Crystal structure of 3-({[(thio-phen-2-yl)methyl-idene]hydrazin-yl}carbon-yl)pyridinium chloride dihydrate.

In the title compound, C11H10N3OS(+)·Cl(-)·2H2O, the organic cation exhibits a dihedral angle of 21.26 (8)° between the mean planes of the pyridine and thio-phene rings, and dihedral angles of 15.11 (9) and 6.49 (9)° between the mean planes of the hydrazide moiety and the pyridine and thio-phene rings, respectively. In the crystal, the organic cation, the chloride counter-anion and the two water mol-ecules of crystallization are linked through an intricate hydrogen-bonding network consisting of O-H⋯O, O-H⋯N, N-H⋯Cl, C-H⋯Cl, C-H⋯O, N-H⋯O, O-H⋯Cl and C-H⋯S inter-actions that consolidate a three-dimensional network.

Related literature

For structures of related hydrazone derivatives, see: Cheng et al. (2008 ▶); Jing et al. (2007 ▶); Novina et al. (2013 ▶, 2014 ▶). For the biological activity of hydrazones, see: Babahan et al. (2013 ▶); Kaplancikli et al. (2012 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C11H10N3OS+·Cl−·2H2O

M = 303.76

Triclinic,

a = 7.8781 (7) Å

b = 8.6928 (7) Å

c = 11.0999 (10) Å

α = 67.361 (4)°

β = 78.210 (4)°

γ = 77.119 (4)°

V = 677.97 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.44 mm−1

T = 296 K

0.35 × 0.30 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.860, T max = 0.879

5444 measured reflections

3222 independent reflections

2761 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.119

S = 1.05

3222 reflections

192 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.40 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814017565/wm5042sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017565/wm5042Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814017565/wm5042Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814017565/wm5042fig1.tif

The mol­ecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

a et al. . DOI: 10.1107/S1600536814017565/wm5042fig2.tif

The crystal packing of the title compound viewed along the a axis. Hydrogen bonds are shown as dashed lines. (10), (10), (6), (7), (8) (7) and (10) ring motifs (Bernstein et al., 1995) are observed in the packing.

CCDC reference: 1017163

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

C11H10N3OS+·Cl−·2H2O	Z = 2
Mr = 303.76	F(000) = 316
Triclinic, P1	Dx = 1.488 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8781 (7) Å	Cell parameters from 3509 reflections
b = 8.6928 (7) Å	θ = 2.6–28.0°
c = 11.0999 (10) Å	µ = 0.44 mm−1
α = 67.361 (4)°	T = 296 K
β = 78.210 (4)°	Block, pale yellow
γ = 77.119 (4)°	0.35 × 0.30 × 0.30 mm
V = 677.97 (10) Å3

Bruker APEXII CCD diffractometer	3222 independent reflections
Radiation source: fine-focus sealed tube	2761 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω and φ scan	θmax = 28.2°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −9→10
Tmin = 0.860, Tmax = 0.879	k = −7→11
5444 measured reflections	l = −14→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.076P)2 + 0.1235P] where P = (Fo2 + 2Fc2)/3
3222 reflections	(Δ/σ)max = 0.001
192 parameters	Δρmax = 0.32 e Å−3
6 restraints	Δρmin = −0.40 e Å−3

