Crystal structure of 1-(4-formyl­benzyl­idene)thio­semicarbazone

Carballo, R.; Pino-Cuevas, A.; Vázquez-López, E.M.

doi:10.1107/S1600536814017255

organic compounds

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Volume 70| Part 9| September 2014| Page o970

doi:10.1107/S1600536814017255

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Crystal structure of 1-(4-formylbenzylidene)thiosemicarbazone

Rosa Carballo,^a Arantxa Pino-Cuevas ^a and Ezequiel M. Vázquez-López ^a ^*

^aDepartamento de Química Inorgánica, Facultade de Química, Edificio de Ciencias Experimentais, Universidade de Vigo, E-36310 Vigo, Galicia, Spain
^*Correspondence e-mail: ezequiel@uvigo.es

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 15 July 2014; accepted 25 July 2014; online 6 August 2014)

The asymmetric unit of the title compound, C₉H₉N₃OS, contains two approximately planar molecules (r.m.s. deviations for 14 non-H atoms = 0.094 and 0.045 Å), with different conformations. In one of them, the C=O group is syn to the S atom and in the other it is anti. Each molecule features an intramolecular N—H⋯N hydrogen bond, which generates an S(5) ring. In the crystal, molecules are linked by N—H⋯O and N—H⋯S hydrogen bonds, generating discrete networks; the syn molecules form [010] chains and the anti molecules form (100) sheets.

Keywords: crystal structure; thiosemicarbazone; hydrogen bonds.

CCDC reference: 1016158

1. Related literature

For further synthetic details, see: Jagst et al. (2005 ). For structure–biological activity relationships in thiosemicarbazones, see: Lukmantara et al. (2013 ). For their biological properties, see: Serda et al. (2012 ).

2. Experimental

2.1. Crystal data

C₉H₉N₃OS
M_r = 207.25
Monoclinic, P 2₁ /c
a = 12.3888 (9) Å
b = 11.7972 (8) Å
c = 14.9428 (11) Å
β = 110.286 (1)°
V = 2048.5 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.51 × 0.44 × 0.33 mm

2.2. Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.693, T_max = 0.746
19018 measured reflections
4920 independent reflections
3344 reflections with I > 2σ(I)
R_int = 0.022

2.3. Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.119
S = 1.03
4920 reflections
277 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯N3A	0.84 (3)	2.32 (2)	2.630 (2)	102.0 (19)
N1A—H1NA⋯O1Aⁱ	0.84 (3)	2.41 (3)	3.190 (3)	154 (2)
N1A—H2NA⋯S1Aⁱⁱ	0.87 (3)	2.52 (3)	3.391 (2)	172 (2)
N2A—H3NA⋯S1Bⁱⁱⁱ	0.84 (2)	2.50 (2)	3.3270 (19)	166.1 (19)
N1B—H1NB⋯N3B	0.91 (3)	2.21 (3)	2.619 (3)	106 (3)
N1B—H2NB⋯O1B^iv	0.88 (3)	2.01 (3)	2.857 (3)	161 (3)
N2B—H3NB⋯S1A^v	0.84 (2)	2.58 (2)	3.409 (2)	171 (2)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+2, -z; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x, y+1, z; (v) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1016158

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814017255/hb7254sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814017255/hb7254Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814017255/hb7254Isup3.cml

checkCIF report

Chemical context top

The study of the thiosemicarbazones is interesting because they are compounds which show diverse biological properties (Serda et al., 2012) and pharmacological activities (Lukmantara et al., 2013). Also the thiosemicarbazones are of interest from a supramolecular point of view since they can be functionalized to give different supramolecular arrays by hydrogen bonds.

