Crystal structure of (E)-3-{[2-(2,4-di-chloro-benzyl-idene)hydrazin-1-yl]carbon-yl}pyridinium chloride trihydrate.

In the title hydrated salt, C13H10Cl2N3O(+)·Cl(-)·3H2O, the organic cation exhibits a dihedral angle of 8.26 (14)° between the mean planes of the pyridinium and benzene rings, and dihedral angles of 8.70 (15) and 15.93 (5)° between the mean planes of the hydrazide group and the benzene and pyridinium rings, respectively. In the crystal, N-H⋯O, N-H⋯Cl, C-H⋯O, C-H⋯Cl, O-H⋯O, O-H⋯N and O-H⋯Cl hydrogen bonds link the complex cations, chloride anions and solvent water mol-ecules into a three-dimensional network.

Related literature

For the biological activity of hydrazones, see: Kaplancikli et al. (2012 ▸); Babahan et al. (2013 ▸). For related structures, see: Novina et al. (2013 ▸, 2014 ▸).

Experimental

Crystal data

C13H10Cl2N3O+·Cl−·3H2O

M = 384.64

Triclinic,

a = 8.4631 (4) Å

b = 9.5968 (5) Å

c = 10.8300 (6) Å

α = 76.604 (2)°

β = 89.155 (2)°

γ = 83.195 (2)°

V = 849.56 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.56 mm−1

T = 293 K

0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T min = 0.875, T max = 0.908

6548 measured reflections

4037 independent reflections

3007 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.124

S = 1.04

4037 reflections

234 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.37 e Å−3

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: APEX2 and SAINT (Bruker, 2008 ▸); data reduction: SAINT and XPREP (Bruker, 2008 ▸); 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 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015000286/bq2398sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015000286/bq2398Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015000286/bq2398Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015000286/bq2398fig1.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 . DOI: 10.1107/S2056989015000286/bq2398fig2.tif

Crystal packing of the title compound viewed along the a axis. Hydrogen bonds are shown as dashed lines.

Click here for additional data file.

− . DOI: 10.1107/S2056989015000286/bq2398fig3.tif

Part of the crystal packing of the title compound, showing the formation of (10) motif. The Cl− and the water mol­ecules are omitted for the sake of clarity.

CCDC reference: 1028701

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

C13H10Cl2N3O+·Cl−·3H2O	Z = 2
Mr = 384.64	F(000) = 396
Triclinic, P1	Dx = 1.504 Mg m−3
a = 8.4631 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5968 (5) Å	Cell parameters from 6548 reflections
c = 10.8300 (6) Å	θ = 1.0–28.2°
α = 76.604 (2)°	µ = 0.56 mm−1
β = 89.155 (2)°	T = 293 K
γ = 83.195 (2)°	Block, colorless
V = 849.56 (8) Å3	0.35 × 0.30 × 0.25 mm