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
S1	0.17836 (6)	0.47295 (5)	0.80609 (4)	0.04223 (14)
Cl	0.17151 (7)	0.25503 (5)	1.42848 (4)	0.05065 (16)
O1	0.38027 (16)	0.80909 (14)	1.00852 (10)	0.0399 (3)
O1W	0.3488 (2)	0.82526 (19)	0.75281 (13)	0.0514 (3)
N2	0.31200 (17)	0.55367 (15)	1.14192 (12)	0.0315 (3)
N3	0.27791 (16)	0.52406 (15)	1.03627 (12)	0.0306 (3)
O2W	0.0187 (2)	0.9549 (2)	0.67510 (14)	0.0640 (4)
N1	0.47813 (17)	0.91856 (17)	1.31029 (13)	0.0367 (3)
H1N1	0.5298	1.0037	1.2922	0.044*
C9	0.1401 (2)	0.18261 (19)	0.98202 (16)	0.0367 (3)
H9	0.1335	0.0925	1.0618	0.044*
C4	0.37426 (18)	0.74005 (17)	1.23659 (14)	0.0287 (3)
C6	0.35574 (18)	0.70370 (17)	1.11885 (13)	0.0284 (3)
C5	0.4561 (2)	0.87569 (19)	1.21193 (15)	0.0329 (3)
H5	0.4964	0.9381	1.1257	0.040*
C7	0.23292 (19)	0.38064 (18)	1.06447 (14)	0.0318 (3)
H7	0.2300	0.3041	1.1506	0.038*
C8	0.18671 (19)	0.33584 (18)	0.96480 (14)	0.0306 (3)
C11	0.1187 (2)	0.3284 (3)	0.76111 (18)	0.0471 (4)
H11	0.0986	0.3481	0.6763	0.057*
C10	0.1041 (2)	0.1815 (2)	0.86327 (19)	0.0466 (4)
H10	0.0732	0.0886	0.8558	0.056*
C3	0.3133 (3)	0.6516 (2)	1.36593 (16)	0.0471 (4)
H3	0.2565	0.5600	1.3860	0.056*
C2	0.3378 (3)	0.7008 (3)	1.46513 (17)	0.0610 (6)
H2	0.2962	0.6429	1.5522	0.073*
C1	0.4229 (3)	0.8340 (2)	1.43523 (17)	0.0481 (4)
H1	0.4421	0.8655	1.5019	0.058*
H2N2	0.298 (3)	0.482 (3)	1.218 (2)	0.057 (6)*
H1O1	0.337 (4)	0.778 (3)	0.8380 (17)	0.086 (9)*
H2O2	−0.019 (4)	0.898 (3)	0.644 (3)	0.093 (10)*
H1O2	0.047 (3)	1.041 (3)	0.610 (2)	0.078 (8)*
H2O1	0.243 (2)	0.854 (3)	0.734 (3)	0.079 (9)*

	U11	U22	U33	U12	U13	U23
S1	0.0576 (3)	0.0397 (2)	0.0315 (2)	−0.01844 (18)	−0.00473 (17)	−0.00956 (16)
Cl	0.0716 (3)	0.0443 (3)	0.0392 (2)	−0.0295 (2)	−0.0095 (2)	−0.00611 (18)
O1	0.0609 (7)	0.0349 (5)	0.0264 (5)	−0.0208 (5)	−0.0068 (5)	−0.0060 (4)
O1W	0.0708 (9)	0.0549 (8)	0.0352 (7)	−0.0351 (7)	−0.0011 (6)	−0.0127 (6)
N2	0.0442 (7)	0.0286 (6)	0.0247 (6)	−0.0124 (5)	−0.0048 (5)	−0.0091 (5)
N3	0.0361 (6)	0.0319 (6)	0.0282 (6)	−0.0097 (5)	−0.0034 (5)	−0.0135 (5)
O2W	0.0985 (12)	0.0610 (9)	0.0386 (7)	−0.0414 (8)	−0.0182 (7)	−0.0039 (6)
N1	0.0451 (7)	0.0370 (7)	0.0360 (7)	−0.0189 (6)	−0.0028 (5)	−0.0161 (5)
C9	0.0448 (8)	0.0295 (7)	0.0375 (8)	−0.0108 (6)	−0.0059 (6)	−0.0108 (6)
C4	0.0331 (7)	0.0275 (6)	0.0272 (7)	−0.0086 (5)	−0.0032 (5)	−0.0099 (5)
C6	0.0307 (7)	0.0284 (6)	0.0276 (7)	−0.0080 (5)	−0.0033 (5)	−0.0099 (5)
C5	0.0384 (7)	0.0332 (7)	0.0294 (7)	−0.0140 (6)	−0.0017 (5)	−0.0104 (6)
C7	0.0377 (7)	0.0298 (7)	0.0293 (7)	−0.0087 (5)	−0.0032 (5)	−0.0107 (5)
C8	0.0342 (7)	0.0297 (7)	0.0306 (7)	−0.0096 (5)	−0.0021 (5)	−0.0125 (5)
C11	0.0487 (9)	0.0635 (11)	0.0410 (9)	−0.0144 (8)	−0.0078 (7)	−0.0276 (8)
C10	0.0490 (9)	0.0458 (9)	0.0606 (11)	−0.0173 (7)	−0.0065 (8)	−0.0307 (8)
C3	0.0756 (13)	0.0421 (9)	0.0295 (8)	−0.0334 (9)	0.0031 (7)	−0.0111 (7)
C2	0.1039 (17)	0.0616 (12)	0.0248 (8)	−0.0459 (12)	0.0060 (9)	−0.0126 (8)
C1	0.0703 (12)	0.0516 (10)	0.0336 (8)	−0.0218 (9)	−0.0054 (8)	−0.0214 (7)

