ORIGINAL PAPER

Synthesis, Characterization and Crystal Structures of 3-Hydroxy-N0-[methyl(2-pyridyl)methylene]-2-naphthohydrazidemonohydrate and 3-Hydroxy-N0-(3,5-dibromo-2-hydroxybenzylidene)-2-naphthohydrazide dimethylformamidesolvate

Guo-Ping Cheng • Ling-Wei Xue • Wei-Chun Yang

Received: 22 October 2011 / Accepted: 14 February 2012 / Published online: 28 February 2012

� Springer Science+Business Media, LLC 2012

Abstract Two hydrazone compounds, 3-hydroxy-N0-[methyl

(2-pyridyl)methylene]-2-naphthohydrazide monohydrate (1),

and 3-hydroxy-N0-(3,5-dibromo-2-hydroxybenzylidene)-2-naph-

thohydrazide dimethylformamide solvate (2), have been

prepared and characterized by elemental analysis, IR spec-

tra, 1HNMR spectra, and X-ray single crystal structural

determination. Compound (1) crystallizes in the monoc-

linic space group C2/c with unit cell dimensions a =

11.072(2) A, b = 12.017(2) A, c = 23.753(3) A, b =

95.710(2)�, V = 3144.7(9) A´ 3, Z = 8, R1 = 0.0780, and

wR2 = 0.1465. Compound (2) crystallizes in the triclinic

space group P-1 with unit cell dimensions a =

7.601(2) A, b = 16.522(4) A, c = 17.048(3) A, a = 92.516(11)�,b = 96.726(12)�, c = 94.117(12)�, V = 2117.8(8) A

´ 3, Z =

4, R1 = 0.0490, and wR2 = 0.1012. The hydrazone mole-

cules in the compounds adopt trans configurations about the

C=N double bonds. The crystal structures of the compounds

are stabilized by intermolecular hydrogen bonds and p���pstacking interactions.

Keywords Synthesis � Crystal structure � X-ray

diffraction � Hydrazone

Introduction

Hydrazone compounds are readily prepared by the reaction

of aldehydes with hydrazines, with quantitative yields and

high purity. In the last few years, hydrazone derivatives

have been proved to have interesting biological activities

such as antibacterial, antifungal, and antitumor [1–5].

Hydrazone compounds bearing NNO donor atoms have

also been introduced to coordination chemistry [6–8].

Detailed study on the preparation and structures of such

compounds seems important to understand their biologi-

cal activities and coordination capabilities. Ibrahim and

coworkers reported a series of complexes with 3-hydroxy-

N0-[methyl(2-pyridyl)methylene]-2-naphthohydrazide [9].

In addition, a few references have mentioned 3-hydroxy-

N’-(3,5-dibromo-2-hydroxybenzylidene)-2-naphthohydraz-

ide [10, 11]. However, no single-crystal X-ray diffraction

has been characterized for the compounds. In this paper,

two hydrazone compounds, 3-hydroxy-N0-[methyl(2-pyri-

dyl)methylene]-2-naphthohydrazide monohydrate (1) and

3-hydroxy-N0-(3,5-dibromo-2-hydroxybenzylidene)-2-

naphthohydrazide dimethylformamide solvate (2), have

been prepared and structurally characterized (Chart 1).

Experimental

Materials and Methods

3-Hydroxy-2-naphthoic acid hydrazide, 2-acetylpyridine,

and 3,5-dibromo-2-hydroxybenzaldehyde with AR grade

were purchased from Fluka. Other reagents and solvents

were used without further purification. Elemental (C, H and

N) analyses were made on a Perkin-Elmer Model 240B

automatic analyser. IR spectra were recorded on an IR-408

Shimadzu 568 spectrophotometer. The [1]HNMR spectra

were recorded on Bruker AVANCE 400 MHz spectrome-

ter with tetramethylsilane as the internal reference. X-ray

diffraction was carried out on a Bruker SMART 1000 CCD

area diffractometer.

G.-P. Cheng � L.-W. Xue (&) � W.-C. Yang

College of Chemistry and Chemical Engineering,

Pingdingshan University, Pingdingshan 467000, Henan,

People’s Republic of China

e-mail: pdsuchemistry@163.com

123

J Chem Crystallogr (2012) 42:668–672

DOI 10.1007/s10870-012-0297-6

Preparation of 3-hydroxy-N0-[methyl(2-pyridyl)

methylene]-2-naphthohydrazide monohydrate (1)

