N2,N2′-Bis[4-(dimethyl­amino)­benzyl­idene]pyridine-2,6-dicarbohydrazide monohydrate

Wang, Y.; Sun, Y.L.

doi:10.1107/S1600536810038778

organic compounds

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Volume 66| Part 11| November 2010| Page o2718

https://doi.org/10.1107/S1600536810038778

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N²,N^2′-Bis[4-(dimethylamino)benzylidene]pyridine-2,6-dicarbohydrazide monohydrate

Yong Wang ^a ^* and Yan Liang Sun ^a

^aDepartment of Chemistry, Liaocheng University, Liaocheng 252059, People's Republic of China
^*Correspondence e-mail: yongwang@lcu.edu.cn

(Received 27 August 2010; accepted 28 September 2010; online 2 October 2010)

In the title compound, C₂₅H₂₇N₇O₂·H₂O, the bis[4-(dimethylamino)benzylidene]pyridine-2,6-dicarbohydrazide molecule and the water molecule are located on a twofold rotation axis. The benzene and pyridine rings form a dihedral angle of 17.13 (7)°. In the crystal, intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the molecules into a two-dimensional supermolecular structure parallel to the ab plane.

Related literature

For related structures, see: Cheng et al. (2007 ); Cheng & Liu (2008 ); Jia, Hu et al. (2006 ); Jia, Shi et al. (2006 ).

Experimental

Crystal data

C₂₅H₂₇N₇O₂·H₂O
M_r = 475.54
Monoclinic, C 2/c
a = 8.5718 (11) Å
b = 10.2802 (14) Å
c = 27.112 (3) Å
β = 97.865 (1)°
V = 2366.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.36 × 0.31 × 0.16 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.968, T_max = 0.986
5774 measured reflections
2076 independent reflections
1348 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.204
S = 1.05
2076 reflections
163 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.86	2.23	2.967 (4)	143
O2—H2⋯O1ⁱⁱ	0.85 (3)	2.04 (4)	2.844 (3)	157 (3)
Symmetry codes: (i) x-1, y, z; (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810038778/rz2479sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810038778/rz2479Isup2.hkl

checkCIF report

Comment top

Schiff base ligands containing the pyridine ring have received considerable attention during the last decades, mainly because their coordinative and electronic properties. For this reason, much effort has been devoted to develop efficient routes for the synthesis of these classes of compounds. In this paper, we report the crystal structure of the title compound, obtained by the reaction of pyridine-2,6-dicarbohydrazide and 4-(dimethylamino)benzaldehyde.

In the title compound (Fig. 1), the bis(4-(dimethylamino)benzylidene)pyridine-2,6-dicarbohydrazide molecule and the water molecule possess crystallographic imposed twofold rotation symmetry. Bond lengths and angles are normal and correspond to those observed in related compounds (Cheng et al., 2007; Cheng & Liu, 2008; Jia, Hu et al., 2006; Jia, Shi et al., 2006). The dihedral angle formed by the benzene ring and the pyridine ring is 17.13 (7)°. In the crystal packing, a two-dimensional supermolecular structure parallel to the ab plane is formed by N—H···O and O—H···O intermolecular contacts (Table 1).

Related literature top

For related structures, see: Cheng et al. (2007); Cheng & Liu (2008); Jia, Hu et al. (2006); Jia, Shi et al. (2006).

Experimental top

To a solution of pyridine-2,6-dicarbohydrazide (3 mmol) in ethanol (30 ml) was added 4-(dimethylamino)benzaldehyde (6 mmol). The mixture was refluxed with stirring for 8 h. An red precipitate was then obtained. Red crystals suitable for X-ray diffraction analysis formed after several weeks on slow evaporation of an ethanol solution at room temperature. Elemental analysis: calculated for C₂₅H₂₉N₇O₃: C 63.14, H 6.15, N 20.62%; found: C 63.28, H 6.22, N 20.49%.

Structure description top

For related structures, see: Cheng et al. (2007); Cheng & Liu (2008); Jia, Hu et al. (2006); Jia, Shi et al. (2006).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme and 30% probability displacement ellipsoids. Unlabelled atoms are related to labelled atoms by (-x, y, 0.5-z).

N²,N^2'-Bis[4-(dimethylamino)benzylidene]pyridine-2,6- dicarbohydrazide monohydrate top

Crystal data top

C₂₅H₂₇N₇O₂·H₂O	F(000) = 1008
M_r = 475.54	D_x = 1.332 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1533 reflections
a = 8.5718 (11) Å	θ = 3.0–24.4°
b = 10.2802 (14) Å	µ = 0.09 mm⁻¹
c = 27.112 (3) Å	T = 298 K
β = 97.865 (1)°	Block, red
V = 2366.7 (5) Å³	0.36 × 0.31 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2076 independent reflections
Radiation source: fine-focus sealed tube	1348 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
phi and ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.968, T_max = 0.986	k = −12→12
5774 measured reflections	l = −32→17

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.204	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.1275P)²] where P = (F_o² + 2F_c²)/3
2076 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.17 e Å⁻³
1 restraint	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₂₅H₂₇N₇O₂·H₂O	V = 2366.7 (5) Å³
M_r = 475.54	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 8.5718 (11) Å	µ = 0.09 mm⁻¹
b = 10.2802 (14) Å	T = 298 K
c = 27.112 (3) Å	0.36 × 0.31 × 0.16 mm
β = 97.865 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2076 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1348 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.986	R_int = 0.039
5774 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	1 restraint
wR(F²) = 0.204	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.17 e Å⁻³
2076 reflections	Δρ_min = −0.59 e Å⁻³
163 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.