Structural commentary top

We report here the synthesis and structural characterization of (4-formylbenzylidine)-thiosemicarbazone (Fig.1). The two molecules in the asymmetric unit are structurally different due to the different orientation of the carbonyl group respect to the thiosemicarbazone chain. The thiosemicarbazone moiety in both molecules shows an E conformation with the sulfur atom trans to the iminic nitrogen N3 atom. The molecules labeled as B are linked into lineal chains by N—H···O hydrogen bonds with a d(N···O) of 2.857 (3) Å but the molecules labeled as A use the same kind of hydrogen bond with a longer d(N···O) of 3.190 (3) Å to form helical chains (Fig. 2). The two types of chains are packed by N—H···S hydrogen bonds with d(N—S) in the range 3.32-3.41 Å and (NHS) angles close to linearity (between 166 and 172°).

Synthesis and crystallization top

A solution of thiosemicarbazide (342mg, 3.72 mmol) in 50 ml of water was slowly added at 50°C to a solution of terephthaldicarboxaldehyde (500 mg, 3.73 mmol) in 100 ml water. Then the mixture was stirred at 50°C for 30 mins. Once cooled to room temperature, the yellow solid was filtered off and vacuum dried. Yellow prisms were obtained by recrystallization from EtOH/H₂O (1:1) solution. Yield: 78%. M.pt: 212–214°C. IR data (KBr, cm^-1): 3452w, 3328m, 3152m ν(NH); 2974w, 2863w ν(C—H aldehyde); 1686s ν(C=O); 1533s, 1281m ν(C=N), 830m, 793m ν(C=S). ¹H NMR data (DMSO-d₆, ppm): 10.60 (s, 1H, N(2)—H); 10.01 (s, 1H, C(1)—H); 8.32 (s, 1H, N(2)—H); 8.15 (s, 1H, N(2)—H); 8.09 (s, 1H, C(8)—H); 8.02 (d, 2H, J = 8.2 Hz, C(3,7)-H); 7.91 (d, 2H, J = 8.2 Hz, C(4,6)-H).

Related literature top

For further synthetic details, see: Jagst et al. (2005). For structure–biological activity relationships in thiosemicarbazones, see: Lukmantara et al. (2013). For their biological properties, see: Serda et al. (2012).

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. ORTEP view of the two molecules of the title compound. Displacement ellipsoids shown at the 50% probability level.
	Fig. 2. View of the crystal packing showing the two different chains.

1-(4-Formylbenzylidene)thiosemicarbazone top

Crystal data top

C₉H₉N₃OS	F(000) = 864
M_r = 207.25	D_x = 1.344 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.3888 (9) Å	Cell parameters from 6097 reflections
b = 11.7972 (8) Å	θ = 2.3–27.2°
c = 14.9428 (11) Å	µ = 0.29 mm⁻¹
β = 110.286 (1)°	T = 293 K
V = 2048.5 (3) Å³	Prism, yellow
Z = 8	0.51 × 0.44 × 0.33 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	3344 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	R_int = 0.022
ϕ and ω scans	θ_max = 28.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
T_min = 0.693, T_max = 0.746	k = −15→15
19018 measured reflections	l = −19→19
4920 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0442P)² + 0.8755P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
4920 reflections	Δρ_max = 0.36 e Å⁻³
277 parameters	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₉H₉N₃OS	V = 2048.5 (3) Å³
M_r = 207.25	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.3888 (9) Å	µ = 0.29 mm⁻¹
b = 11.7972 (8) Å	T = 293 K
c = 14.9428 (11) Å	0.51 × 0.44 × 0.33 mm
β = 110.286 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	4920 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3344 reflections with I > 2σ(I)
T_min = 0.693, T_max = 0.746	R_int = 0.022
19018 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.36 e Å⁻³
4920 reflections	Δρ_min = −0.35 e Å⁻³
277 parameters

