4-[(2E)-2-(4-Chloro­benzyl­idene)hydrazinyl­idene]-1-methyl-1,4-dihydro­pyridine monohydrate

Aydın, A.; Akkurt, M.; Alptüzün, V.; Büyükgüngör, O.; Holzgrabe, U.; Radacki, K.

doi:10.1107/S1600536810015709

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Pages o1324-o1325

https://doi.org/10.1107/S1600536810015709

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4-[(2E)-2-(4-Chlorobenzylidene)hydrazinylidene]-1-methyl-1,4-dihydropyridine monohydrate

Abdullah Aydın,^a ^* Mehmet Akkurt,^b Vildan Alptüzün,^c Orhan Büyükgüngör,^d Ulrike Holzgrabe ^e and Krzysztof Radacki ^f

^aDepartment of Science Education, Faculty of Education, Kastamonu University, 37200 Kastamonu, Turkey, ^bDepartment of Physics, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, Ege University, 35100 Ízmir, Turkey, ^dDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun, Turkey, ^eInstitute of Pharmacy and Food Chemistry, University of Würzburg, Am Hubland 97074 Würzburg, Germany, and ^fInstitute of Inorganic Chemistry, University of Würzburg, Am Hubland 97074 Würzburg, Germany
^*Correspondence e-mail: aaydin@kastamonu.edu.tr

(Received 23 April 2010; accepted 28 April 2010; online 12 May 2010)

In the title compound, C₁₃H₁₂ClN₃·H₂O, the organic molecule is almost planar, with a dihedral angle of 3.22 (10)° between the benzene and pyridine rings. The crystal structure is stabilized by O—H⋯N and C—H⋯O hydrogen bonding and π–π stacking interactions [centroid–centroid distances = 3.630 (1) and 3.701 (1) Å].

Related literature

For the synthesis and pharmacological activity of (benzylidene-hydrazono)-1,4-dihydropyridine derivatives, see: Douglas et al. (1977 ); Alptüzün et al. (2010 ); Savini et al. (2002 ); Pandey et al. (2002 ); Salgın-Gökşen et al. (2007 ); Silva et al. (2004 ); Vicini et al. (2009 ). For bond-length data, see: Allen et al. (1987 ); Diao et al. (2008 ); Odabaşoğlu et al. (2003 ). For quantum-chemical calculations, see: Pople & Beveridge (1970 ).

Experimental

Crystal data

C₁₃H₁₂ClN₃·H₂O
M_r = 263.72
Monoclinic, P 2₁ /c
a = 5.8492 (4) Å
b = 20.3101 (10) Å
c = 12.2035 (7) Å
β = 113.855 (4)°
V = 1325.90 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 296 K
0.60 × 0.30 × 0.04 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.905, T_max = 0.989
14028 measured reflections
2759 independent reflections
1746 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.095
S = 0.95
2759 reflections
170 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1	0.84 (3)	2.26 (3)	3.089 (3)	173 (3)
O1—H1B⋯N2ⁱ	0.91 (4)	1.95 (4)	2.859 (3)	174 (2)
C3—H3⋯O1ⁱⁱ	0.93	2.58	3.421 (3)	150
C11—H11⋯O1ⁱⁱⁱ	0.93	2.49	3.378 (3)	159
Symmetry codes: (i) x+1, y, z; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z.

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810015709/sj2782sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810015709/sj2782Isup2.hkl

checkCIF report

Comment top

Hydrazones, a special group of compounds in the class of the schiff bases, are known to show significant biological activities including antimicrobial, antitubercular, anticancer, analgesic, anti-inflammatory, antiplatelet and antiviral activities (Savini et al., 2002; Pandey et al., 2002; Salgın-Gökşen et al., 2007; Silva et al., 2004; Vicini et al., 2009). In addition, (benzylidene-hydrazono)-1,4-dihydropyridine derivatives have anticoccidial activity (Douglas et al., 1977) and also display anti-Alzheimer's activity by inhibiting ABeta fibril formation and acetylcholinesterase (Alptüzün et al., 2010).