A methanol solution (30 ml) of 3-hydroxy-2-naphthoic

acid hydrazide (0.20 g, 1 mmol) and 2-acetylpyridine

(0.12 g, 1 mmol) was refluxed for 1 h. The solution was

then cooled to room temperature and the solid product

formed was filtered off, washed with cold methanol, and

dried over silica gel. Yield 0.23 g (75%). Analysis

calculated for C18H15N3O2: C, 70.8; H, 5.0; N, 13.8%;

found: C, 70.6; H, 5.0; N, 13.7%. IR data (KBr, cm-1):

3432 (br, w), 3207 (w, sh), 1655 (vs), 1608 (m), 1547 (s),

1511 (s), 1453 (s), 1382 (w), 1346 (s), 1312 (m), 1259 (s),

1172 (m), 1116 (w), 932 (m), 851 (w), 807 (m), 691 (w),

627 (m), 572 (w), 475 (w). 1H NMR (CDCl3): d (ppm) 1.80

(s, 3H), 7.45–7.61 (m, 3H), 7.64 (t, 1H), 7.77–7.96 (m, 4H),

8.38 (s, 1H), 8.62 (d, 1H), 10.27 (s, 1H), 13.35 (s, 1H).

Crystals suitable for X-ray diffaction were obtained by

Table 1 Crystal and structure

refinement data for (1) and (2)

a R1 =P

||Fo|-|Fc||/P

|Fo|,

wR2 = [P

w(Fo2-Fc

2)2/Pw(Fo

2)2]1/2

Compound (1) (2)

CCDC 849709 849710

Molecular formula C18H17N3O3 C21H19Br2N3O4

Molecular weight 323.3 537.2

Crystal system Monoclinic Triclinic

Space group C2/c P-1

a/A´

11.072(2) 7.601(2)

b/A´

12.017(2) 16.522(4)

c/A´

23.753(3) 17.048(3)

a/� 90 92.516(11)

b/� 95.710(2) 96.726(12)

c/� 90 94.117(12)

V/A´ 3 3144.7(9) 2117.8(8)

Z 8 4

Dcalc (g cm-3) 1.353 1.685

Crystal dimensions (mm) 0.13 9 0.10 9 0.10 0.23 9 0.20 9 0.20

l/mm 0.095 3.861

Radiation k (A´

) Mo Ka (0.71073) Mo Ka (0.71073)

Tmin/Tmax 0.9878/0.9906 0.4704/0.5123

Reflections measured 13173 13028

Range/indices (h, k, l) -13, 14; -15, 15; -29, 30 -9, 9; -18, 21; -19, 21

h limit (�) 1.72–27.00 1.20–27.00

Unique reflections 3391 [Rint = 0.0858] 9033 [Rint = 0.0291]

Observed reflections (I [ 2r(I)) 1666 4762

Parameters 229 559

Restraints 5 4

Goodness of fit on F2 1.020 1.007

R1, wR2 [I C 2r(I)]a 0.0779, 0.1471 0.0490, 0.1012

R1, wR2 (all data)a 0.1667, 0.1819 0.1196, 0.1235

OH

NH

O

NN

H2O OH

NH

O

N

OH

Br

Br

DMF

(1) (2)

Chart 1 The hydrazone compounds

J Chem Crystallogr (2012) 42:668–672 669

123

slow evaporation of a methanol solution of the compound

at room temperature.

Preparation of 3-hydroxy-N0-(3,5-dibromo-2-

hydroxybenzylidene)-2-naphthohydrazide

dimethylformamide solvate (2)

A methanol solution (30 ml) of 3-hydroxy-2-naphthoic acid

hydrazide (0.20 g, 1 mmol) and 3,5-dibromo-2-hydro-

xybenzaldehyde (0.28 g, 1 mmol) was refluxed for 1 h. The

solution was then cooled to room temperature and the solid

product formed was filtered off, washed with cold methanol, and

dried over silica gel. Yield 0.37 g (80%). Analysis calculated for

C18H12Br2N2O3: C, 46.6; H, 2.6; N, 6.0%; found: C, 46.5; H,

2.7; N, 6.1%. IR data (KBr, cm-1): 3410 (br, w), 3222 (w, sh),

1658 (vs), 1601 (m), 1559 (s), 1518 (m), 1443 (s), 1386 (m),

1357 (m), 1320 (s), 1305 (s), 1228 (s), 1171 (m), 1151 (m), 1105

(w), 945 (w), 904 (w), 879 (w), 794 (m), 761 (w), 739 (w), 687

(w), 666 (w), 636 (w), 470 (w), 418 (w). 1H NMR (DMSO-d6): d(ppm) 7.45–7.59 (m, 3H), 7.73–7.95 (m, 4H), 8.40 (s, 1H), 8.77

(s, 1H), 10.45 (s, 1H), 13.27–13.45 (b, 2H). Crystals suitable for

X-ray diffaction were obtained by slow diffusion of diethyl ether

to DMF solution of the compound at room temperature.