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N3A	0.89210 (14)	0.63007 (12)	−0.01356 (11)	0.0479 (4)
S1A	0.90693 (5)	0.91696 (4)	−0.13892 (4)	0.06120 (17)
O1A	0.89088 (17)	0.16790 (14)	0.29083 (12)	0.0778 (5)
N1A	0.97843 (19)	0.83357 (16)	0.03697 (14)	0.0646 (5)
C1A	0.92577 (17)	0.81529 (15)	−0.05446 (14)	0.0488 (4)
N2A	0.88481 (15)	0.71091 (13)	−0.08158 (13)	0.0519 (4)
C2A	0.84890 (17)	0.53375 (15)	−0.04474 (14)	0.0499 (4)
H2A	0.8172	0.5214	−0.1102	0.060*
C3A	0.84875 (16)	0.44243 (14)	0.02136 (13)	0.0446 (4)
C4A	0.80002 (18)	0.33905 (16)	−0.01569 (14)	0.0536 (5)
H4A	0.7659	0.3300	−0.0813	0.064*
C5A	0.80199 (18)	0.24931 (15)	0.04467 (14)	0.0549 (5)
H5A	0.7691	0.1803	0.0195	0.066*
C6A	0.85265 (17)	0.26217 (15)	0.14207 (14)	0.0487 (4)
C7A	0.9008 (2)	0.36573 (16)	0.17931 (14)	0.0576 (5)
H7A	0.9348	0.3746	0.2450	0.069*
C8A	0.89848 (19)	0.45524 (16)	0.11987 (14)	0.0550 (5)
H8A	0.9302	0.5245	0.1455	0.066*
C9A	0.8559 (2)	0.16499 (18)	0.20519 (17)	0.0615 (5)
H9A	0.8286	0.0959	0.1763	0.074*
H1NA	0.990 (2)	0.782 (2)	0.0779 (17)	0.069 (7)*
H2NA	1.007 (2)	0.900 (2)	0.0570 (17)	0.075 (7)*
H3NA	0.8488 (18)	0.6956 (18)	−0.1392 (16)	0.054 (6)*
S1B	0.70719 (7)	0.87078 (5)	0.20508 (5)	0.0836 (2)
O1B	0.36864 (17)	−0.02352 (14)	0.06781 (17)	0.1027 (7)
N1B	0.5055 (2)	0.77556 (19)	0.11523 (17)	0.0728 (6)
C1B	0.6141 (2)	0.76241 (17)	0.16872 (15)	0.0633 (6)
N2B	0.6506 (2)	0.65472 (15)	0.19199 (15)	0.0659 (5)
C2B	0.61285 (19)	0.46749 (17)	0.18659 (16)	0.0596 (5)
H2B	0.6866	0.4587	0.2310	0.072*
N3B	0.57577 (16)	0.56654 (14)	0.15795 (13)	0.0591 (4)
C3B	0.54146 (18)	0.36782 (16)	0.15082 (15)	0.0539 (5)
C4B	0.5824 (2)	0.26093 (18)	0.18761 (17)	0.0636 (6)
H4B	0.6538	0.2549	0.2358	0.076*
C5B	0.5189 (2)	0.16464 (18)	0.15366 (18)	0.0663 (6)
H5B	0.5477	0.0941	0.1784	0.080*
C6B	0.41212 (19)	0.17280 (17)	0.08275 (16)	0.0574 (5)
C7B	0.37016 (19)	0.27858 (17)	0.04567 (16)	0.0592 (5)
H6B	0.2983	0.2843	−0.0020	0.071*
C8B	0.43420 (19)	0.37484 (17)	0.07894 (16)	0.0583 (5)
H7B	0.4056	0.4451	0.0532	0.070*
C9B	0.3412 (2)	0.07213 (19)	0.0444 (2)	0.0723 (6)
H9B	0.2691	0.0838	−0.0017	0.087*
H1NB	0.463 (3)	0.712 (3)	0.093 (2)	0.107 (10)*
H2NB	0.478 (2)	0.844 (2)	0.1003 (19)	0.085 (8)*