The title molecule (I), Fig. 1, crystallized as a monohydrate in the monoclinic space group P2₁/c. All bond lengths are as expected (Allen et al., 1987). The Cl1—C4, and N1—N2 bond lengths are 1.742 (2) Å, and 1.388 (2) Å, respectively. The Cl1—C4—C5 and N2—N1—C7 bond angles are 119.88 (18) ° and 113.95 (19) °, respectively. The bond lengths and the bond angles of (I) are comparable to those observed in related structures (Diao et al., 2008; Odabaşoğlu et al., 2003).

The main molecule is almost planar, except the methyl H atoms, forming a dihedral angle of 3.22 (10)° between the benzene (C1–C6) and dihydropyridine (N3/C8–C12) rings.

The crystal structure is stabilized by O—H···N and C—H···O hydrogen bonding (Table 1, Fig. 2) and π-π stacking interactions [Cg1···Cg1(-x, 1-y, -z) = 3.630 (1) Å and Cg1···Cg2(1-x, 1-y, 1-z) = 3.701 (1) Å, Cg1 and Cg2 are the centroids of the pyridine and benzene rings, respectively].

We have also carried out the quantum mechanical calculations using the CNDO (Pople et al., 1970) approximation. The spatial view of the single molecule considered in a vacuum, is shown in Fig.3. According to the theoretical CNDO and experimental X-rays results, the values of the geometric parameters of (I) are closely comparable within the observed experimental errors. The calculated dipole moment of (I) is about 11.481 Debye. The HOMO and LUMO energy levels are -8.3484 and 1.3565 eV, respectively.

Related literature top

For the synthesis and pharmacological activity of (benzylidene-hydrazono)-1,4-dihydropyridine derivatives, see: Douglas et al. (1977); Alptüzün et al. (2010); Savini et al. (2002); Pandey et al. (2002); Salgın-Gökşen et al. (2007); Silva et al. (2004); Vicini et al. (2009). For bond-length data, see: Allen et al. (1987); Diao et al. (2008); Odabaşoğlu et al. (2003). For quantum-chemical calculations, see: Pople & Beveridge (1970).

Experimental top

4-Hydrazinylpyridine (1.09 g, 0.01 mol) and 4-chlorobenzaldehyde (1.41 g, 0.01 mol) were stirred in ethanol (30 ml) at room temperature for 5-10 h. The precipitate was filtered and washed with cool ethanol and crystallized from ethanol. A mixture of 4-[(4-Chlorobenzylidene)hydrazinyl] pyridine (0.232 g, 0.001 mol) and methyl iodide (0.141 g, 0.002 mol) was refluxed in ethanol (20 ml) for 20 h. The mixture was cooled to room temperature and the resulting precipitate was filtered and washed with cool ethanol. The crude products were crystallized from ethanol to give the compound 4-(2-(4-Chlorobenzylidenehydrazinyl)-1-methylpyridinium iodide. This product (0.374 g, 0.001 mol) was partitioned between CH₂Cl₂ (50 ml) and 2 M NaOH (50 ml). The organic layer was evaporated to dryness and the residue recrystallized from ethanol-water.

Yield 88%, yellow needles, mp 407-409 K (lit. (Douglas et al. , 1977) 403-405 K). IR (KBr) v_max 1654, 1517, 1492, 1203, 824 cm^-1. ¹H-NMR (DMSO-d₆): δ ppm 3.29 (3H, s, N—CH₃), 6.12 (1H, dd, J=2.4/8.0 Hz, H-3 or H-5), 6.98 (1H, dd, J=2.0/7.8 Hz, H-3 or H-5), 7.23 (2H, td, J=7.2/2.0 Hz, H-2, H-6 ), 7.39 (2H, d, J=8.4 Hz, H-2', H-6'), 7.69 (2H, d, J=8.4 Hz, H-3', H-5'), 8.16 (1H, s, N=CH). 13 C NMR (CH₃OH- d4): δ ppm 43.18 (q), 107.78 (d), 112.11 (d), 129.35 (d), 129.79 (d), 135.59 (s), 136.58 (s), 140.15 (d), 140.75 (d), 148.84 (d), 162.25 (s). EI—MS m/z (% relative intensity): 247 (M+2, 14), 246 (M+1, 28), 245 (M+, 43), 181 (25), 93 (100), 92 (24), 66 (30), 42 (18). C₁₃H₁₂N₃Cl.H₂O. C, H, N combustion analysis: Calc. (%) C 59.21, H 5.36, N 15.93; found (%) C 59.45, H 5.33, N 15.72.

