Crystal structure of benzoic acid 4-nitrobenzylidenhydrazide

Article abstract of DOI:10.1007/s10947-006-0056-7

The crystal structure of benzoic acid 4-nitrobenzylidenhydrazide has been determined. Crystal data: crystal system - monoclinic, a = 7.101(9) A, b = 25.48(3) A, c = 7.730(11) A; β = 112.43(9)°, space group P2₁/n, Z = 4, R = 0.038. The compound under investigation has a non-planar structure in general, and the substituents at azomethine N-C bond are in E-position. Root-mean-square planes of the six-memebered heterocycles make angles of 29.9° and 37.7° to fairly planar hydrazine fragment. In crystalline state the compound forms layers, the molecules within the layers being linked by C-H...O bonds. Neighboring layers are connected by hydrogen bonds between carbonyl oxygen atoms and amide hydrogens.

Full text of DOI:10.1007/s10947-006-0056-7

Journal of Structural Chemistry, Vol. 46, No. 2, pp. 371-375, 2005
Original Russian Text Copyright © 2005 Yu. M. Chumakov, Z. A. Starikova, B. Ya. Antosyak, V. I. Tzapkov, N. M. Samus, and A. P. Gulya
CRYSTAL STRUCTURE OF BENZOIC ACID
4-NITROBENZYLIDENHYDRAZIDE
Yu. M. Chumakov,1 Z. A. Starikova,2 B. Ya. Antosyak,1
V. I. Tzapkov,3 N. M. Samus,3 and A. P. Gulya3
UDC 548.736:547.574
The crystal structure of benzoic acid 4-nitrobenzylidenhydrazide has been determined. Crystal data: crystal
system — monoclinic, a = 7.101(9) Å, b = 25.48(3) Å, c = 7.730(11) Å; E = 112.43(9)q, space group P21/n,
Z = 4, R = 0.038. The compound under investigation has a non-planar structure in general, and the substituents
at azomethine N–C bond are in E-position. Root-mean-square planes of the six-memebered heterocycles
make angles of 29.9q and 37.7q to fairly planar hydrazine fragment. In crystalline state the compound forms
layers, the molecules within the layers being linked by C–H…O bonds. Neighboring layers are connected
by hydrogen bonds between carbonyl oxygen atoms and amide hydrogens.
Keywords: benzoylhydrazone, C–H…O bonds, ȿ-position of substituents, biological activity.
As it is well-known from literature [1], hydrazides of carbonic acid derivatives include a wide range of functional
groups in their composition, and attract attention of researchers by a variety of structural peculiarities and the possible
application as synthons for the broadest variety of heterocyclic compounds. Many of them (semi-, thiosemicarbazides,
aminoguanidines, aroylhydrazides and their derivatives) possess the biological activity [2-4] and widely used in medical
treatment of diseases induced by different pathogenic microorganisms. For these reasons, the search for optimum preparation
conditions and structural investigation of novel representatives of these classes of chemical compounds are both of academic
and practical interest.
The purpose of this work is the synthesis and ascertainment of structural peculiarities of benzoic acid 4-nitroben-
zylidenhydrazide 4-NO2–C6H4–CH=NNHC(O)C6H5 (I).
Experimental. Benzoylhydrazone I was obtained as follows: a solution of 10 mmol of 4-nitrobenzaldehyde in 20 ml
of ethanol was added under stirring to a warm solution (50-55qɋ, water bath) of 10 mmol of benzoic acid hydrazide in 50 ml
of ethanol. A light-orange solution is formed, which yields a fine crystalline light-yellow precipitate on the slow evaporation
during one day. The precipitate was collected on a frit, washed with ethanol and dried in air (yield 68%). Elemental
composition of the material was established by chemical analysis.
Found, %: ɋ 62.31; H 4.01; N 15.50. For ɋ14H11N3O3 calculated, %: C 62.45; H 4.09; N 15.61.
IR spectroscopy data, cm–1: Qas(NH) = 3275; Qs(NH) = 3215; Q(C=O) = 1645; Q(C=N) = 1625; Qas(NO2) = 1515,
1345; G(C–N) = 1195, 1115; Q(N–N) = 975; Q(C–N) = 970, 930.
Azomethine I is readily soluble in dimethylformamide and dimethylsulfoxide, as well as in water or alcohols under
heating. Single crystals suitable for X-ray diffraction study were obtained by the recrystallization from methanol.
1Institute of Applied Physics, Moldova Academy of Sciences, Chisinau; chumakov.xray@phys.asm.md.
3
2Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow. Moldova State University,
Chisinau. Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 2, pp.378-382, March-April, 2005. Original article
submitted August 11, 2003.
0022-4766/05/4602-0371 © 2005 Springer Science+Business Media, Inc.
371

TABLE 1. Crystal Data, Experimental and Refinement Details for the Structure of I
Empirical formula
Molecular weight
Temperature, K
Wavelength, Å
Crystal system
C14H11N3O3
269,26
293(2)
0.71073
Monoclinic
Space group
P21/n
Unit cell parameters, a, b, c, Å
E, deg
7.101(9), 25.48(3), 7.730(11)
112.43(9)
1292(3)
Volume, Å3
Z
4
Density (calc)g/cm3
Extinction coefficient, mm–1
Crystal size, mm
1.384
0.100
0.4u0.3u0.3
2.96-25.05
2467
T range, deg
Measured reflections
Independent reflections
Data/parameters
2277 [Rint = 0.0632]
2277/226
0.962
GOOF on F 2
Final R-factor [I ! 2V(I )]
R-factor (overall)
R1 = 0.0382. wR2 = 0.0993
R1 = 0.0657. wR2 = 0.1045
Largest peak and hole, eÅ–3
0.170 and –0.194
TABLE 2. Positional (u104) and Equivalent Isotropic Thermal Parameters (Å2u103) for the Compound I
Atom
x
y
z
U(eq)
Atom
x
y
z
U(eq)
N(1)
N(2)
N(3)
O(1)
O(2)
O(3)
C(1)
C(2)
C(3)
C(4)
2570(2)
2946(2)
2497(3)
933(2)
2098(1)
2416(1)
125(1)
3070(1)
274(1)
–336(1)
712(1)
345(1)
518(1)
1042(1)
5090(2)
6627(2)
–161(2)
4899(2)
–1713(2)
260(3)
45(1)
45(1)
65(1)
53(1)
103(1)
113(1)
51(1)
53(1)
47(1)
51(1)
C(5)
C(6)
2607(3)
2928(2)
3149(3)
2075(2)
2564(2)
2790(3)
3205(3)
3347(3)
3114(3)
2727(3)
1406(1)
1245(1)
1624(1)
2895(1)
3196(1)
3737(1)
4028(1)
3792(1)
3256(1)
2955(1)
2178(2)
3982(2)
5473(2)
6418(2)
8184(2)
8142(3)
9741(3)
11373(3)
11442(3)
9844(2)
48(1)
41(1)
44(1)
40(1)
40(1)
48(1)
64(1)
70(1)
66(1)
50(1)
C(7)
C(8)
2268(3)
2592(4)
3117(3)
2958(3)
2654(3)
2480(3)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
4404(2)
3048(2)
1280(2)
817(2)
X-ray diffraction experiment was performed using a Siemens P3/PC diffractometer (ɆɨKD-radiation, graphite
monochromator, room temperature). Data collections were carried out in the T/2T-scanning mode. Absorption correction was
not applied. The structure of I was solved by the direct methods using SHELX-86 program [5]. The refinement was made
with SHELX-93 program package [6] in the anisotropic approximation for non-hydrogen atoms and in isotropic — for
hydrogen atoms. Positions of the latter were found from differential Fourier syntheses. Basic crystallographic characteristics
of the compound ȱ and refinement parameters are listed in Table 1, independent atom coordinates are listed in Table 2, bond
lengths and angles — in Table 3.
372

TABLE 3. Bond Lengths d, Å, and Angles Z, deg, in the Compound I
Bond
d
Bond
d
N(1)–C(7)
N(1)–N(2)
N(2)–C(8)
N(3)–O(2)
N(3)–O(3)
N(3)–C(3)
O(1)–C(8)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
1.275(3)
1.378(2)
1.349(3)
1.208(3)
1.213(3)
1.469(3)
1.228(2)
1.378(3)
1.389(3)
1.373(3)
1.376(3)
C(4)–C(5)
C(5)–C(6)
1.378(3)
1.387(3)
1.465(3)
1.486(3)
1.387(3)
1.388(3)
1.374(3)
1.366(3)
1.380(4)
1.389(3)
C(6)–C(7)
C(8)–C(9)
C(9)–C(14)
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
C(12)–C(13)
C(13)–C(14)
Angle
Angle
Z
Z
C(7)–N(1)–N(2)
C(8)–N(2)–N(1)
O(2)–N(3)–O(3)
O(2)–N(3)–C(3)
O(3)–N(3)–C(3)
C(2)–C(1)–C(6)
C(3)–C(2)–C(1)
C(2)–C(3)–C(4)
C(2)–C(3)–N(3)
C(4)–C(3)–N(3)
C(3)–C(4)–C(5)
C(4)–C(5)–C(6)
C(5)–C(6)–C(1)
C(5)–C(6)–C(7)
114.70(16)
119.97(15)
122.84(17)
118.8(2)
C(1)–C(6)–C(7)
N(1)–C(7)–C(6)
119.13(17)
120.88(17)
123.16(14)
121.93(17)
114.90(15)
119.38(16)
121.95(18)
118.63(15)
120.16(19)
120.5(2)
O(1)–C(8)–N(2)
O(1)–C(8)–C(9)
118.38(18)
120.84(18)
118.35(19)
122.36(15)
118.26(19)
119.38(17)
118.74(18)
120.41(18)
119.28(15)
121.55(17)
N(2)–C(8)–C(9)
C(14)–C(9)–C(10)
C(14)–C(9)–C(8)
C(10)–C(9)–C(8)
C(11)–C(10)–C(9)
C(12)–C(11)–C(10)
C(11)–C(12)–C(13)
C(12)–C(13)–C(14)
C(9)–C(14)–C(13)
120.28(19)
119.9(2)
119.8(2)
Fig. 1. Molecule of I.
Cambridge structural database (version 5.15, >7@) was employed in the analysis of geometrical parameters of I.
Discussion. In the compound I, as well as in benzaldehyde benzoylhydrazone (II) [8], salicylic aldehyde benzoyl-
hydrazone (III) [9], p-(dimehtylamino)benzaldehyde benzoylhydrazone monohydrate (IV) [10], and p-methoxybenzaldehyde
benzoylhydrazone monohydrate (V) [11], the substituents at azomethine bond N(1)–C(7) are in the E-position (Fig. 1),
the molecule of I being non-planar. Root-mean-square planes of phenyl cycles ɋ(1)yɋ(6) (A) and ɋ(9)yɋ(14) (B)
373

Fig. 2. Fragment of structure of I.
make angles of 29.9q and 37.7q, correspondingly, to hydrazine fragment N(1)N(2)ɋ(8)Ɉ(1) which is planar. Corresponding
angles in II are 19.1q and 24.1q, and in the molecules of III, IV, and V — 0 and 23.6q, 35.6q and 0, 43.1q, and 16.4q. At the
same time, the angle between the planes A and B equals 10.2q in I. The nitrogroup attached to phenyl ring A is coplanar to it
forming a joint S-system, the largest atomic deviation in 4-nitrobenzylidene fragment being less than 0.03 Å. The introduction
of NO2 group in the para-position elongates the bonds ɋ(2)–ɋ(3) and ɋ(3)–ɋ(4) in I, as compared to those in the compound
II, which lacks the substituents in the relevant cycle. Thus, the mentioned distances are equal to 1.373(3) Å and 1.376(3) Å in
I, while in II they have values 1.34 Å and 1.36 Å, respectively. A considerable difference amounting to 0.054 Å in ɋ(8)–ɋ(9)
bond lengths is observed for the two compounds. The other bond distances in the molecule under investigation agree with the
literature data. The atom ɋ(7) of the molecule deviates from phenyl ring plane by 0.04 Å, and azomethine bond N(1)–C(7)
also does not lie in this plane. The torsion angle C(5)C(6)ɋ(7)N(1) is equal to 17.3q, while in the molecules of II and V this
angle is close to 12q. Torsion angles C(6)C(7)N(1)N(2), C(7)N(1)N(2)C(8), N(1)N(2)C(8)C(9) and N(2)C(8)C(9)C(10) adopt
the values of 177.4q, 167.6q, 178.8q, and 144.2q, correspondingly. In the molecule in question, hydrazine bond N–N is in the
gauche conformation to ɋ=Ɉ bond, the torsion angle N(1)N(2)C(8)O(1) is zero. The similar conformation of this fragment
with analogous torsion angle values is realized in all the compounds mentioned above.
According to the criteria given in the paper [12], the molecules in the crystal of I are organized into layers by C–
H…O bonds with the following parameters: ɋ(10)…Ɉ(3)/* 3.462(4) Å, ɇ(10)…Ɉ(3)/ 2.56(2) Å, angle ɋ(10)ɇ(10)Ɉ(3)/
156(2)q, C(12)…O(3)// 3.675(5) Å, ɇ(12)…Ɉ(3)// 2.69(3) Å, angle ɋ(12)ɇ(12)Ɉ(3)// 155(2)q, ɋ(1)…Ɉ(2)/// 3.465(5) Å,
ɇ(1)…Ɉ(2)/// 2.61(2) Å, angle ɋ(1)ɇ(1)Ɉ(2)/// 152(1)q. The layers are linked by hydrogen bonds made by carbonyl oxygen
atoms Ɉ(1) an amide hydrogen atoms at N(2): N(2)…O(1a) 2.887(4) Å, H(2)…O(1a) 2.02(2) Å, angle N(2)H(2)O(1a)
169(2)q (Fig. 2). Phenyl rings A and B of neighboring layers are arranged one over another, with the interplanar distances
varying from 3.31 Å and 3.50 Å, which is typical of stacking interactions in the crystals [13]. The interaction between the
layers in the crystal is of van der Waals nature.
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374

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