(E) N′ (4 Benz­yl­oxy 3 meth­oxy­benzyl­­idene)benzohydrazide

organic papers

Acta Cryst.(2005). E61, o3855–o3856 doi:10.1107/S1600536805034021 He and Liu _C

22H20N2O3

o3855

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

(

E

)-

N

-(4-Benzyloxy-3-methoxybenzylidene)-benzohydrazide

Yong-Zhi He* and Dong-Zhi Liu

School of Chemical Engineering and

Technology, Tianjin University, Tianjin 300072, People’s Republic of China

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 293 K

Mean(C–C) = 0.003 A˚

Rfactor = 0.047

wRfactor = 0.130

Data-to-parameter ratio = 13.0

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

The title compound, C22H20N2O3, was prepared by the

reaction of 4-benzyloxy-3-methoxybenzaldehyde and benzo-hydrazide. The central vanillin system makes dihedral angles of 18.2 (1) and 14.3 (1)_{with the planes of the benzohydrazide}

and benzyl groups, respectively. The crystal structure is stabilized by intermolecular N—H O hydrogen bonding.

Comment

Macrocyclic and macroacyclic ligands, such as Schiff bases and crown ethers, have played an important role in our under-standing of the nature of metal–metal ion interactions in systems of biological interest (Kahwa et al., 1986). The homodinuclear complexes of ligands and lanthanide cations (Ln3+) could provide information regarding Ln3+ Ln3+ interactions that is critical for our scientific understanding and technological applications of rare earths (Lehn, 1980). Consequently, a large array of metal complexes of Schiff bases have been prepared as mimics of active centres in various proteins and enzymes (Santos et al., 2001). As part of our investigation, we now report the synthesis and molecular structure of the title compound, (I).

As shown in Fig. 1, the central vanillin system (C8–C13/C15/ O1/O2) is planar, with an r.m.s. deviation of fitted atoms of 0.016 A˚ . The benzyl group (C1–C7) is planar, with an r.m.s. deviation of fitted atoms of 0.007 A˚ . The dihedral angle between the two planes is 14.3 (1)_{. The benzohydrazide}

group (C16–C22) is planar, with an r.m.s. deviation of fitted atoms of 0.008 A˚ and makes a dihedral angle of 18.2 (1)_with

the central system. This angle is somewhat larger than the value of 9.3 (1) _{found in (E)-N}0

-{1-[4-(2-hydroxyethoxy)-3-methoxyphenyl]ethylidene}benzohydrazide monohydrate

(Diaoet al., 2005).

It should be noted that intermolecular N—H O hydrogen bonding is found in the crystal structure (Table 1), and this stabilizes the zigzag supramolecular structure (Fig. 2).

Experimental

An anhydrous ethanol solution of 4-benzyloxy-3-methoxy-benzaldehyde (2.42 g, 10 mmol) was added to an anhydrous ethanol

solution of benzohydrazide (1.36 g, 10 mmol) and the mixture stirred at 350 K for 5 h under nitrogen, whereupon a pale-yellow precipitate appeared. The product was then isolated, recrystallized from ethanol and then dried in a vacuum to give the pure compound in 85% yield. Colourless single crystals of (I), suitable for X-ray analysis, were obtained by slow evaporation of an ethanol solution.

Crystal data

C22H20N2O3 Mr= 360.40

Monoclinic,P21=c a= 7.528 (3) A˚ b= 25.027 (10) A˚ c= 9.938 (4) A˚ = 97.293 (8)

V= 1857.3 (13) A˚3 Z= 4

Dx= 1.289 Mg m 3 MoKradiation Cell parameters from 1673

reflections = 2.6–23.1

= 0.09 mm1 T= 293 (2) K Block, colourless 0.300.240.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer ’and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin= 0.968,Tmax= 0.983 8409 measured reflections

3225 independent reflections 1786 reflections withI> 2(I) Rint= 0.045

max= 25.0

h=7!8 k=26!29 l=10!11

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.047} wR(F2) = 0.130 S= 1.00 3225 reflections 249 parameters

H atoms treated by a mixture of independent and constrained refinement

w= 1/[2_(F

o2) + (0.062P)2] whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.17 e A˚3

min=0.26 e A˚

3

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N2—H2A O3i

0.89 (1) 2.11 (1) 2.958 (2) 158 (2)

Symmetry code: (i)x;yþ1 2;z

1 2.