Structure description top

The main molecule is almost planar, except the methyl H atoms, forming a dihedral angle of 3.22 (10)° between the benzene (C1–C6) and dihydropyridine (N3/C8–C12) rings.

For the synthesis and pharmacological activity of (benzylidene-hydrazono)-1,4-dihydropyridine derivatives, see: Douglas et al. (1977); Alptüzün et al. (2010); Savini et al. (2002); Pandey et al. (2002); Salgın-Gökşen et al. (2007); Silva et al. (2004); Vicini et al. (2009). For bond-length data, see: Allen et al. (1987); Diao et al. (2008); Odabaşoğlu et al. (2003). For quantum-chemical calculations, see: Pople & Beveridge (1970).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. An ORTEP View of the title molecule with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 2. The packing and hydrogen bonding interactions of (I) down the a-axis. H atoms not participating in hydrogen bonding have been omitted for clarity.
	Fig. 3. The spatial view of the title molecule (I), calculated by the CNDO aproximation.

4-[(2E)-2-(4-Chlorobenzylidene)hydrazinylidene]-1-methyl- 1,4-dihydropyridine monohydrate top

Crystal data top

C₁₃H₁₂ClN₃·H₂O	F(000) = 552
M_r = 263.72	D_x = 1.321 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 11448 reflections
a = 5.8492 (4) Å	θ = 1.8–27.3°
b = 20.3101 (10) Å	µ = 0.28 mm⁻¹
c = 12.2035 (7) Å	T = 296 K
β = 113.855 (4)°	Needle, yellow
V = 1325.90 (14) Å³	0.60 × 0.30 × 0.04 mm
Z = 4

Data collection top

Stoe IPDS 2 diffractometer	2759 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1746 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.064
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.5°, θ_min = 2.0°
ω scans	h = −7→7
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −25→25
T_min = 0.905, T_max = 0.989	l = −15→15
14028 measured reflections

Refinement top

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ²(F_o²) + (0.0426P)²] where P = (F_o² + 2F_c²)/3
2759 reflections	(Δ/σ)_max < 0.001
170 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₃H₁₂ClN₃·H₂O	V = 1325.90 (14) Å³
M_r = 263.72	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.8492 (4) Å	µ = 0.28 mm⁻¹
b = 20.3101 (10) Å	T = 296 K
c = 12.2035 (7) Å	0.60 × 0.30 × 0.04 mm
β = 113.855 (4)°

Data collection top

Stoe IPDS 2 diffractometer	2759 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	1746 reflections with I > 2σ(I)
T_min = 0.905, T_max = 0.989	R_int = 0.064
14028 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.16 e Å⁻³
2759 reflections	Δρ_min = −0.18 e Å⁻³
170 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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.

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

	x	y	z	U_iso*/U_eq
Cl1	1.22894 (12)	0.72508 (3)	0.80784 (5)	0.0626 (2)
N1	0.3123 (3)	0.56701 (10)	0.35465 (13)	0.0453 (6)
N2	0.0774 (3)	0.54841 (9)	0.27204 (13)	0.0441 (6)
N3	0.0599 (4)	0.39257 (9)	0.05147 (14)	0.0478 (6)
C1	0.5371 (4)	0.63831 (11)	0.52012 (15)	0.0414 (7)
C2	0.5222 (4)	0.69371 (12)	0.58483 (16)	0.0452 (7)
C3	0.7336 (4)	0.72021 (11)	0.67306 (16)	0.0466 (7)
C4	0.9614 (4)	0.69105 (12)	0.69752 (16)	0.0449 (7)
C5	0.9807 (4)	0.63606 (12)	0.63540 (16)	0.0460 (8)
C6	0.7697 (4)	0.60996 (12)	0.54740 (16)	0.0460 (7)
C7	0.3079 (4)	0.61193 (11)	0.42743 (16)	0.0435 (7)
C8	0.0859 (4)	0.49832 (11)	0.20400 (15)	0.0396 (7)
C9	0.3019 (4)	0.46263 (11)	0.21152 (16)	0.0437 (7)
C10	0.2819 (4)	0.41223 (12)	0.13694 (18)	0.0480 (7)
C11	−0.1504 (4)	0.42521 (12)	0.04046 (17)	0.0473 (7)
C12	−0.1430 (4)	0.47578 (12)	0.11261 (16)	0.0449 (7)
C13	0.0497 (5)	0.33651 (13)	−0.0272 (2)	0.0668 (10)
O1	0.6224 (4)	0.61903 (10)	0.21954 (15)	0.0611 (7)
H2	0.36750	0.71300	0.56810	0.0540*
H3	0.72240	0.75730	0.71540	0.0560*
H5	1.13590	0.61680	0.65300	0.0550*
H6	0.78280	0.57290	0.50560	0.0550*
H7	0.15450	0.62820	0.42110	0.0520*
H9	0.45830	0.47440	0.26870	0.0520*
H10	0.42620	0.38990	0.14420	0.0580*
H11	−0.30330	0.41230	−0.01840	0.0570*
H12	−0.29140	0.49680	0.10280	0.0540*
H13A	0.18000	0.34090	−0.05550	0.1000*
H13B	−0.10970	0.33600	−0.09420	0.1000*
H13C	0.07200	0.29620	0.01700	0.1000*
H1A	0.551 (6)	0.6046 (17)	0.262 (2)	0.0920*
H1B	0.768 (6)	0.5959 (17)	0.242 (2)	0.0920*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0551 (4)	0.0646 (4)	0.0574 (3)	−0.0114 (3)	0.0116 (2)	−0.0153 (3)
N1	0.0411 (10)	0.0499 (12)	0.0415 (8)	−0.0024 (9)	0.0133 (7)	−0.0039 (8)
N2	0.0365 (10)	0.0484 (12)	0.0446 (8)	−0.0022 (9)	0.0135 (7)	−0.0053 (8)
N3	0.0558 (12)	0.0433 (12)	0.0455 (9)	−0.0060 (10)	0.0216 (8)	−0.0054 (8)
C1	0.0461 (13)	0.0438 (13)	0.0351 (9)	−0.0015 (11)	0.0173 (9)	0.0023 (8)
C2	0.0453 (13)	0.0457 (14)	0.0446 (10)	0.0042 (11)	0.0182 (9)	0.0017 (9)
C3	0.0577 (14)	0.0395 (13)	0.0434 (10)	0.0004 (12)	0.0212 (10)	−0.0043 (9)
C4	0.0472 (13)	0.0469 (14)	0.0387 (10)	−0.0069 (11)	0.0154 (9)	0.0011 (9)
C5	0.0431 (13)	0.0481 (15)	0.0456 (11)	0.0046 (11)	0.0167 (10)	−0.0020 (9)
C6	0.0485 (14)	0.0474 (14)	0.0406 (10)	0.0035 (11)	0.0164 (9)	−0.0065 (9)
C7	0.0422 (12)	0.0473 (14)	0.0429 (10)	0.0003 (11)	0.0191 (9)	−0.0014 (9)
C8	0.0393 (12)	0.0407 (13)	0.0388 (9)	−0.0004 (10)	0.0158 (8)	0.0028 (9)
C9	0.0374 (12)	0.0458 (14)	0.0428 (10)	−0.0013 (10)	0.0110 (9)	0.0001 (9)
C10	0.0456 (13)	0.0460 (14)	0.0545 (11)	0.0041 (11)	0.0223 (10)	0.0025 (10)
C11	0.0424 (13)	0.0503 (15)	0.0437 (10)	−0.0070 (12)	0.0118 (9)	−0.0004 (10)
C12	0.0357 (12)	0.0511 (15)	0.0439 (10)	−0.0021 (11)	0.0120 (9)	−0.0015 (9)
C13	0.084 (2)	0.0570 (17)	0.0615 (14)	−0.0065 (15)	0.0316 (14)	−0.0174 (12)
O1	0.0514 (11)	0.0661 (13)	0.0668 (10)	0.0032 (9)	0.0250 (8)	0.0088 (8)

Geometric parameters (Å, º) top

Cl1—C4	1.742 (2)	C8—C9	1.427 (3)
O1—H1B	0.91 (4)	C8—C12	1.428 (3)
O1—H1A	0.84 (3)	C9—C10	1.343 (3)
N1—N2	1.388 (2)	C11—C12	1.342 (3)
N1—C7	1.281 (3)	C2—H2	0.9300
N2—C8	1.327 (3)	C3—H3	0.9300
N3—C10	1.356 (3)	C5—H5	0.9300
N3—C11	1.355 (3)	C6—H6	0.9300
N3—C13	1.475 (3)	C7—H7	0.9300
C1—C2	1.398 (3)	C9—H9	0.9300
C1—C7	1.462 (3)	C10—H10	0.9300
C1—C6	1.388 (3)	C11—H11	0.9300
C2—C3	1.379 (3)	C12—H12	0.9300
C3—C4	1.376 (3)	C13—H13C	0.9600
C4—C5	1.380 (3)	C13—H13A	0.9600
C5—C6	1.373 (3)	C13—H13B	0.9600

Cl1···C2ⁱ	3.521 (2)	C11···C8^iv	3.516 (3)
Cl1···C7ⁱ	3.572 (2)	C11···O1^iv	3.378 (3)
Cl1···H10ⁱⁱ	2.9800	C13···C4^xi	3.598 (3)
O1···N2ⁱⁱⁱ	2.859 (3)	C13···C3^xi	3.490 (4)
O1···C11^iv	3.378 (3)	C3···H13A^x	2.9800
O1···N1	3.089 (3)	C7···H1B^vii	3.07 (3)
O1···H13B^iv	2.9100	C7···H1A	2.91 (3)
O1···H3^v	2.5800	C8···H1B^vii	2.88 (4)
O1···H11^iv	2.4900	C12···H1B^vii	3.06 (3)
O1···H13A^vi	2.8100	H1A···N1	2.26 (3)
N1···O1	3.089 (3)	H1A···C7	2.91 (3)
N2···O1^vii	2.859 (3)	H1B···H12ⁱⁱⁱ	2.5700
N1···H1A	2.26 (3)	H1B···N2ⁱⁱⁱ	1.95 (4)
N1···H6	2.6200	H1B···C7ⁱⁱⁱ	3.07 (3)
N1···H9	2.4700	H1B···C8ⁱⁱⁱ	2.88 (4)
N2···H1B^vii	1.95 (4)	H1B···C12ⁱⁱⁱ	3.06 (3)
C2···Cl1^viii	3.521 (2)	H1B···H7ⁱⁱⁱ	2.5100
C3···C10^ix	3.576 (3)	H2···H7	2.4300
C3···C13^x	3.490 (4)	H3···O1^xii	2.5800
C4···C13^x	3.598 (3)	H6···N1	2.6200
C4···C10^ix	3.582 (3)	H7···H1B^vii	2.5100
C5···C8^ix	3.473 (3)	H7···H2	2.4300
C5···C9^ix	3.569 (3)	H9···N1	2.4700
C6···C9^ix	3.464 (3)	H10···H13A	2.4800
C6···C8^ix	3.561 (3)	H10···Cl1ⁱⁱ	2.9800
C7···Cl1^viii	3.572 (2)	H11···H13B	2.3200
C8···C11^iv	3.516 (3)	H11···O1^iv	2.4900
C8···C6^ix	3.561 (3)	H12···H1B^vii	2.5700
C8···C5^ix	3.473 (3)	H13A···H10	2.4800
C9···C5^ix	3.569 (3)	H13A···C3^xi	2.9800
C9···C6^ix	3.464 (3)	H13A···O1^vi	2.8100
C10···C4^ix	3.582 (3)	H13B···H11	2.3200
C10···C3^ix	3.576 (3)	H13B···O1^iv	2.9100

H1A—O1—H1B	106 (3)	C1—C2—H2	120.00
N2—N1—C7	113.95 (19)	C3—C2—H2	120.00
N1—N2—C8	112.75 (18)	C4—C3—H3	120.00
C10—N3—C13	120.1 (2)	C2—C3—H3	120.00
C11—N3—C13	121.1 (2)	C4—C5—H5	120.00
C10—N3—C11	118.73 (19)	C6—C5—H5	120.00
C2—C1—C6	118.52 (19)	C5—C6—H6	120.00
C6—C1—C7	122.5 (2)	C1—C6—H6	120.00
C2—C1—C7	119.0 (2)	N1—C7—H7	119.00
C1—C2—C3	121.0 (2)	C1—C7—H7	119.00
C2—C3—C4	119.0 (2)	C10—C9—H9	120.00
Cl1—C4—C5	119.88 (18)	C8—C9—H9	120.00
C3—C4—C5	121.1 (2)	N3—C10—H10	119.00
Cl1—C4—C3	119.03 (17)	C9—C10—H10	119.00
C4—C5—C6	119.7 (2)	C12—C11—H11	119.00
C1—C6—C5	120.7 (2)	N3—C11—H11	119.00
N1—C7—C1	121.9 (2)	C8—C12—H12	119.00
N2—C8—C12	118.3 (2)	C11—C12—H12	119.00
C9—C8—C12	114.43 (19)	N3—C13—H13B	109.00
N2—C8—C9	127.27 (19)	N3—C13—H13C	109.00
C8—C9—C10	120.8 (2)	N3—C13—H13A	109.00
N3—C10—C9	122.7 (2)	H13A—C13—H13C	110.00
N3—C11—C12	121.5 (2)	H13B—C13—H13C	110.00
C8—C12—C11	122.0 (2)	H13A—C13—H13B	109.00

C7—N1—N2—C8	−174.99 (18)	C6—C1—C7—N1	−10.1 (3)
N2—N1—C7—C1	−179.43 (18)	C1—C2—C3—C4	−0.4 (3)
N1—N2—C8—C12	−178.00 (18)	C2—C3—C4—C5	0.0 (3)
N1—N2—C8—C9	2.6 (3)	C2—C3—C4—Cl1	179.29 (17)
C13—N3—C11—C12	179.2 (2)	C3—C4—C5—C6	0.2 (3)
C10—N3—C11—C12	−0.6 (3)	Cl1—C4—C5—C6	−179.11 (17)
C11—N3—C10—C9	0.3 (3)	C4—C5—C6—C1	0.1 (3)
C13—N3—C10—C9	−179.5 (2)	N2—C8—C9—C10	179.3 (2)
C2—C1—C6—C5	−0.5 (3)	N2—C8—C12—C11	−179.7 (2)
C7—C1—C2—C3	180.0 (2)	C9—C8—C12—C11	−0.2 (3)
C7—C1—C6—C5	−179.8 (2)	C12—C8—C9—C10	−0.2 (3)
C2—C1—C7—N1	170.6 (2)	C8—C9—C10—N3	0.1 (3)
C6—C1—C2—C3	0.7 (3)	N3—C11—C12—C8	0.5 (3)

Symmetry codes: (i) x+1, −y+3/2, z+1/2; (ii) −x+2, −y+1, −z+1; (iii) x+1, y, z; (iv) −x, −y+1, −z; (v) x, −y+3/2, z−1/2; (vi) −x+1, −y+1, −z; (vii) x−1, y, z; (viii) x−1, −y+3/2, z−1/2; (ix) −x+1, −y+1, −z+1; (x) −x+1, y+1/2, −z+1/2; (xi) −x+1, y−1/2, −z+1/2; (xii) 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
O1—H1A···N1	0.84 (3)	2.26 (3)	3.089 (3)	173 (3)
O1—H1B···N2ⁱⁱⁱ	0.91 (4)	1.95 (4)	2.859 (3)	174 (2)
C3—H3···O1^xii	0.93	2.58	3.421 (3)	150
C11—H11···O1^iv	0.93	2.49	3.378 (3)	159

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂ClN₃·H₂O
M_r	263.72
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	5.8492 (4), 20.3101 (10), 12.2035 (7)
β (°)	113.855 (4)
V (Å³)	1325.90 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.60 × 0.30 × 0.04

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.905, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	14028, 2759, 1746
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.095, 0.95
No. of reflections	2759
No. of parameters	170
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.18

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.84 (3)	2.26 (3)	3.089 (3)	173 (3)
O1—H1B···N2ⁱ	0.91 (4)	1.95 (4)	2.859 (3)	174 (2)
C3—H3···O1ⁱⁱ	0.93	2.58	3.421 (3)	150
C11—H11···O1ⁱⁱⁱ	0.93	2.49	3.378 (3)	159

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

Acknowledgements

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).

References

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Volume 66| Part 6| June 2010| Pages o1324-o1325

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-[(2E)-2-(4-Chloro­benzyl­­idene)hydrazinyl­­idene]-1-methyl-1,4-di­hydro­pyridine monohydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-[(2E)-2-(4-Chlorobenzylidene)hydrazinylidene]-1-methyl-1,4-dihydropyridine monohydrate