H3NB	0.717 (2)	0.642 (2)	0.2304 (17)	0.065 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N3A	0.0572 (9)	0.0343 (7)	0.0505 (8)	0.0015 (7)	0.0167 (7)	0.0081 (6)
S1A	0.0797 (4)	0.0362 (2)	0.0594 (3)	−0.0022 (2)	0.0134 (3)	0.0123 (2)
O1A	0.1133 (14)	0.0633 (10)	0.0600 (10)	0.0069 (9)	0.0341 (9)	0.0169 (8)
N1A	0.0936 (15)	0.0363 (9)	0.0541 (10)	−0.0053 (9)	0.0130 (10)	0.0050 (8)
C1A	0.0554 (11)	0.0351 (9)	0.0545 (11)	0.0034 (8)	0.0174 (9)	0.0043 (8)
N2A	0.0682 (11)	0.0343 (7)	0.0479 (9)	−0.0020 (7)	0.0135 (8)	0.0067 (7)
C2A	0.0602 (11)	0.0375 (9)	0.0477 (10)	−0.0014 (8)	0.0131 (8)	0.0043 (8)
C3A	0.0498 (10)	0.0347 (8)	0.0480 (10)	0.0006 (7)	0.0151 (8)	0.0032 (7)
C4A	0.0647 (12)	0.0430 (9)	0.0447 (10)	−0.0084 (9)	0.0082 (9)	0.0010 (8)
C5A	0.0638 (12)	0.0367 (9)	0.0586 (12)	−0.0116 (8)	0.0141 (10)	−0.0017 (8)
C6A	0.0576 (11)	0.0383 (9)	0.0507 (10)	−0.0004 (8)	0.0193 (9)	0.0057 (8)
C7A	0.0817 (15)	0.0445 (10)	0.0439 (10)	−0.0040 (10)	0.0183 (10)	−0.0002 (8)
C8A	0.0774 (14)	0.0351 (9)	0.0498 (10)	−0.0068 (9)	0.0187 (10)	−0.0045 (8)
C9A	0.0775 (15)	0.0449 (10)	0.0641 (13)	−0.0005 (10)	0.0271 (11)	0.0082 (9)
S1B	0.1164 (6)	0.0470 (3)	0.0657 (4)	−0.0135 (3)	0.0042 (3)	0.0020 (3)
O1B	0.0916 (13)	0.0436 (9)	0.158 (2)	−0.0036 (9)	0.0239 (13)	−0.0026 (11)
N1B	0.0818 (15)	0.0507 (11)	0.0826 (14)	0.0090 (11)	0.0243 (12)	0.0030 (11)
C1B	0.0916 (17)	0.0453 (11)	0.0517 (11)	0.0007 (11)	0.0233 (11)	−0.0012 (9)
N2B	0.0739 (13)	0.0445 (9)	0.0669 (12)	−0.0017 (9)	0.0088 (10)	−0.0003 (8)
C2B	0.0632 (13)	0.0471 (11)	0.0647 (13)	0.0019 (10)	0.0172 (10)	0.0008 (9)
N3B	0.0685 (11)	0.0429 (9)	0.0635 (10)	−0.0031 (8)	0.0199 (9)	−0.0036 (8)
C3B	0.0603 (12)	0.0434 (10)	0.0616 (12)	0.0037 (9)	0.0259 (10)	−0.0003 (9)
C4B	0.0605 (13)	0.0517 (11)	0.0738 (14)	0.0066 (10)	0.0172 (11)	0.0103 (10)
C5B	0.0705 (15)	0.0419 (10)	0.0884 (16)	0.0083 (10)	0.0299 (13)	0.0111 (10)
C6B	0.0607 (13)	0.0434 (10)	0.0742 (14)	0.0031 (9)	0.0312 (11)	−0.0022 (9)
C7B	0.0583 (12)	0.0483 (11)	0.0697 (13)	0.0068 (9)	0.0207 (10)	−0.0036 (10)
C8B	0.0650 (13)	0.0423 (10)	0.0672 (13)	0.0103 (9)	0.0225 (11)	0.0015 (9)
C9B	0.0709 (15)	0.0517 (12)	0.0965 (18)	−0.0014 (11)	0.0320 (13)	−0.0068 (12)