The H atom attached to N2 was found in a difference Fourier map and refined freely to give N—H = 0.89 (1) A˚ . Carbon-bound H atoms were included in calculated positions (C—H = 0.93–0.97 A˚ ) and refined using a riding-model approximation, withUiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Data collection:SMART(Bruker, 1999); cell refinement:SAINT

(Bruker, 1999); data reduction: SAINT; program(s) used to solve

structure:SHELXS97(Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics:

SHELXTL(Sheldrick, 1997b); software used to prepare material for publication:SHELXTL.

References

Bruker (1999).SMART(Version 5.0) andSAINT(Version 4.0) for Windows NT. Bruker AXS Inc., Madison, Wisconsin, USA.

Diao, C.-H., Yu, M., Chen, X., Jing, Z.-L & Deng, Q.-L. (2005).Acta Cryst. E61, o3500–o3501.

Kahwa, I. A., Selbin, J., Hsieh, T. C.-Y. & Laine, R. A. (1986).Inorg. Chim. Acta,118, 179–185.

Lehn, J. M. (1980).J. Pure Appl. Chem.52, 2441.

Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001).J. Chem. Soc. Dalton Trans.pp. 838–844.

Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of

Go¨ttingen, Germany.

Sheldrick, G. M. (1997b).SHELXTL. Version 5.10 for Windows NT. Bruker AXS Inc., Madison, Wisconsin, USA.

Figure 2

Intermolecular hydrogen-bonding interactions (dashed lines) in (I). Figure 1

supporting information

sup-1 Acta Cryst. (2005). E61, o3855–o3856

supporting information

Acta Cryst. (2005). E61, o3855–o3856 [https://doi.org/10.1107/S1600536805034021]

(

E

)-

N

′

-(4-Benzyloxy-3-methoxybenzylidene)benzohydrazide

Yong-Zhi He and Dong-Zhi Liu

(E)—N′-(4-Benzyloxy-3-methoxybenzylidene)benzohydrazide

Crystal data

C22H20N2O3

Mr = 360.40

Monoclinic, P21/c

Hall symbol: -p 2ybc

a = 7.528 (3) Å

b = 25.027 (10) Å

c = 9.938 (4) Å

β = 97.293 (8)°

V = 1857.3 (13) Å3

Z = 4

F(000) = 760

Dx = 1.289 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1673 reflections

θ = 2.6–23.1°

µ = 0.09 mm−1

T = 293 K Block, colorless 0.30 × 0.24 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.968, Tmax = 0.983

8409 measured reflections 3225 independent reflections 1786 reflections with I > 2σ(I)

Rint = 0.045

θmax = 25.0°, θmin = 1.6°

h = −7→8

k = −26→29

l = −10→11

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.047}

wR(F2_{) = 0.130}

S = 1.00 3225 reflections 249 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.062P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.17 e Å−3

Δρmin = −0.26 e Å−3

Special details

Refinement. Refinement of F2 against ALL reflections. The weightedR-factorwRand goodness of fitSare based on F2_{, conventional R-factors R are based}

on F, with F set to zero for negative F2. The threshold expression of F2 _{> 2σ(F2}) is used only for calculatingR-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₎

x y z Uiso*/Ueq

O1 0.3466 (2) 0.54945 (6) 0.14849 (14) 0.0513 (5) O2 0.3670 (2) 0.47361 (6) 0.32319 (14) 0.0554 (5) O3 −0.0202 (2) 0.22775 (6) 0.20000 (14) 0.0547 (5) N1 0.0925 (3) 0.30887 (7) 0.05521 (16) 0.0402 (5) N2 0.0402 (3) 0.26011 (7) −0.00160 (17) 0.0392 (5) C1 0.3451 (3) 0.59250 (8) 0.0542 (2) 0.0457 (6)

H1A 0.2236 0.5987 0.0115 0.055*

H1B 0.4180 0.5833 −0.0162 0.055*

C2 0.4168 (3) 0.64225 (9) 0.1259 (2) 0.0409 (6) C3 0.3906 (4) 0.69061 (10) 0.0610 (3) 0.0562 (7)

H3 0.3269 0.6922 −0.0254 0.067*

C4 0.4583 (4) 0.73694 (10) 0.1235 (3) 0.0710 (9)

H4 0.4411 0.7694 0.0783 0.085*

C5 0.5499 (4) 0.73543 (11) 0.2505 (3) 0.0720 (9)