Bruker Kappa APEXII CCD diffractometer	4037 independent reflections
Radiation source: fine-focus sealed tube	3007 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω and φ scan	θmax = 28.2°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
Tmin = 0.875, Tmax = 0.908	k = −9→12
6548 measured reflections	l = −8→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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0621P)2 + 0.184P] where P = (Fo2 + 2Fc2)/3
4037 reflections	(Δ/σ)max < 0.001
234 parameters	Δρmax = 0.28 e Å−3
8 restraints	Δρmin = −0.37 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
Cl1	0.52954 (7)	−0.24772 (6)	0.38718 (6)	0.04957 (17)
Cl3	0.72649 (9)	−0.56838 (6)	0.84324 (7)	0.0656 (2)
O1	0.8879 (2)	0.32962 (16)	0.49886 (15)	0.0485 (4)
N1	0.8808 (2)	0.69456 (19)	0.21816 (19)	0.0445 (4)
N2	0.7666 (2)	0.21144 (17)	0.37617 (17)	0.0372 (4)
N3	0.7793 (2)	0.08783 (17)	0.47208 (16)	0.0367 (4)
C1	0.8932 (2)	0.5703 (2)	0.3054 (2)	0.0386 (5)
H1	0.9622	0.5563	0.3744	0.046*
C2	0.7810 (3)	0.7223 (2)	0.1195 (2)	0.0491 (6)
H2	0.7734	0.8112	0.0617	0.059*
C3	0.6892 (3)	0.6188 (3)	0.1031 (2)	0.0501 (6)
H3	0.6191	0.6371	0.0344	0.060*
C4	0.7022 (3)	0.4873 (2)	0.1899 (2)	0.0421 (5)
H4	0.6426	0.4157	0.1785	0.050*
C5	0.8039 (2)	0.4620 (2)	0.29380 (19)	0.0340 (4)
C6	0.8238 (2)	0.3282 (2)	0.39897 (19)	0.0343 (4)
C7	0.7166 (3)	−0.0174 (2)	0.4476 (2)	0.0392 (5)
H7	0.6685	−0.0079	0.3690	0.047*
C8	0.7204 (2)	−0.1530 (2)	0.5436 (2)	0.0364 (4)
C9	0.8056 (3)	−0.1751 (2)	0.6573 (2)	0.0423 (5)
H9	0.8619	−0.1024	0.6711	0.051*
C10	0.8088 (3)	−0.3016 (2)	0.7499 (2)	0.0450 (5)
H10	0.8654	−0.3141	0.8254	0.054*
C11	0.7259 (3)	−0.4091 (2)	0.7274 (2)	0.0436 (5)
C12	0.6423 (3)	−0.3936 (2)	0.6166 (2)	0.0439 (5)
H12	0.5886	−0.4679	0.6028	0.053*
C13	0.6391 (2)	−0.2655 (2)	0.5254 (2)	0.0373 (4)
Cl2	0.59217 (8)	0.15917 (7)	0.12886 (6)	0.05501 (18)
O1W	0.0683 (2)	0.87717 (19)	0.26788 (17)	0.0547 (4)
O2W	0.3189 (3)	0.9558 (3)	0.1201 (2)	0.0859 (7)
O3W	0.9617 (3)	0.1595 (4)	0.0595 (4)	0.1333 (13)
H1N	0.947 (3)	0.753 (3)	0.234 (3)	0.066 (8)*