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.

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

	x	y	z	U_iso*/U_eq
N1	0.0000	0.0318 (3)	0.2500	0.0419 (8)
N2	0.1517 (3)	0.1645 (2)	0.18533 (9)	0.0456 (6)
H2A	0.0721	0.1938	0.1981	0.068*
N3	0.2319 (3)	0.2465 (2)	0.15743 (8)	0.0448 (7)
N4	0.4368 (3)	0.7693 (2)	0.05148 (10)	0.0556 (7)
O1	0.3055 (3)	−0.0104 (2)	0.17635 (9)	0.0669 (7)
O2	1.0000	0.3442 (4)	0.2500	0.0927 (13)
H2	0.934 (4)	0.398 (3)	0.2352 (16)	0.111*
C1	0.1949 (3)	0.0402 (3)	0.19306 (10)	0.0445 (7)
C2	0.0935 (3)	−0.0351 (3)	0.22381 (10)	0.0411 (7)
C3	0.0976 (3)	−0.1702 (3)	0.22298 (11)	0.0488 (8)
H3	0.1650	−0.2141	0.2046	0.059*
C4	0.0000	−0.2371 (4)	0.2500	0.0535 (11)
H4	0.0000	−0.3276	0.2500	0.064*
C5	0.1730 (3)	0.3604 (3)	0.15200 (10)	0.0462 (7)
H5	0.0817	0.3786	0.1657	0.055*
C6	0.2429 (3)	0.4630 (3)	0.12527 (10)	0.0424 (7)
C7	0.3772 (3)	0.4455 (3)	0.10227 (11)	0.0452 (7)
H7	0.4255	0.3643	0.1035	0.054*
C8	0.4387 (3)	0.5447 (3)	0.07816 (11)	0.0474 (8)
H8	0.5276	0.5292	0.0628	0.057*
C9	0.3728 (3)	0.6699 (3)	0.07561 (10)	0.0420 (7)
C10	0.2390 (3)	0.6870 (3)	0.09890 (11)	0.0494 (8)
H10	0.1917	0.7685	0.0982	0.059*
C11	0.1755 (3)	0.5864 (3)	0.12276 (11)	0.0489 (8)
H11	0.0854	0.6010	0.1376	0.059*
C12	0.5716 (4)	0.7484 (3)	0.02620 (13)	0.0685 (10)
H12A	0.6567	0.7141	0.0492	0.103*
H12B	0.6031	0.8295	0.0130	0.103*
H12C	0.5450	0.6877	−0.0005	0.103*
C13	0.3639 (4)	0.8964 (3)	0.04783 (13)	0.0639 (9)
H13A	0.2669	0.8923	0.0255	0.096*
H13B	0.4335	0.9576	0.0354	0.096*
H13C	0.3430	0.9235	0.0802	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0486 (18)	0.0423 (18)	0.0350 (17)	0.000	0.0068 (15)	0.000
N2	0.0534 (14)	0.0424 (14)	0.0433 (13)	−0.0004 (11)	0.0155 (11)	0.0021 (11)
N3	0.0518 (14)	0.0457 (15)	0.0376 (13)	−0.0025 (11)	0.0082 (11)	0.0021 (11)
N4	0.0561 (15)	0.0533 (16)	0.0613 (16)	−0.0005 (12)	0.0220 (13)	0.0100 (13)
O1	0.0674 (14)	0.0616 (14)	0.0780 (16)	0.0146 (11)	0.0330 (13)	0.0048 (12)
O2	0.100 (3)	0.081 (3)	0.101 (3)	0.000	0.030 (3)	0.000
C1	0.0497 (16)	0.0449 (17)	0.0392 (16)	0.0056 (13)	0.0068 (13)	−0.0040 (12)
C2	0.0472 (15)	0.0377 (15)	0.0370 (15)	0.0009 (12)	0.0013 (13)	−0.0015 (12)
C3	0.0497 (17)	0.0461 (17)	0.0495 (17)	0.0057 (14)	0.0031 (14)	−0.0055 (14)
C4	0.055 (3)	0.036 (2)	0.066 (3)	0.000	−0.005 (2)	0.000
C5	0.0480 (16)	0.0520 (18)	0.0400 (15)	0.0003 (14)	0.0107 (13)	0.0012 (13)
C6	0.0466 (15)	0.0469 (16)	0.0341 (14)	−0.0018 (13)	0.0072 (12)	0.0000 (12)
C7	0.0443 (15)	0.0449 (16)	0.0472 (16)	0.0026 (13)	0.0091 (13)	−0.0015 (13)
C8	0.0422 (15)	0.0556 (18)	0.0472 (17)	0.0008 (13)	0.0162 (13)	−0.0020 (14)
C9	0.0415 (15)	0.0484 (17)	0.0369 (15)	−0.0024 (13)	0.0080 (12)	0.0008 (13)
C10	0.0512 (17)	0.0456 (17)	0.0533 (18)	0.0064 (14)	0.0134 (14)	0.0008 (14)
C11	0.0503 (16)	0.0510 (18)	0.0496 (17)	0.0024 (14)	0.0220 (14)	0.0010 (14)
C12	0.069 (2)	0.072 (2)	0.071 (2)	−0.0130 (17)	0.0331 (19)	0.0018 (18)
C13	0.073 (2)	0.057 (2)	0.065 (2)	−0.0058 (17)	0.0188 (18)	0.0117 (17)