H5 0.5933 0.7668 0.2928 0.086*

C6 0.5780 (4) 0.68734 (12) 0.3158 (3) 0.0690 (8)

H6 0.6425 0.6860 0.4019 0.083*

C7 0.5110 (4) 0.64087 (10) 0.2544 (2) 0.0559 (7)

H7 0.5293 0.6085 0.2998 0.067*

C8 0.2945 (3) 0.50057 (9) 0.0978 (2) 0.0402 (6) C9 0.3031 (3) 0.45892 (9) 0.1932 (2) 0.0395 (6) C10 0.2502 (3) 0.40855 (9) 0.1524 (2) 0.0409 (6)

H10 0.2553 0.3812 0.2161 0.049*

C11 0.1884 (3) 0.39742 (9) 0.0159 (2) 0.0386 (6) C12 0.1846 (3) 0.43845 (9) −0.0760 (2) 0.0489 (7)

H12 0.1470 0.4316 −0.1672 0.059*

C13 0.2357 (3) 0.48985 (9) −0.0362 (2) 0.0491 (7)

H13 0.2302 0.5171 −0.1002 0.059*

C14 0.3678 (4) 0.43402 (10) 0.4267 (2) 0.0667 (8)

H14A 0.2478 0.4216 0.4302 0.100*

H14B 0.4141 0.4493 0.5127 0.100*

H14C 0.4420 0.4046 0.4068 0.100*

C15 0.1306 (3) 0.34418 (8) −0.0287 (2) 0.0418 (6)

H15 0.1212 0.3358 −0.1204 0.050*

C16 −0.0154 (3) 0.22130 (9) 0.0783 (2) 0.0376 (6) C17 −0.0667 (3) 0.16900 (8) 0.01121 (19) 0.0356 (6) C18 −0.1099 (3) 0.12781 (10) 0.0931 (2) 0.0521 (7)

H18 −0.1087 0.1339 0.1856 0.063*

C19 −0.1548 (4) 0.07793 (11) 0.0413 (3) 0.0671 (8)

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sup-3 Acta Cryst. (2005). E61, o3855–o3856

C20 −0.1588 (4) 0.06924 (11) −0.0953 (3) 0.0660 (8)

H20 −0.1890 0.0357 −0.1315 0.079*

C21 −0.1186 (4) 0.10962 (10) −0.1778 (2) 0.0622 (8)

H21 −0.1225 0.1035 −0.2704 0.075*

C22 −0.0723 (3) 0.15948 (9) −0.1263 (2) 0.0514 (7)

H22 −0.0449 0.1867 −0.1839 0.062*

H2A 0.038 (3) 0.2554 (8) −0.0910 (10) 0.041 (6)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