Geometric parameters (Å, º) top

N3A—C2A	1.274 (2)	S1B—C1B	1.681 (2)
N3A—N2A	1.374 (2)	O1B—C9B	1.195 (3)
S1A—C1A	1.6976 (18)	N1B—C1B	1.314 (3)
O1A—C9A	1.201 (3)	N1B—H1NB	0.91 (3)
N1A—C1A	1.312 (3)	N1B—H2NB	0.88 (3)
N1A—H1NA	0.84 (3)	C1B—N2B	1.353 (3)
N1A—H2NA	0.87 (3)	N2B—N3B	1.369 (2)
C1A—N2A	1.340 (2)	N2B—H3NB	0.84 (2)
N2A—H3NA	0.84 (2)	C2B—N3B	1.274 (3)
C2A—C3A	1.462 (2)	C2B—C3B	1.457 (3)
C2A—H2A	0.9300	C2B—H2B	0.9300
C3A—C4A	1.388 (2)	C3B—C8B	1.392 (3)
C3A—C8A	1.393 (3)	C3B—C4B	1.399 (3)
C4A—C5A	1.386 (3)	C4B—C5B	1.375 (3)
C4A—H4A	0.9300	C4B—H4B	0.9300
C5A—C6A	1.379 (3)	C5B—C6B	1.382 (3)
C5A—H5A	0.9300	C5B—H5B	0.9300
C6A—C7A	1.388 (3)	C6B—C7B	1.391 (3)
C6A—C9A	1.476 (3)	C6B—C9B	1.470 (3)
C7A—C8A	1.374 (3)	C7B—C8B	1.376 (3)
C7A—H7A	0.9300	C7B—H6B	0.9300
C8A—H8A	0.9300	C8B—H7B	0.9300
C9A—H9A	0.9300	C9B—H9B	0.9300