Geometric parameters (Å, º) top

N1—C2	1.333 (3)	C5—H5	0.9300
N1—C2ⁱ	1.333 (3)	C6—C11	1.392 (4)
N2—C1	1.339 (3)	C6—C7	1.394 (4)
N2—N3	1.378 (3)	C7—C8	1.356 (4)
N2—H2A	0.8600	C7—H7	0.9300
N3—C5	1.276 (3)	C8—C9	1.404 (4)
N4—C9	1.368 (3)	C8—H8	0.9300
N4—C12	1.438 (4)	C9—C10	1.394 (4)
N4—C13	1.446 (4)	C10—C11	1.371 (4)
O1—C1	1.222 (3)	C10—H10	0.9300
O2—H2	0.85 (3)	C11—H11	0.9300
C1—C2	1.499 (4)	C12—H12A	0.9600
C2—C3	1.390 (4)	C12—H12B	0.9600
C3—C4	1.370 (3)	C12—H12C	0.9600
C3—H3	0.9300	C13—H13A	0.9600
C4—C3ⁱ	1.370 (3)	C13—H13B	0.9600
C4—H4	0.9300	C13—H13C	0.9600
C5—C6	1.455 (4)

C2—N1—C2ⁱ	117.8 (3)	C8—C7—H7	119.4
C1—N2—N3	121.5 (2)	C6—C7—H7	119.4
C1—N2—H2A	119.3	C7—C8—C9	122.2 (3)
N3—N2—H2A	119.3	C7—C8—H8	118.9
C5—N3—N2	114.0 (2)	C9—C8—H8	118.9
C9—N4—C12	121.2 (3)	N4—C9—C10	122.1 (3)
C9—N4—C13	120.6 (2)	N4—C9—C8	121.5 (2)
C12—N4—C13	118.0 (2)	C10—C9—C8	116.3 (2)
O1—C1—N2	124.1 (3)	C11—C10—C9	121.6 (3)
O1—C1—C2	121.7 (3)	C11—C10—H10	119.2
N2—C1—C2	114.3 (2)	C9—C10—H10	119.2
N1—C2—C3	122.9 (3)	C10—C11—C6	121.4 (3)
N1—C2—C1	117.8 (2)	C10—C11—H11	119.3
C3—C2—C1	119.3 (2)	C6—C11—H11	119.3
C4—C3—C2	118.3 (3)	N4—C12—H12A	109.5
C4—C3—H3	120.8	N4—C12—H12B	109.5
C2—C3—H3	120.8	H12A—C12—H12B	109.5
C3—C4—C3ⁱ	119.8 (4)	N4—C12—H12C	109.5
C3—C4—H4	120.1	H12A—C12—H12C	109.5
C3ⁱ—C4—H4	120.1	H12B—C12—H12C	109.5
N3—C5—C6	122.7 (3)	N4—C13—H13A	109.5
N3—C5—H5	118.7	N4—C13—H13B	109.5
C6—C5—H5	118.7	H13A—C13—H13B	109.5
C11—C6—C7	117.3 (2)	N4—C13—H13C	109.5
C11—C6—C5	119.2 (2)	H13A—C13—H13C	109.5
C7—C6—C5	123.4 (3)	H13B—C13—H13C	109.5
C8—C7—C6	121.2 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱⁱ	0.86	2.23	2.967 (4)	143
O2—H2···O1ⁱⁱⁱ	0.85 (3)	2.04 (4)	2.844 (3)	157 (3)

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

Experimental details

Crystal data
Chemical formula	C₂₅H₂₇N₇O₂·H₂O
M_r	475.54
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	8.5718 (11), 10.2802 (14), 27.112 (3)
β (°)	97.865 (1)
V (Å³)	2366.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.36 × 0.31 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.968, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	5774, 2076, 1348
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.204, 1.05
No. of reflections	2076
No. of parameters	163
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.59

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.86	2.23	2.967 (4)	143
O2—H2···O1ⁱⁱ	0.85 (3)	2.04 (4)	2.844 (3)	157 (3)

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

Acknowledgements

The authors acknowledge the financial support of the University Student Science and Technology Culture Foundation of Liaocheng University (No. SRT10057HX2).

References

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