O1 0.0812 (13) 0.0332 (10) 0.0386 (9) −0.0067 (9) 0.0034 (8) 0.0006 (8) O2 0.0896 (14) 0.0400 (10) 0.0334 (9) −0.0050 (9) −0.0046 (8) −0.0008 (8) O3 0.0900 (14) 0.0500 (11) 0.0254 (8) −0.0053 (9) 0.0125 (8) −0.0038 (7) N1 0.0552 (14) 0.0306 (11) 0.0338 (10) −0.0017 (9) 0.0020 (9) −0.0044 (9) N2 0.0604 (14) 0.0335 (12) 0.0234 (10) −0.0030 (9) 0.0046 (9) −0.0024 (9) C1 0.0579 (18) 0.0373 (14) 0.0415 (13) −0.0014 (12) 0.0045 (12) 0.0048 (11) C2 0.0426 (16) 0.0361 (14) 0.0451 (14) −0.0017 (11) 0.0093 (12) −0.0012 (11) C3 0.062 (2) 0.0407 (16) 0.0638 (16) 0.0004 (13) 0.0012 (14) 0.0027 (13) C4 0.076 (2) 0.0380 (17) 0.098 (2) −0.0013 (15) 0.0070 (19) 0.0036 (16) C5 0.076 (2) 0.0502 (19) 0.088 (2) −0.0116 (16) 0.0055 (18) −0.0202 (17) C6 0.076 (2) 0.068 (2) 0.0598 (17) −0.0156 (17) −0.0039 (15) −0.0140 (16) C7 0.070 (2) 0.0476 (16) 0.0490 (15) −0.0097 (14) 0.0024 (14) 0.0003 (13) C8 0.0529 (17) 0.0298 (13) 0.0385 (13) −0.0020 (11) 0.0076 (12) −0.0033 (11) C9 0.0493 (16) 0.0376 (14) 0.0310 (12) 0.0025 (11) 0.0031 (11) −0.0012 (10) C10 0.0519 (17) 0.0356 (14) 0.0354 (13) 0.0013 (11) 0.0059 (11) 0.0036 (11) C11 0.0487 (16) 0.0340 (13) 0.0335 (12) 0.0001 (11) 0.0072 (11) −0.0011 (11) C12 0.071 (2) 0.0426 (15) 0.0314 (12) −0.0052 (13) 0.0004 (12) −0.0025 (12) C13 0.074 (2) 0.0365 (15) 0.0354 (13) −0.0031 (13) 0.0037 (13) 0.0065 (11) C14 0.095 (2) 0.0633 (19) 0.0372 (14) −0.0081 (16) −0.0101 (14) 0.0091 (13) C15 0.0566 (18) 0.0368 (14) 0.0320 (12) −0.0013 (12) 0.0055 (12) −0.0016 (11) C16 0.0494 (16) 0.0369 (14) 0.0260 (12) 0.0021 (11) 0.0028 (11) 0.0000 (10) C17 0.0407 (15) 0.0384 (14) 0.0272 (11) −0.0011 (11) 0.0020 (10) 0.0008 (10) C18 0.068 (2) 0.0520 (17) 0.0373 (13) −0.0162 (14) 0.0098 (12) 0.0010 (12) C19 0.094 (2) 0.0534 (18) 0.0548 (17) −0.0303 (16) 0.0123 (16) 0.0058 (14) C20 0.089 (2) 0.0493 (17) 0.0600 (17) −0.0265 (15) 0.0093 (16) −0.0109 (14) C21 0.092 (2) 0.0582 (18) 0.0377 (14) −0.0204 (16) 0.0124 (14) −0.0117 (13) C22 0.081 (2) 0.0404 (15) 0.0340 (13) −0.0071 (13) 0.0119 (13) −0.0002 (11)

Geometric parameters (Å, º)

O1—C8 1.362 (3) C9—C10 1.368 (3)

O1—C1 1.427 (2) C10—C11 1.405 (3)

O2—C9 1.370 (2) C10—H10 0.9300

O2—C14 1.428 (3) C11—C12 1.372 (3)

O3—C16 1.225 (2) C11—C15 1.453 (3)

N1—C15 1.272 (2) C12—C13 1.386 (3)

N2—C16 1.354 (3) C13—H13 0.9300

N2—H2A 0.894 (9) C14—H14A 0.9600

C1—C2 1.501 (3) C14—H14B 0.9600

C1—H1A 0.9700 C14—H14C 0.9600

C1—H1B 0.9700 C15—H15 0.9300

C2—C3 1.374 (3) C16—C17 1.497 (3)

C2—C7 1.380 (3) C17—C18 1.378 (3)

C3—C4 1.382 (3) C17—C22 1.383 (3)

C3—H3 0.9300 C18—C19 1.376 (3)

C4—C5 1.360 (4) C18—H18 0.9300

C4—H4 0.9300 C19—C20 1.372 (3)

C5—C6 1.371 (4) C19—H19 0.9300

C5—H5 0.9300 C20—C21 1.359 (3)

C6—C7 1.379 (3) C20—H20 0.9300

C6—H6 0.9300 C21—C22 1.377 (3)

C7—H7 0.9300 C21—H21 0.9300

C8—C13 1.375 (3) C22—H22 0.9300

C8—C9 1.405 (3)

C8—O1—C1 117.20 (16) C12—C11—C10 118.1 (2) C9—O2—C14 117.50 (17) C12—C11—C15 120.2 (2) C15—N1—N2 114.98 (17) C10—C11—C15 121.7 (2) C16—N2—N1 119.18 (17) C11—C12—C13 121.5 (2)

C16—N2—H2A 121.3 (13) C11—C12—H12 119.2

N1—N2—H2A 119.4 (13) C13—C12—H12 119.2

O1—C1—C2 109.97 (18) C8—C13—C12 120.1 (2)