S1—C11	1.6999 (18)	C9—C10	1.408 (2)
S1—C8	1.7101 (15)	C9—H9	0.9300
Cl—Cl	0.0000 (12)	C4—C5	1.3780 (19)
O1—C6	1.2226 (17)	C4—C3	1.384 (2)
O1W—H1O1	0.868 (17)	C4—C6	1.4985 (19)
O1W—H2O1	0.857 (16)	C5—H5	0.9300
N2—C6	1.3389 (18)	C7—C8	1.438 (2)
N2—N3	1.3804 (17)	C7—H7	0.9300
N2—H2N2	0.83 (2)	C11—C10	1.352 (3)
N3—C7	1.2764 (18)	C11—H11	0.9300
O2W—H2O2	0.837 (17)	C10—H10	0.9300
O2W—H1O2	0.851 (16)	C3—C2	1.386 (2)
N1—C1	1.328 (2)	C3—H3	0.9300
N1—C5	1.3344 (19)	C2—C1	1.364 (3)
N1—H1N1	0.8600	C2—H2	0.9300
C9—C8	1.393 (2)	C1—H1	0.9300
C11—S1—C8	92.07 (8)	N3—C7—C8	120.85 (13)
H1O1—O1W—H2O1	104 (2)	N3—C7—H7	119.6
C6—N2—N3	117.65 (12)	C8—C7—H7	119.6
C6—N2—H2N2	122.4 (16)	C9—C8—C7	126.41 (14)
N3—N2—H2N2	119.8 (16)	C9—C8—S1	111.11 (11)
C7—N3—N2	114.96 (12)	C7—C8—S1	122.47 (11)
H2O2—O2W—H1O2	106 (2)	C10—C11—S1	111.95 (13)
C1—N1—C5	122.12 (13)	C10—C11—H11	124.0
C1—N1—H1N1	118.9	S1—C11—H11	124.0
C5—N1—H1N1	118.9	C11—C10—C9	113.50 (15)
C8—C9—C10	111.34 (14)	C11—C10—H10	123.2
C8—C9—H9	124.3	C9—C10—H10	123.2
C10—C9—H9	124.3	C4—C3—C2	119.31 (15)
C5—C4—C3	118.07 (14)	C4—C3—H3	120.3
C5—C4—C6	116.35 (12)	C2—C3—H3	120.3
C3—C4—C6	125.57 (13)	C1—C2—C3	120.10 (16)
O1—C6—N2	123.36 (13)	C1—C2—H2	120.0
O1—C6—C4	119.87 (12)	C3—C2—H2	120.0
N2—C6—C4	116.77 (12)	N1—C1—C2	119.56 (15)
N1—C5—C4	120.82 (13)	N1—C1—H1	120.2
N1—C5—H5	119.6	C2—C1—H1	120.2
C4—C5—H5	119.6

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1Wi	0.86	1.80	2.659 (2)	176
N2—H2N2···Cl	0.84 (2)	2.59 (2)	3.4011 (14)	163 (2)
O1W—H1O1···O1	0.87 (2)	2.11 (2)	2.8465 (18)	142 (2)
O1W—H1O1···N3	0.87 (2)	2.50 (2)	3.2648 (19)	148 (2)
O2W—H2O2···Clii	0.83 (3)	2.41 (3)	3.2305 (18)	171 (3)
O2W—H1O2···Cliii	0.85 (2)	2.37 (2)	3.2102 (16)	171 (2)
O1W—H2O1···O2W	0.86 (2)	1.91 (2)	2.764 (2)	170 (3)
C2—H2···S1iv	0.93	2.71	3.6359 (19)	179
C3—H3···Cl	0.93	2.72	3.629 (2)	166
C5—H5···O1i	0.93	2.41	3.207 (2)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1W i	0.86	1.80	2.659 (2)	176
N2—H2N2⋯Cl	0.84 (2)	2.59 (2)	3.4011 (14)	163 (2)
O1W—H1O1⋯O1	0.87 (2)	2.11 (2)	2.8465 (18)	142 (2)
O1W—H1O1⋯N3	0.87 (2)	2.50 (2)	3.2648 (19)	148 (2)
O2W—H2O2⋯Clii	0.83 (3)	2.41 (3)	3.2305 (18)	171 (3)
O2W—H1O2⋯Cliii	0.85 (2)	2.37 (2)	3.2102 (16)	171 (2)
O1W—H2O1⋯O2W	0.86 (2)	1.91 (2)	2.764 (2)	170 (3)
C2—H2⋯S1iv	0.93	2.71	3.6359 (19)	179
C3—H3⋯Cl	0.93	2.72	3.629 (2)	166
C5—H5⋯O1i	0.93	2.41	3.207 (2)	143

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