13)
N2	0.0183 (17)	0.0187 (16)	0.0142 (16)	−0.0004 (13)	−0.0009 (13)	−0.0027 (13)
N3	0.0209 (17)	0.0195 (18)	0.0183 (17)	0.0003 (13)	0.0021 (14)	−0.0034 (13)
C1	0.0161 (18)	0.0135 (18)	0.0191 (19)	−0.0022 (14)	0.0016 (15)	−0.0006 (14)
C2	0.020 (2)	0.0125 (19)	0.029 (2)	−0.0047 (14)	0.0117 (17)	−0.0102 (16)
C3	0.028 (2)	0.019 (2)	0.020 (2)	0.0015 (16)	0.0085 (17)	−0.0002 (16)
C4	0.021 (2)	0.027 (2)	0.027 (2)	0.0054 (17)	0.0089 (18)	−0.0021 (18)
C5	0.0177 (19)	0.0146 (18)	0.0151 (18)	−0.0033 (14)	−0.0004 (15)	−0.0007 (14)
C6	0.0170 (19)	0.019 (2)	0.0150 (18)	0.0014 (14)	0.0004 (14)	−0.0017 (15)
C7	0.0176 (19)	0.023 (2)	0.0096 (18)	−0.0021 (15)	−0.0001 (14)	0.0016 (15)
C8	0.018 (2)	0.022 (2)	0.0153 (19)	0.0012 (14)	0.0007 (15)	0.0013 (16)
C9	0.020 (2)	0.0170 (19)	0.0176 (19)	0.0015 (15)	0.0042 (15)	0.0017 (15)
C10	0.0156 (19)	0.0174 (18)	0.0150 (18)	−0.0003 (14)	0.0021 (14)	−0.0013 (14)

Geometric parameters (Å, º) top

S1—C4	1.694 (5)	C1—C5	1.472 (5)
S1—C1	1.718 (4)	C2—C3	1.444 (6)
O1—C5	1.239 (5)	C2—H2	0.9500
O2—C10	1.349 (5)	C3—C4	1.367 (6)
O2—C7	1.367 (5)	C3—H3	0.9500
O3—N3	1.225 (5)	C4—H4	0.9500
O4—N3	1.234 (4)	C6—C7	1.443 (5)
N1—C5	1.351 (5)	C6—H6	0.9500
N1—N2	1.374 (5)	C7—C8	1.364 (6)
N1—H1N	0.870 (14)	C8—C9	1.413 (6)
N2—C6	1.281 (5)	C8—H8	0.9500
N3—C10	1.419 (5)	C9—C10	1.358 (6)
C1—C2	1.427 (6)	C9—H9	0.9500

C4—S1—C1	91.3 (2)	S1—C4—H4	123.4
C10—O2—C7	104.6 (3)	O1—C5—N1	122.6 (4)
C5—N1—N2	118.1 (3)	O1—C5—C1	121.1 (4)
C5—N1—H1N	120 (3)	N1—C5—C1	116.3 (3)
N2—N1—H1N	119 (3)	N2—C6—C7	119.4 (3)
C6—N2—N1	115.3 (3)	N2—C6—H6	120.3
O3—N3—O4	125.1 (4)	C7—C6—H6	120.3
O3—N3—C10	118.9 (3)	O2—C7—C8	110.9 (3)
O4—N3—C10	116.0 (3)	O2—C7—C6	118.3 (3)
C2—C1—C5	130.5 (4)	C8—C7—C6	130.5 (4)
C2—C1—S1	113.5 (3)	C7—C8—C9	106.7 (4)
C5—C1—S1	115.9 (3)	C7—C8—H8	126.7
C1—C2—C3	107.8 (4)	C9—C8—H8	126.7
C1—C2—H2	126.1	C10—C9—C8	104.7 (4)
C3—C2—H2	126.1	C10—C9—H9	127.6
C4—C3—C2	114.0 (4)	C8—C9—H9	127.6
C4—C3—H3	123.0	O2—C10—C9	113.1 (3)
C2—C3—H3	123.0	O2—C10—N3	116.1 (3)
C3—C4—S1	113.3 (3)	C9—C10—N3	130.7 (4)
C3—C4—H4	123.4

C5—N1—N2—C6	−178.9 (3)	C10—O2—C7—C8	−0.1 (4)
C4—S1—C1—C2	0.7 (3)	C10—O2—C7—C6	174.1 (3)
C4—S1—C1—C5	−176.2 (3)	N2—C6—C7—O2	5.4 (6)
C5—C1—C2—C3	175.6 (4)	N2—C6—C7—C8	178.2 (4)
S1—C1—C2—C3	−0.7 (4)	O2—C7—C8—C9	−0.1 (4)
C1—C2—C3—C4	0.4 (5)	C6—C7—C8—C9	−173.3 (4)
C2—C3—C4—S1	0.2 (5)	C7—C8—C9—C10	0.2 (4)
C1—S1—C4—C3	−0.5 (3)	C7—O2—C10—C9	0.2 (4)
N2—N1—C5—O1	11.6 (5)	C7—O2—C10—N3	−176.4 (3)
N2—N1—C5—C1	−167.3 (3)	C8—C9—C10—O2	−0.3 (4)
C2—C1—C5—O1	174.0 (4)	C8—C9—C10—N3	175.8 (4)
S1—C1—C5—O1	−9.8 (5)	O3—N3—C10—O2	−1.7 (5)
C2—C1—C5—N1	−7.1 (6)	O4—N3—C10—O2	178.1 (3)
S1—C1—C5—N1	169.1 (3)	O3—N3—C10—C9	−177.6 (4)
N1—N2—C6—C7	−172.1 (3)	O4—N3—C10—C9	2.1 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.87 (3)	2.05 (3)	2.882 (4)	159 (3)
C4—H4···O4ⁱⁱ	0.95	2.42	3.293 (6)	152
C8—H8···O4ⁱⁱⁱ	0.95	2.53	3.242 (5)	132

Symmetry codes: (i) −y+1/2, x, z−1/4; (ii) x+1/2, y−1/2, z−1/2; (iii) x, −y+1, z−1/2.

Summary of short interatomic contacts (Å) in the crystal of the title compound top

Contact	Distance	Symmetry operation
C2···C10	3.361 (5)	1/2 - x, 1/2 -y, -1/2 + z
C5···H2	2.89	1/2 - x, y, 1/4 + z
N2···H6	2.72	1/2 - x, y, 1/4 + z
N2···H1N	2.69 (4)	1/2 - x, y, 1/4 + z
O1···H2	2.68	1/2 - x, y, 1/4 + z
O1···H6	2.68	1/2 - x, y, 1/4 + z

Percentage contribution of the different intermolecular interactions to the Hirshfeld surface of the title compound. top

Contact	%
H···H	13.8
O···H/H···O	36.4
C···H/H···C	7.4
N···H/H···N	7.5
C···C	6.6
C···O/O···C	8.3
S···H/H···S	8.9
N···O/O···N	3.1
S···O/O···S	2.6
C···N/N···C	2.1
O···O	1.5
N···S/S···N	0.6
S···S	0.6
C···S/S···C	0.5
N···N	0.1

Enrichment ratios (ER) for the title compound top

Contact	ER
H···H	0.72
O···H/H···O	1.55
N···H/H···N	1.26
C···C	2.66
C···O/O···C	0.99
C···H/H···C	0.53
S···O/O···S	0.71
N···O/O···N	0.86
S···H/H···S	0.64

Footnotes

‡Additional correspondence author, e-mail: j.wardell@abdn.ac.uk.

Acknowledgements

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CNPq (Brazil).

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