O1—C1—H1A 109.7 C8—C13—H13 120.0

C2—C1—H1A 109.7 C12—C13—H13 120.0

O1—C1—H1B 109.7 O2—C14—H14A 109.5

C2—C1—H1B 109.7 O2—C14—H14B 109.5

H1A—C1—H1B 108.2 H14A—C14—H14B 109.5

C3—C2—C7 118.9 (2) O2—C14—H14C 109.5

C3—C2—C1 119.1 (2) H14A—C14—H14C 109.5

C7—C2—C1 122.0 (2) H14B—C14—H14C 109.5

C2—C3—C4 120.4 (3) N1—C15—C11 121.38 (19)

C2—C3—H3 119.8 N1—C15—H15 119.3

C4—C3—H3 119.8 C11—C15—H15 119.3

C5—C4—C3 120.6 (3) O3—C16—N2 122.3 (2)

C5—C4—H4 119.7 O3—C16—C17 121.1 (2)

C3—C4—H4 119.7 N2—C16—C17 116.58 (17)

C4—C5—C6 119.5 (3) C18—C17—C22 118.4 (2)

C4—C5—H5 120.2 C18—C17—C16 117.25 (19)

C6—C5—H5 120.2 C22—C17—C16 124.4 (2)

C5—C6—C7 120.4 (3) C19—C18—C17 121.5 (2)

C5—C6—H6 119.8 C19—C18—H18 119.2

C7—C6—H6 119.8 C17—C18—H18 119.2

C6—C7—C2 120.3 (3) C20—C19—C18 119.2 (2)

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sup-5 Acta Cryst. (2005). E61, o3855–o3856

C2—C7—H7 119.9 C18—C19—H19 120.4

O1—C8—C13 125.1 (2) C21—C20—C19 120.0 (2)

O1—C8—C9 115.47 (19) C21—C20—H20 120.0

C13—C8—C9 119.4 (2) C19—C20—H20 120.0

C10—C9—O2 125.53 (19) C20—C21—C22 121.0 (2)

C10—C9—C8 119.8 (2) C20—C21—H21 119.5

O2—C9—C8 114.70 (19) C22—C21—H21 119.5

C9—C10—C11 121.2 (2) C21—C22—C17 119.9 (2)

C9—C10—H10 119.4 C21—C22—H22 120.1

C11—C10—H10 119.4 C17—C22—H22 120.1

C15—N1—N2—C16 −175.2 (2) C9—C10—C11—C15 −179.5 (2) C8—O1—C1—C2 −176.45 (19) C10—C11—C12—C13 −1.6 (4) O1—C1—C2—C3 −165.7 (2) C15—C11—C12—C13 178.8 (2) O1—C1—C2—C7 15.3 (3) O1—C8—C13—C12 −179.5 (2) C7—C2—C3—C4 0.3 (4) C9—C8—C13—C12 0.3 (4) C1—C2—C3—C4 −178.7 (2) C11—C12—C13—C8 1.0 (4) C2—C3—C4—C5 −0.8 (4) N2—N1—C15—C11 −179.8 (2) C3—C4—C5—C6 1.2 (5) C12—C11—C15—N1 −163.3 (2) C4—C5—C6—C7 −1.2 (5) C10—C11—C15—N1 17.1 (4) C5—C6—C7—C2 0.8 (4) N1—N2—C16—O3 −0.4 (3) C3—C2—C7—C6 −0.3 (4) N1—N2—C16—C17 −178.79 (18) C1—C2—C7—C6 178.6 (2) O3—C16—C17—C18 −3.4 (3) C1—O1—C8—C13 −2.1 (3) N2—C16—C17—C18 175.0 (2) C1—O1—C8—C9 178.13 (19) O3—C16—C17—C22 177.0 (2) C14—O2—C9—C10 −4.4 (3) N2—C16—C17—C22 −4.6 (3) C14—O2—C9—C8 175.9 (2) C22—C17—C18—C19 1.1 (4) O1—C8—C9—C10 178.7 (2) C16—C17—C18—C19 −178.5 (2) C13—C8—C9—C10 −1.1 (3) C17—C18—C19—C20 −0.8 (4) O1—C8—C9—O2 −1.5 (3) C18—C19—C20—C21 0.0 (5) C13—C8—C9—O2 178.7 (2) C19—C20—C21—C22 0.5 (5) O2—C9—C10—C11 −179.2 (2) C20—C21—C22—C17 −0.2 (4) C8—C9—C10—C11 0.5 (3) C18—C17—C22—C21 −0.6 (4) C9—C10—C11—C12 0.9 (3) C16—C17—C22—C21 179.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N2—H2A···O3i _{0.89 (1) 2.11 (1) 2.958 (2) 158 (2)}