X-Ray Diffraction

Data were collected from selected crystals mounted on

glass fibres. The data for the two compounds were pro-

cessed with SAINT [12] and corrected for absorption using

SADABS [13]. The structures of the compounds were

solved by direct method using the program SHELXS-97,

and were refined by full-matrix least-squares technique on

F2 using anisotropic displacement parameters [14]. The N

and O attached hydrogen atoms in both compounds were

located from difference Fourier maps and refined isotrop-

ically. The remaining H atoms were placed at the calcu-

lated positions. Idealized H atoms were refined with

isotropic displacement parameters set to 1.2 (1.5 for methyl

groups) times the equivalent isotropic U values of the

parent carbon atoms. The crystallographic data for the

compounds are listed in Table 1. Selected bond lengths and

angles are in listed in Table 2. Hydrogen bonding inter-

actions are summarized in Table 3.

Results and Discussion

The two compounds were first prepared as white solid

products. Compound (1) is soluble in methanol, ethanol,

acetonitrile, and chloroform. The single crystals of (1) were

recrystallized from methanol. Compound (2) is insoluble in

Table 2 Selected bond lengths (A´

) and angles (�) for (1) and (2)

(1)

Bond lengths

C12–N2 1.282(4) N2–N1 1.369(3)

N1–C11 1.355(4) C11–O2 1.224(3)

C2–O1 1.371(4)

Bond angles

C12–N2–N1 117.1(3) N2–N1–C11 118.8(3)

N1–C11–O2 122.3(3)

(2)

Bond lengths

C7–N1 1.272(5) N1–N2 1.367(5)

N2–C8 1.356(6) C8–O2 1.241(5)

C2–O1 1.348(5) C10–O3 1.356(5)

C25–N3 1.269(5) N3–N4 1.366(5)

N4–C26 1.347(5) C26–O5 1.229(5)

C20–O4 1.341(5) C28–O6 1.356(5)

C7–N1–N2 118.5(4) N1–N2–C8 117.9(4)

N2–C8–O2 119.8(4) C25–N3–N4 118.6(4)

N3–N4–C26 118.2(4) N4–C26–O5 120.3(4)

Table 3 Hydrogen geometries for (1) and (2)

D–H���A d(D–H) (A) d(H���A)

(A)

d(D���A)

(A)

Angle(D–

H���A) (�)

(1)

O1–H1A���O3i 0.82(1) 1.83(2) 2.626(4) 163(4)

N1–H1���O1 0.82(1) 1.93(2) 2.642(3) 144(4)

O3–H3A���N3ii 0.90(1) 1.96(1) 2.853(4) 172(3)

O3–H3B���O2iii 0.90(1) 1.92(1) 2.810(3) 166(4)

(2)

O1–H1���N1 0.82 1.90 2.588(5) 141

O4–H4���N3 0.82 1.87 2.588(5) 146

N2–H2���O7iv 0.90(1) 1.97(3) 2.810(5) 153(5)

O6–H6���O5 0.85(1) 1.76(3) 2.553(5) 154(5)

O3–H3���O2 0.85(1) 1.81(3) 2.543(5) 144(5)

Symmetry codes: (i) -1/2 ? x, � - y, � ? z; (ii) 3/2 - x,-1/2 ? y,

3/2 - z; (iii) 1 - x, y, 3/2 - z; (iv) -1 ? x, y, z

Fig. 1 Perspective view of (1) with 30% probability thermal

ellipsoids. Hydrogen bond is drawn as a dashed line

670 J Chem Crystallogr (2012) 42:668–672

123

the solvents mentioned above, but soluble in DMF and

DMSO. The single crystals of (2) were obtained by slow

diffusion of the diethyl ether to the DMF solution of the

compound. Both compounds were crystallized as air-stable

colorless crystals. The elemental analyses are in agreement

with the formulae proposed by the X-ray determination.

Crystal Structure Description of (1)

The molecular structure of (1) is depicted in Fig. 1. The

compound contains a hydrazone molecule and a water

molecule. The hydrazone molecule displays a trans con-

figuration about the C=N double bond. The bond lengths

are within normal ranges [15–17]. The C12=N2 bond

length is 1.282(4) A, confirming it as a double bond. The

C11–N1 bond length of 1.355(4) A and the N1–N2 bond

length of 1.370(3) A in the hydrazone molecule are rela-

tively short, suggesting some degree of delocalization in

the acetohydrazide system. The delocalization of the mol-

ecule, as well as the presence of the intramolecular N1–

H1���O1 hydrogen bond, lead to the planarity of the

Table 4 Parameters between the planes for (1) and (2)

Cg Distance between

ring centroids (A)

Dihedral

angle (�)

Perpendicular distance

of Cg(I) on Cg(J) (A)

Beta

angle (�)

Gamma

angle (�)

Perpendicular

distance of Cg(J) on

Cg(I) (A)

(1)

Cg(1)–Cg(2)b 4.443 8.11 3.512 40.08 37.78 3.400

Cg(1)–Cg(3)b 3.881 6.34 3.532 20.56 24.49 3.634

Cg(2)–Cg(2)c 4.072 0.00 3.562 28.99 28.99 3.562

(2)

Cg(4)–Cg(5)d 3.774 0.75 3.514 21.57 21.41 3.510

Cg(4)–Cg(5)e 4.802 0.75 3.485 44.07 43.47 3.450

Cg(4)–Cg(6)d 4.578 0.38 3.508 39.60 39.97 3.527

Cg(7)–Cg(8)f 4.769 2.50 3.518 44.78 42.46 3.385

Cg(7)–Cg(8)g 4.716 2.50 3.482 40.31 42.41 3.597

Cg(1), Cg(2), and Cg(3) are the centroids of N3–C13–C14–C15–C16–C17, C1–C2–C3–C4–C9–C10, and C4–C5–C6–C7–C8–C9 in (1),

respectively. Cg(4), Cg(5), Cg(6), Cg(7), and Cg(8) are the centroids of C1–C2–C3–C4–C5–C6, C9–C10–C11–C12–C17–C18, C12–C13–C14–

C15–C16–C17, C19–C20–C21–C22–C23–C24, and C27–C28–C29–C30–C35–C36 in (2), respectively. Symmetry codes: (b) � - x, � - y,-z;

(c) -x, 1 - y, -z; (d) -x, -y, 1 - z; (e) 1 - x, -y, 1 - z; (f) -x, 1 - y, -z; (g) 1 - x, 1 - y, -z

Fig. 2 Molecular packing of (1). Hydrogen bonds are drawn as

dashed lines

Fig. 3 Perspective view of (2) with 30% probability thermal

ellipsoids. Hydrogen bonds are drawn as dashed lines

Fig. 4 Molecular packing of (2), viewed along the a axis. Hydrogen

bonds are drawn as dashed lines

J Chem Crystallogr (2012) 42:668–672 671

123

hydrazone molecule. The dihedral angle between the

naphthyl ring and the pyridine ring is 6.8(2)�.

In the crystal structure of (1), the hydrazone molecules

are linked by the water molecules through intermolecular

O–H���O and O–H���N hydrogen bonds, to form 1D chains

(Fig. 2). In addition, there are p���p stacking interactions

(Table 4) among the adjacent aromatic systems [15].

Crystal Structure Description of (2)

The molecular structure of (2) is depicted in Fig. 3. The

compound contains two hydrazone molecules and two

DMF molecules. The hydrazone molecules display trans

configurations about the C=N double bonds. The bond

lengths are within normal ranges [15–17], and are com-

parable to those observed in (1). The C7=N1 and C25=N3

bond lengths are 1.272(5) and 1.269(5) A, respectively,

confirming them as double bonds. The bonds are shorter

than the C=N bond in (1). The C8–N2 and C26–N4 bond

lengths of 1.356(6) and 1.347(5) A, and the N1–N2 and

N3–N4 bond lengths of 1.367(5) and 1.366(5) A in the

hydrazone molecules are relatively short, suggesting some

degree of delocalization in the acetohydrazide systems.

The delocalization of the molecules, as well as the presence

of the intramolecular O–H���O and O–H���N hydrogen

bonds, lead to the planarity of the hydrazone molecules.

The dihedral angles between the naphthyl ring and the

benzene ring are 0.4(2)� for molecule A and 2.9(2)� for

molecule B.

In the crystal structure of (2), the DMF molecules are

linked to the hydrazone molecules via intermolecular N–

H���O hydrogen bonds (Fig. 3). In addition, there are p���pstacking interactions (Table 4) among the adjacent aro-

matic systems [18] Fig 4.

Supplementary Material

CCDC-849709 for (1) and 849710 for (2) contain the

supplementary crystallographic data for this paper. These

data can be obtained free of charge at http://www.ccdccam.

ac.uk/const/retrieving.html or from the Cambridge Crys-

tallographic Data Centre (CCDC), 12 Union Road, Cam-

bridge CB2 1EZ, UK; fax: ?44(0)1223-336033 or e-mail:

deposit@ccdc.cam.ac.uk.

Acknowledgments This research was supported by the National

Sciences Foundation of China (No. 20676057 and 20877036) and

Top-class foundation of Pingdingshan University (No. 2008010).

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