H2N	0.725 (3)	0.210 (3)	0.3047 (18)	0.051 (7)*
H1WA	0.145 (3)	0.882 (4)	0.230 (3)	0.076*
H1WB	0.088 (4)	0.849 (3)	0.3430 (18)	0.076*
H2WA	0.344 (4)	0.923 (3)	0.057 (2)	0.076*
H2WB	0.389 (3)	1.001 (3)	0.133 (3)	0.076*
H3WA	0.853 (2)	0.161 (3)	0.074 (3)	0.076*
H3WB	0.991 (4)	0.077 (2)	0.117 (3)	0.076*

	U11	U22	U33	U12	U13	U23
Cl1	0.0565 (3)	0.0471 (3)	0.0514 (3)	−0.0168 (2)	−0.0045 (3)	−0.0186 (2)
Cl3	0.0796 (4)	0.0369 (3)	0.0704 (4)	−0.0098 (3)	0.0025 (3)	0.0091 (3)
O1	0.0700 (10)	0.0389 (8)	0.0384 (8)	−0.0215 (7)	−0.0140 (7)	−0.0039 (6)
N1	0.0479 (10)	0.0351 (9)	0.0495 (11)	−0.0170 (8)	−0.0014 (9)	−0.0017 (8)
N2	0.0479 (10)	0.0294 (8)	0.0344 (9)	−0.0117 (7)	−0.0069 (8)	−0.0040 (7)
N3	0.0443 (9)	0.0282 (8)	0.0368 (9)	−0.0086 (7)	−0.0015 (7)	−0.0039 (7)
C1	0.0400 (10)	0.0347 (10)	0.0411 (11)	−0.0117 (8)	−0.0036 (9)	−0.0047 (9)
C2	0.0593 (14)	0.0387 (11)	0.0442 (12)	−0.0108 (10)	−0.0020 (11)	0.0034 (10)
C3	0.0572 (13)	0.0476 (12)	0.0412 (12)	−0.0078 (10)	−0.0140 (10)	0.0001 (10)
C4	0.0476 (12)	0.0382 (10)	0.0414 (11)	−0.0117 (9)	−0.0078 (9)	−0.0073 (9)
C5	0.0379 (10)	0.0297 (9)	0.0352 (10)	−0.0089 (8)	−0.0017 (8)	−0.0065 (8)
C6	0.0383 (10)	0.0304 (9)	0.0347 (10)	−0.0094 (8)	−0.0026 (8)	−0.0059 (8)
C7	0.0491 (11)	0.0307 (10)	0.0395 (11)	−0.0106 (8)	−0.0033 (9)	−0.0085 (8)
C8	0.0415 (10)	0.0280 (9)	0.0414 (11)	−0.0071 (8)	0.0027 (9)	−0.0098 (8)
C9	0.0498 (12)	0.0315 (10)	0.0479 (12)	−0.0115 (9)	−0.0007 (10)	−0.0103 (9)
C10	0.0505 (12)	0.0389 (11)	0.0446 (12)	−0.0062 (9)	−0.0015 (10)	−0.0071 (9)
C11	0.0498 (12)	0.0268 (9)	0.0509 (13)	−0.0043 (9)	0.0075 (10)	−0.0027 (9)
C12	0.0501 (12)	0.0295 (10)	0.0557 (14)	−0.0133 (9)	0.0073 (10)	−0.0133 (9)
C13	0.0407 (10)	0.0320 (10)	0.0427 (11)	−0.0084 (8)	0.0028 (9)	−0.0141 (9)
Cl2	0.0667 (4)	0.0567 (4)	0.0458 (3)	−0.0209 (3)	−0.0107 (3)	−0.0128 (3)
O1W	0.0705 (12)	0.0484 (9)	0.0457 (10)	−0.0255 (9)	−0.0100 (9)	−0.0022 (8)
O2W	0.1004 (17)	0.1131 (19)	0.0687 (14)	−0.0676 (15)	0.0228 (12)	−0.0443 (13)
O3W	0.0783 (17)	0.141 (3)	0.150 (3)	−0.0212 (18)	−0.0129 (18)	0.034 (2)

Cl1—C13	1.736 (2)	C5—C6	1.501 (3)
Cl3—C11	1.738 (2)	C7—C8	1.463 (3)
O1—C6	1.221 (2)	C7—H7	0.9300
N1—C2	1.330 (3)	C8—C9	1.397 (3)
N1—C1	1.333 (3)	C8—C13	1.398 (3)
N1—H1N	0.882 (17)	C9—C10	1.382 (3)
N2—C6	1.346 (2)	C9—H9	0.9300
N2—N3	1.378 (2)	C10—C11	1.382 (3)
N2—H2N	0.856 (16)	C10—H10	0.9300
N3—C7	1.275 (2)	C11—C12	1.371 (3)
C1—C5	1.385 (3)	C12—C13	1.384 (3)
C1—H1	0.9300	C12—H12	0.9300
C2—C3	1.374 (3)	O1W—H1WA	0.766 (17)
C2—H2	0.9300	O1W—H1WB	0.809 (18)
C3—C4	1.381 (3)	O2W—H2WA	0.829 (17)
C3—H3	0.9300	O2W—H2WB	0.805 (17)
C4—C5	1.385 (3)	O3W—H3WA	0.930 (17)
C4—H4	0.9300	O3W—H3WB	0.897 (17)
C2—N1—C1	122.53 (18)	N3—C7—C8	119.86 (19)
C2—N1—H1N	125.4 (19)	N3—C7—H7	120.1
C1—N1—H1N	112.1 (19)	C8—C7—H7	120.1
C6—N2—N3	117.78 (17)	C9—C8—C13	117.38 (18)
C6—N2—H2N	123.2 (16)	C9—C8—C7	121.09 (18)
N3—N2—H2N	119.0 (16)	C13—C8—C7	121.53 (19)
C7—N3—N2	115.19 (18)	C10—C9—C8	121.99 (19)
N1—C1—C5	120.32 (19)	C10—C9—H9	119.0
N1—C1—H1	119.8	C8—C9—H9	119.0
C5—C1—H1	119.8	C11—C10—C9	118.3 (2)
N1—C2—C3	119.7 (2)	C11—C10—H10	120.9
N1—C2—H2	120.1	C9—C10—H10	120.9
C3—C2—H2	120.1	C12—C11—C10	121.94 (19)
C2—C3—C4	119.3 (2)	C12—C11—Cl3	118.97 (16)
C2—C3—H3	120.3	C10—C11—Cl3	119.09 (19)
C4—C3—H3	120.3	C11—C12—C13	118.96 (19)
C3—C4—C5	120.05 (19)	C11—C12—H12	120.5
C3—C4—H4	120.0	C13—C12—H12	120.5
C5—C4—H4	120.0	C12—C13—C8	121.4 (2)
C1—C5—C4	118.05 (18)	C12—C13—Cl1	117.93 (15)
C1—C5—C6	115.94 (17)	C8—C13—Cl1	120.64 (16)
C4—C5—C6	125.98 (17)	H1WA—O1W—H1WB	110 (3)
O1—C6—N2	123.58 (18)	H2WA—O2W—H2WB	108 (3)
O1—C6—C5	120.06 (17)	H3WA—O3W—H3WB	96 (3)
N2—C6—C5	116.35 (17)
C6—N2—N3—C7	176.82 (19)	N3—C7—C8—C9	−6.6 (3)
C2—N1—C1—C5	1.9 (3)	N3—C7—C8—C13	173.4 (2)
C1—N1—C2—C3	−1.8 (4)	C13—C8—C9—C10	−0.9 (3)
N1—C2—C3—C4	0.0 (4)	C7—C8—C9—C10	179.1 (2)
C2—C3—C4—C5	1.6 (4)	C8—C9—C10—C11	0.6 (3)
N1—C1—C5—C4	−0.2 (3)	C9—C10—C11—C12	0.3 (3)
N1—C1—C5—C6	−178.47 (19)	C9—C10—C11—Cl3	−179.30 (18)
C3—C4—C5—C1	−1.6 (3)	C10—C11—C12—C13	−1.0 (3)
C3—C4—C5—C6	176.5 (2)	Cl3—C11—C12—C13	178.67 (16)
N3—N2—C6—O1	1.0 (3)	C11—C12—C13—C8	0.7 (3)
N3—N2—C6—C5	−178.36 (17)	C11—C12—C13—Cl1	−178.90 (17)
C1—C5—C6—O1	14.8 (3)	C9—C8—C13—C12	0.3 (3)
C4—C5—C6—O1	−163.3 (2)	C7—C8—C13—C12	−179.7 (2)
C1—C5—C6—N2	−165.78 (19)	C9—C8—C13—Cl1	179.82 (16)
C4—C5—C6—N2	16.1 (3)	C7—C8—C13—Cl1	−0.2 (3)
N2—N3—C7—C8	−178.81 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1Wi	0.88 (2)	1.77 (2)	2.646 (2)	176 (3)
N2—H2N···Cl2	0.86 (2)	2.40 (2)	3.2432 (19)	168 (2)
C1—H1···O1ii	0.93	2.40	3.214 (3)	146
C3—H3···Cl2iii	0.93	2.79	3.608 (2)	147
C7—H7···Cl2	0.93	2.76	3.588 (2)	149
O1W—H1WA···O2W	0.77 (2)	1.97 (2)	2.711 (3)	163 (3)
O1W—H1WB···O1iv	0.81 (2)	2.12 (2)	2.826 (2)	146 (3)
O1W—H1WB···N3iv	0.81 (2)	2.53 (2)	3.218 (2)	143 (3)
O2W—H2WA···Cl2iii	0.83 (2)	2.36 (2)	3.190 (2)	177 (3)
O2W—H2WB···Cl2v	0.81 (2)	2.42 (2)	3.214 (2)	169 (3)
O3W—H3WA···Cl2	0.93 (2)	2.28 (2)	3.206 (3)	174 (3)
O3W—H3WB···O1Wvi	0.90 (2)	2.25 (2)	3.146 (4)	177 (3)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1NO1W i	0.88(2)	1.77(2)	2.646(2)	176(3)
N2H2NCl2	0.86(2)	2.40(2)	3.2432(19)	168(2)
C1H1O1ii	0.93	2.40	3.214(3)	146
C3H3Cl2iii	0.93	2.79	3.608(2)	147
C7H7Cl2	0.93	2.76	3.588(2)	149
O1WH1WAO2W	0.77(2)	1.97(2)	2.711(3)	163(3)
O1WH1WBO1iv	0.81(2)	2.12(2)	2.826(2)	146(3)
O1WH1WBN3iv	0.81(2)	2.53(2)	3.218(2)	143(3)
O2WH2WACl2iii	0.83(2)	2.36(2)	3.190(2)	177(3)
O2WH2WBCl2v	0.81(2)	2.42(2)	3.214(2)	169(3)
O3WH3WACl2	0.93(2)	2.28(2)	3.206(3)	174(3)
O3WH3WBO1W vi	0.90(2)	2.25(2)	3.146(4)	177(3)

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