(E)-N′-[4-(Di­methyl­amino)­benzyl­idene]propiono­hydrazide monohydrate

Naveen, S.; Samshuddin, S.; Rodrigues, M.; Arunkumar, D.; Lokanath, N.K.; Warad, I.

doi:10.1107/S2414314616017168

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 10| October 2016| x161716

https://doi.org/10.1107/S2414314616017168

Open

access

(E)-N′-[4-(Dimethylamino)benzylidene]propionohydrazide monohydrate

S. Naveen,^a Seranthimata Samshuddin,^b Manuel Rodrigues,^c Dandavathi Arunkumar,^c N. K. Lokanath ^d and Ismail Warad ^e ^*

^aInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, ^bDepartment of Chemistry, SDM Institute of Technology, Ujire 574 240, India, ^cDepartment of P.G. Studies in Chemistry, Alva's College, Moodabidri 574 227, India, ^dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India, and ^eDepartment of Chemistry, Science College, An-Najah National University, PO Box 7, Nablus, Palestine
^*Correspondence e-mail: warad@najah.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 24 October 2016; accepted 25 October 2016; online 28 October 2016)

In the title hydrated hydrazine compound, C₁₂H₁₇N₃O·H₂O, the C=N bond adopts an E conformation. In the crystal, water molecules bridge the hydrazine molecules, via N—H⋯O and O—H⋯O hydrogen bonds, forming sheets parallel to the bc plane. There are C—H⋯π interactions present within the sheets, and further C—H⋯π interactions link the sheets to form a three-dimensional structure.

Keywords: crystal structure; hydrazine; hydrogen bonding.

CCDC reference: 1511441

Structure description

A number of industrial and biologically active compounds can be synthesized using Schiff bases as substrates via cycloaddition, ring closure and replacement reactions. In addition, Schiff bases are also known to have biological activities, such as antifungal (Singh & Dash, 1988 ), antimicrobial (El-Masry et al., 2000 ) and antitumor (Desai et al., 2001 ), and they have been used as herbicides. Schiff bases have also been employed as ligands for the complexation of metal ions (Aydogan et al., 2001 ), since many of these complexes may be useful and serve as models for biologically important species (Dharmaraj et al., 2001 ). In view of the importance of Schiff base hydrazones, we report herein on the synthesis and crystal structure of the title compound.

In the title compound (Fig. 1), the C9=N2 double bond adopts an E conformation. The methyleneformohydrazide unit [atoms O1/N2/N3/C9/C10; maximum deviation = 0.043 (1) Å for atom N2] is inclined to the benzene ring (C3–C8) by 8.94 (9)°. The solvent water molecule is linked to the hydrazine molecule by an N—H⋯O hydrogen bond (Fig. 1 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C3–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H8⋯O2	0.86	1.98	2.8330 (18)	175
O2—H18⋯O1ⁱ	0.83 (2)	2.21 (2)	2.9272 (18)	144 (2)
O2—H18⋯N2ⁱ	0.83 (2)	2.45 (2)	3.1684 (18)	145 (2)
O2—H19⋯O1ⁱⁱ	0.82 (3)	1.97 (2)	2.7845 (18)	172 (2)
C1—H14⋯Cg1ⁱⁱⁱ	0.96	2.83	3.567 (2)	135
C2—H16⋯Cg1^iv	0.96	2.91	3.701 (2)	140
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x+1, -y+2, -z+1.

Figure 1
A view of the molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level and the N—H⋯O hydrogen bond is shown as a dashed line (see Table 1

In the crystal, water molecules bridge the hydrazine molecules via N—H⋯O and O—H⋯O hydrogen bonds, forming sheets parallel to the bc plane (Table 1 and Fig. 2). There are C—H⋯π interactions present within the sheets, and further C—H⋯π interactions link the sheets to form a three-dimensional structure (Table 1 and Fig. 3).

Figure 2
A view along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1

) and, for clarity, H atoms not involved in hydrogen bonding have been omitted.

Figure 3
A view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1

) and, for clarity, H atoms not involved in the various intermolecular interactions have been omitted.

Synthesis and crystallization

A mixture of 4-(dimethylamino)benzaldehyde (0.01 mol) and hydrazine hydrate (0.01 mol) in 15 ml of propanoic acid was refluxed for ca 2 h. On cooling, the solid that separated was filtered off and recrystallized from dimethylformamide (DMF). Colourless block-like crystals were grown from DMF by slow evaporation of the solvent (yield 82%, m.p. 409 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The water H atoms were located in a difference Fourier map and refined, with U_iso(H) = 1.5U_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₇N₃O·H₂O
M_r	237.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.5756 (7), 10.5214 (6), 10.5737 (6)
β (°)	112.279 (3)
V (Å³)	1294.60 (13)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.69
Crystal size (mm)	0.29 × 0.26 × 0.22

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.826, 0.864
No. of measured, independent and observed [I > 2σ(I)] reflections	10783, 2072, 1799
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.581

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.141, 1.11
No. of reflections	2072
No. of parameters	163
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.24
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1511441

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616017168/su4088sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017168/su4088Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616017168/su4088Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008).

(E)-N'-[4-(Dimethylamino)benzylidene]propionohydrazide monohydrate top

Crystal data top

C₁₂H₁₇N₃O·H₂O	F(000) = 512
M_r = 237.30	D_x = 1.217 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 2072 reflections
a = 12.5756 (7) Å	θ = 3.8–63.7°
b = 10.5214 (6) Å	µ = 0.69 mm⁻¹
c = 10.5737 (6) Å	T = 296 K
β = 112.279 (3)°	Block, colourless
V = 1294.60 (13) Å³	0.29 × 0.26 × 0.22 mm
Z = 4

Data collection top

Bruker X8 Proteum diffractometer	2072 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1799 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.053
Detector resolution: 18.4 pixels mm^-1	θ_max = 63.7°, θ_min = 3.8°
φ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −12→11
T_min = 0.826, T_max = 0.864	l = −11→12
10783 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0887P)² + 0.250P] where P = (F_o² + 2F_c²)/3
2072 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.21 e Å⁻³
3 restraints	Δρ_min = −0.24 e Å⁻³

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 > 2sigma(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
O1	0.01204 (10)	0.62894 (12)	0.61531 (12)	0.0317 (4)
N1	0.66806 (12)	0.86484 (13)	0.57578 (14)	0.0262 (4)
N2	0.20753 (11)	0.76812 (13)	0.69793 (13)	0.0223 (4)
N3	0.12447 (11)	0.78061 (13)	0.75446 (13)	0.0223 (4)
C1	0.67145 (15)	0.78096 (18)	0.46817 (17)	0.0300 (5)
C2	0.74862 (15)	0.97087 (16)	0.61820 (18)	0.0276 (5)
C3	0.57562 (14)	0.86170 (15)	0.61455 (15)	0.0214 (5)
C4	0.49094 (14)	0.76498 (15)	0.56646 (15)	0.0218 (5)
C5	0.39942 (13)	0.75970 (15)	0.60754 (15)	0.0213 (5)
C6	0.38583 (14)	0.85007 (15)	0.69790 (15)	0.0215 (5)
C7	0.46896 (14)	0.94588 (15)	0.74484 (16)	0.0229 (5)
C8	0.56171 (14)	0.95285 (15)	0.70483 (16)	0.0232 (5)
C9	0.29009 (14)	0.84864 (15)	0.74319 (15)	0.0222 (5)
C10	0.03017 (14)	0.70707 (15)	0.70870 (16)	0.0235 (5)
C11	−0.05031 (14)	0.72381 (16)	0.78285 (17)	0.0261 (5)
C12	−0.03320 (16)	0.61625 (18)	0.88521 (18)	0.0314 (6)
O2	0.16326 (10)	0.94926 (11)	0.97640 (12)	0.0275 (4)
H1	0.67440	0.69420	0.49750	0.0450*
H2	0.04330	0.62020	0.95350	0.0470*
H3	0.80850	0.95850	0.58410	0.0410*
H4	0.49740	0.70410	0.50610	0.0260*
H5	0.34550	0.69500	0.57480	0.0260*
H6	0.61510	1.01800	0.73770	0.0280*
H7	0.46170	1.00680	0.80480	0.0270*
H8	0.13350	0.83510	0.81830	0.0270*
H9	−0.03550	0.80470	0.83030	0.0310*
H10	−0.12920	0.72380	0.71760	0.0310*
H11	−0.04420	0.53610	0.83860	0.0470*
H12	−0.08790	0.62460	0.92800	0.0470*
H13	0.28860	0.90830	0.80740	0.0270*
H14	0.60380	0.79370	0.38730	0.0450*
H15	0.73840	0.79950	0.44860	0.0450*
H16	0.70880	1.04870	0.58230	0.0410*
H17	0.78160	0.97520	0.71620	0.0410*
H18	0.1452 (18)	0.9041 (17)	1.0300 (19)	0.0410*
H19	0.1159 (16)	1.0074 (15)	0.955 (2)	0.0410*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0339 (7)	0.0360 (7)	0.0292 (7)	−0.0111 (5)	0.0165 (5)	−0.0072 (5)
N1	0.0251 (7)	0.0296 (8)	0.0265 (8)	−0.0065 (6)	0.0126 (6)	−0.0058 (6)
N2	0.0233 (7)	0.0256 (7)	0.0212 (7)	0.0004 (5)	0.0120 (6)	0.0020 (5)
N3	0.0242 (7)	0.0253 (7)	0.0206 (7)	−0.0012 (5)	0.0120 (6)	−0.0019 (5)
C1	0.0277 (9)	0.0365 (10)	0.0292 (9)	−0.0041 (7)	0.0145 (7)	−0.0067 (7)
C2	0.0262 (9)	0.0271 (9)	0.0309 (9)	−0.0042 (7)	0.0125 (7)	0.0007 (7)
C3	0.0223 (8)	0.0228 (8)	0.0177 (8)	−0.0001 (6)	0.0061 (6)	0.0033 (6)
C4	0.0259 (9)	0.0204 (8)	0.0178 (8)	−0.0005 (6)	0.0068 (6)	−0.0007 (6)
C5	0.0218 (8)	0.0211 (8)	0.0192 (8)	−0.0027 (6)	0.0056 (6)	0.0018 (6)
C6	0.0231 (8)	0.0221 (8)	0.0184 (8)	0.0007 (6)	0.0069 (6)	0.0049 (6)
C7	0.0281 (9)	0.0209 (8)	0.0202 (8)	−0.0009 (6)	0.0098 (6)	−0.0012 (6)
C8	0.0252 (8)	0.0208 (8)	0.0226 (8)	−0.0042 (6)	0.0078 (6)	−0.0011 (6)
C9	0.0264 (9)	0.0217 (8)	0.0183 (8)	0.0012 (6)	0.0081 (6)	0.0020 (6)
C10	0.0254 (9)	0.0235 (8)	0.0227 (8)	0.0012 (6)	0.0104 (7)	0.0045 (6)
C11	0.0228 (9)	0.0281 (9)	0.0284 (9)	0.0024 (7)	0.0109 (7)	0.0015 (7)
C12	0.0354 (10)	0.0341 (10)	0.0323 (10)	0.0016 (8)	0.0216 (8)	0.0028 (7)
O2	0.0310 (7)	0.0269 (7)	0.0278 (7)	0.0054 (5)	0.0148 (5)	0.0026 (5)

Geometric parameters (Å, º) top

O1—C10	1.238 (2)	C11—C12	1.524 (2)
O2—H18	0.83 (2)	C1—H1	0.9600
O2—H19	0.823 (18)	C1—H15	0.9600
N1—C1	1.453 (2)	C1—H14	0.9600
N1—C3	1.372 (2)	C2—H16	0.9600
N1—C2	1.459 (2)	C2—H17	0.9600
N2—N3	1.393 (2)	C2—H3	0.9600
N2—C9	1.284 (2)	C4—H4	0.9300
N3—C10	1.343 (2)	C5—H5	0.9300
N3—H8	0.8600	C7—H7	0.9300
C3—C4	1.420 (2)	C8—H6	0.9300
C3—C8	1.410 (2)	C9—H13	0.9300
C4—C5	1.377 (3)	C11—H10	0.9700
C5—C6	1.404 (2)	C11—H9	0.9700
C6—C7	1.401 (2)	C12—H12	0.9600
C6—C9	1.455 (3)	C12—H2	0.9600
C7—C8	1.385 (3)	C12—H11	0.9600
C10—C11	1.507 (3)

H18—O2—H19	105 (2)	N1—C1—H15	109.00
C1—N1—C2	118.82 (15)	N1—C2—H3	109.00
C1—N1—C3	119.94 (14)	N1—C2—H16	109.00
C2—N1—C3	119.67 (14)	H3—C2—H16	109.00
N3—N2—C9	114.20 (13)	H3—C2—H17	109.00
N2—N3—C10	119.64 (13)	N1—C2—H17	109.00
N2—N3—H8	120.00	H16—C2—H17	109.00
C10—N3—H8	120.00	C5—C4—H4	119.00
C4—C3—C8	117.45 (16)	C3—C4—H4	119.00
N1—C3—C8	121.51 (15)	C4—C5—H5	119.00
N1—C3—C4	121.03 (14)	C6—C5—H5	119.00
C3—C4—C5	121.26 (15)	C6—C7—H7	119.00
C4—C5—C6	121.30 (15)	C8—C7—H7	119.00
C7—C6—C9	119.37 (14)	C7—C8—H6	120.00
C5—C6—C9	123.14 (15)	C3—C8—H6	120.00
C5—C6—C7	117.49 (16)	C6—C9—H13	119.00
C6—C7—C8	122.11 (15)	N2—C9—H13	119.00
C3—C8—C7	120.38 (15)	C10—C11—H9	110.00
N2—C9—C6	122.51 (14)	C12—C11—H9	110.00
O1—C10—N3	122.71 (17)	C12—C11—H10	110.00
N3—C10—C11	114.87 (14)	C10—C11—H10	110.00
O1—C10—C11	122.39 (16)	H9—C11—H10	108.00
C10—C11—C12	109.93 (15)	C11—C12—H11	109.00
N1—C1—H1	109.00	C11—C12—H12	109.00
N1—C1—H14	109.00	C11—C12—H2	109.00
H1—C1—H14	109.00	H2—C12—H12	110.00
H1—C1—H15	109.00	H11—C12—H12	109.00
H14—C1—H15	109.00	H2—C12—H11	109.00

C1—N1—C3—C4	9.6 (2)	C4—C3—C8—C7	0.6 (2)
C1—N1—C3—C8	−171.26 (15)	C3—C4—C5—C6	0.4 (2)
C2—N1—C3—C4	175.19 (14)	C4—C5—C6—C7	0.0 (2)
C2—N1—C3—C8	−5.7 (2)	C4—C5—C6—C9	179.55 (15)
C9—N2—N3—C10	175.73 (14)	C5—C6—C7—C8	0.0 (2)
N3—N2—C9—C6	179.26 (13)	C9—C6—C7—C8	−179.60 (15)
N2—N3—C10—O1	−1.4 (2)	C5—C6—C9—N2	−3.8 (2)
N2—N3—C10—C11	176.70 (13)	C7—C6—C9—N2	175.81 (15)
N1—C3—C4—C5	178.48 (15)	C6—C7—C8—C3	−0.3 (2)
C8—C3—C4—C5	−0.7 (2)	O1—C10—C11—C12	77.2 (2)
N1—C3—C8—C7	−178.52 (15)	N3—C10—C11—C12	−100.88 (17)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C3–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H8···O2	0.86	1.98	2.8330 (18)	175
O2—H18···O1ⁱ	0.83 (2)	2.21 (2)	2.9272 (18)	144 (2)
O2—H18···N2ⁱ	0.83 (2)	2.45 (2)	3.1684 (18)	145 (2)
O2—H19···O1ⁱⁱ	0.82 (3)	1.97 (2)	2.7845 (18)	172 (2)
C1—H14···Cg1ⁱⁱⁱ	0.96	2.83	3.567 (2)	135
C2—H16···Cg1^iv	0.96	2.91	3.701 (2)	140

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

Acknowledgements

The authors are grateful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, India, for providing the single-crystal X-ray diffractometer facility. Authors also thank Alva's Education Foundation, Moodbidri, for the research facilities.

References

Aydogan, F., Ocal, N., Turgut, Z. & Yolacan, C. (2001). Bull. Korean Chem. Soc. 22, 476–480. CAS Google Scholar
Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Desai, S. B., Desai, P. B. & Desai, K. R. (2001). Heterocycl. Commun. 7, 83–90. CrossRef CAS Google Scholar
Dharmaraj, N., Viswanalhamurthi, P. & Natarajan, K. (2001). Transition Met. Chem. 26, 105–109. CrossRef CAS Google Scholar
El-Masry, A. H., Fahmy, H. H. & Abdelwahed, S. H. A. (2000). Molecules, 5, 1429–1438. Web of Science CrossRef CAS 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 CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Singh, W. M. & Dash, B. C. (1988). Pesticides, 22, 33–37. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.