C2A—N3A—N2A	115.92 (16)	C1B—N1B—H1NB	118 (2)
C1A—N1A—H1NA	122.5 (16)	C1B—N1B—H2NB	119.2 (18)
C1A—N1A—H2NA	120.1 (16)	H1NB—N1B—H2NB	122 (3)
H1NA—N1A—H2NA	117 (2)	N1B—C1B—N2B	116.6 (2)
N1A—C1A—N2A	117.74 (17)	N1B—C1B—S1B	123.36 (18)
N1A—C1A—S1A	123.28 (15)	N2B—C1B—S1B	120.0 (2)
N2A—C1A—S1A	118.98 (15)	C1B—N2B—N3B	119.7 (2)
C1A—N2A—N3A	119.56 (17)	C1B—N2B—H3NB	120.4 (17)
C1A—N2A—H3NA	121.2 (15)	N3B—N2B—H3NB	119.7 (16)
N3A—N2A—H3NA	119.0 (15)	N3B—C2B—C3B	121.0 (2)
N3A—C2A—C3A	120.60 (17)	N3B—C2B—H2B	119.5
N3A—C2A—H2A	119.7	C3B—C2B—H2B	119.5
C3A—C2A—H2A	119.7	C2B—N3B—N2B	116.96 (19)
C4A—C3A—C8A	119.25 (16)	C8B—C3B—C4B	118.45 (19)
C4A—C3A—C2A	118.70 (17)	C8B—C3B—C2B	122.07 (18)
C8A—C3A—C2A	122.03 (16)	C4B—C3B—C2B	119.5 (2)
C5A—C4A—C3A	120.31 (17)	C5B—C4B—C3B	121.1 (2)
C5A—C4A—H4A	119.8	C5B—C4B—H4B	119.5
C3A—C4A—H4A	119.8	C3B—C4B—H4B	119.5
C6A—C5A—C4A	120.11 (17)	C4B—C5B—C6B	119.92 (19)
C6A—C5A—H5A	119.9	C4B—C5B—H5B	120.0
C4A—C5A—H5A	119.9	C6B—C5B—H5B	120.0
C5A—C6A—C7A	119.67 (17)	C5B—C6B—C7B	119.61 (19)
C5A—C6A—C9A	119.37 (17)	C5B—C6B—C9B	121.8 (2)
C7A—C6A—C9A	120.96 (18)	C7B—C6B—C9B	118.6 (2)
C8A—C7A—C6A	120.50 (18)	C8B—C7B—C6B	120.5 (2)
C8A—C7A—H7A	119.8	C8B—C7B—H6B	119.7
C6A—C7A—H7A	119.8	C6B—C7B—H6B	119.7
C7A—C8A—C3A	120.15 (17)	C7B—C8B—C3B	120.43 (19)
C7A—C8A—H8A	119.9	C7B—C8B—H7B	119.8
C3A—C8A—H8A	119.9	C3B—C8B—H7B	119.8
O1A—C9A—C6A	125.3 (2)	O1B—C9B—C6B	125.3 (3)
O1A—C9A—H9A	117.3	O1B—C9B—H9B	117.4
C6A—C9A—H9A	117.3	C6B—C9B—H9B	117.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···N3A	0.84 (3)	2.32 (2)	2.630 (2)	102.0 (19)
N1A—H1NA···O1Aⁱ	0.84 (3)	2.41 (3)	3.190 (3)	154 (2)
N1A—H2NA···S1Aⁱⁱ	0.87 (3)	2.52 (3)	3.391 (2)	172 (2)
N2A—H3NA···S1Bⁱⁱⁱ	0.84 (2)	2.50 (2)	3.3270 (19)	166.1 (19)
N1B—H1NB···N3B	0.91 (3)	2.21 (3)	2.619 (3)	106 (3)
N1B—H2NB···O1B^iv	0.88 (3)	2.01 (3)	2.857 (3)	161 (3)
N2B—H3NB···S1A^v	0.84 (2)	2.58 (2)	3.409 (2)	171 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···N3A	0.84 (3)	2.32 (2)	2.630 (2)	102.0 (19)
N1A—H1NA···O1Aⁱ	0.84 (3)	2.41 (3)	3.190 (3)	154 (2)
N1A—H2NA···S1Aⁱⁱ	0.87 (3)	2.52 (3)	3.391 (2)	172 (2)
N2A—H3NA···S1Bⁱⁱⁱ	0.84 (2)	2.50 (2)	3.3270 (19)	166.1 (19)
N1B—H1NB···N3B	0.91 (3)	2.21 (3)	2.619 (3)	106 (3)
N1B—H2NB···O1B^iv	0.88 (3)	2.01 (3)	2.857 (3)	161 (3)
N2B—H3NB···S1A^v	0.84 (2)	2.58 (2)	3.409 (2)	171 (2)

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

Acknowledgements

This research was supported by the European Rural Development Fund and the Spanish Ministry of Education and Science through project CTQ2010–19386/BQU.

References

Bruker (2008). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jagst, A., Sánchez, A., Vázquez-López, E. M. & Abram, U. (2005). Inorg. Chem. 44, 5738–5744. Web of Science CSD CrossRef PubMed CAS Google Scholar
Lukmantara, A. Y., Kalinowski, D. S., Kumar, N. & Richardson, D. R. (2013). Bioorg. Med. Chem. Lett. 23, 967–974. Web of Science CSD CrossRef CAS PubMed Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Serda, M., Mrozek-Wilczkiewicz, A., Jampilek, J., Pesko, M., Kralova, K., Vejsova, M., Musiol, R., Ratuszna, A. & Polanski, J. (2012). Molecules, 17, 13483–13502. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar