Di­chloro­{2 [(2 iso­propyl­amino­ethyl­imino)meth­yl] 4 nitrophenolato}zinc(II)

metal-organic papers

m706

2(C12H17N3O3)] doi:10.1107/S1600536807006010 Acta Cryst.(2007). E63, m706–m707 Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

Dichloro{2-[(2-isopropylaminoethylimino)-methyl]-4-nitrophenolato}zinc(II)

Shou-Xing Wang

Department of Chemistry, Zaozhuang Univer-sity, Zaozhuang Shandong 277160, People’s Republic of China

Correspondence e-mail: shouxing_wang@126.com

Key indicators

Single-crystal X-ray study T= 298 K

Mean(C–C) = 0.003 A˚ Rfactor = 0.033 wRfactor = 0.084

Data-to-parameter ratio = 18.9

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

Received 8 January 2007 Accepted 4 February 2007

#2007 International Union of Crystallography

All rights reserved

In the title compound, [ZnCl2(C12H17N3O3)], a mononuclear Schiff base zinc(II) complex, the Zn atom is tetrahedrally coordinated by one imine N atom and one phenolate O-atom of the Schiff base ligand and by two terminal chloride anions. In the crystal structure, symmetry-related molecules are linked through intermolecular N—H Cl, N—H O and C—H Cl hydrogen bonds, forming chains running parallel to thebaxis.

Comment

Zinc(II) complexes derived from Schiff base ligands have been studied extensively due to their interesting structures and numerous applications (Lacroixet al., 1996; Chisholmet al., 2001; Jianet al., 2004; Tataret al., 2002; Bhosekar et al., 2006). The condensation reaction of aromatic carbaldehydes with primary amines has been shown to offer an easy and inexpensive way of forming a variety of polydentate Schiff base ligands. As part of a further investigation of such Schiff base zinc(II) complexes, the structure of the title mononuclear zinc(II) complex, (I), is reported here.

The tetrahedral coordination environment of the ZnIIatom in (I) is formed by one imine N atom and one phenolate O atom of the Schiff base ligand, and two terminal Clanions (Fig. 1). The coordination bond distances are typical and comparable with the values in similar zinc(II) complexes (Hu, 2006; Maet al., 2006a,b). The O1—Zn1—N1 and Cl2—Zn1— Cl1 bond angles deviate most from ideal tetrahedral geometry, with values of 97.09 (7) and 117.88 (3), respectively. The other angles around Zn are in the range 108.72 (6)– 111.17 (5).

In the crystal structure of (I), symmetry-related molecules are linked through intermolecular N—H Cl, N—H O and C—H Cl hydrogen bonds (Table 1), forming chains running parallel to thebaxis (Fig. 2).

Experimental

Compound (I) was obtained by stirring

methanol (20 ml) for 30 min. The reaction mixture was then filtered. Yellow block-shaped single crystals suitable for X-ray diffraction were formed from the filtrate after one week.

Crystal data

[ZnCl2(C12H17N3O3)]

Mr= 387.56

Monoclinic,P21=c

a= 11.721 (1) A˚

b= 11.675 (1) A˚

c= 12.356 (2) A˚ = 109.191 (1)

V= 1596.9 (3) A˚3

Z= 4

Dx= 1.612 Mg m 3 MoKradiation = 1.88 mm1

T= 298 (2) K Block, yellow 0.330.290.23 mm

Data collection

Bruker SMART APEX area-detector diffractometer !scans

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

Tmin= 0.575,Tmax= 0.671

13138 measured reflections 3631 independent reflections 2929 reflections withI> 2(I)

Rint= 0.028 max= 27.5

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.033}

wR(F2_{) = 0.084}

S= 1.05 3631 reflections 192 parameters

H-atom parameters constrained

w= 1/[2

(Fo2) + (0.0416P)2 + 0.2873P]

whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.45 e A˚ 3

min=0.24 e A˚ 3

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N2—H2A Cl2i

0.90 2.44 3.231 (2) 146 N2—H2B O1i

0.90 2.08 2.922 (3) 154 C7—H7 Cl1i

0.93 2.75 3.600 (3) 153 C8—H8B Cl2ii

0.97 2.80 3.581 (3) 138 C9—H9B Cl1iii

0.97 2.74 3.551 (3) 141

Symmetry codes: (i) xþ2;y1 2;zþ

1

2; (ii) xþ2;yþ2;z; (iii) x;yþ3

2;z 1 2.

H atoms were positioned geometrically (C—H = 0.93–0.98, N—H = 0.90 A˚ ) and refined as riding, with Uiso(H) = 1.2 or 1.5 times

Ueq(C,N).

Data collection:SMART(Siemens, 1996); cell refinement:SAINT

(Siemens, 1996); data reduction: SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics:

PLATON (Spek, 2003); software used to prepare material for publication:SHELXTL(Sheldrick, 1997b).

References

Bhosekar, G., Jess, I. & Na¨ther, C. (2006).Acta Cryst.E62, m2073–m2074. Chisholm, M. H., Gallucci, J. C. & Zhen, H. (2001).Inorg. Chem.40, 5051–

5054.

Hu, Y.-J. (2006).Acta Cryst.E62, m2515–m2516.

Jian, F., Li, C., Sun, P. & Xiao, H. (2004).Acta Cryst.E60, m1811–m1812. Lacroix, P. G., Di Bella, S. & Ledoux, I. (1996).Chem. Mater.8, 541–545. Ma, J.-Y., Gu, S.-H., Guo, J.-W., Lv, B.-L. & Yin, W.-P. (2006a).Acta Cryst.E62,

m1437–m1438.

Ma, J.-Y., Lv, B.-L., Gu, S.-H., Guo, J.-W. & Yin, W.-P. (2006b).Acta Cryst.E62, m1322–m1323.

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 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996).SMARTandSAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

Tatar, L., Atakol, O. & U¨ lku¨, D. (2002).Acta Cryst.E58, m83–m85.

Figure 1

The molecular structure of compound (I), showing the numbering scheme and displacement ellipsoids drawn at the 30% probability level.

Figure 2

Part of the crystal packing of compound (I), viewed along theaaxis. The intermolecular N—H Cl and N—H O hydrogen bonds are shown as dashed lines [symmetry code: (i) = 2x,y1

2, 1

2z)]. The C—H Cl

supporting information

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Acta Cryst. (2007). E63, m706–m707

supporting information

Acta Cryst. (2007). E63, m706–m707 [https://doi.org/10.1107/S1600536807006010]

Dichloro{2-[(2-isopropylaminoethylimino)methyl]-4-nitrophenolato}zinc(II)

Shou-Xing Wang

Dichloro{4-nitro-2-[(2-isopropylaminoethylimino)methyl]phenolato}zinc(II)

Crystal data

[ZnCl2(C12H17N3O3)] Mr = 387.56

Monoclinic, P21/c

Hall symbol: -P 2ybc a = 11.721 (1) Å b = 11.675 (1) Å c = 12.356 (2) Å β = 109.191 (1)° V = 1596.9 (3) Å3 Z = 4

F(000) = 792 Dx = 1.612 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4303 reflections θ = 2.4–26.0°

µ = 1.88 mm−1 T = 298 K Block, yellow

0.33 × 0.29 × 0.23 mm

Data collection

Bruker SMART APEX area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.575, Tmax = 0.671

13138 measured reflections 3631 independent reflections 2929 reflections with I > 2σ(I) Rint = 0.028

θmax = 27.5°, θmin = 1.8° h = −15→15

k = −15→14 l = −16→15

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.033} wR(F2_{) = 0.084} S = 1.05 3631 reflections 192 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0416P)2 + 0.2873P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.45 e Å−3

Δρmin = −0.24 e Å−3

Special details

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

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

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Acta Cryst. (2007). E63, m706–m707

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Zn1 0.04232 (17) 0.02788 (15) 0.03721 (16) 0.00039 (10) 0.00994 (12) −0.00268 (10) Cl1 0.0501 (4) 0.0403 (3) 0.0546 (4) 0.0020 (3) 0.0239 (3) 0.0060 (3) Cl2 0.0609 (4) 0.0373 (3) 0.0383 (3) 0.0003 (3) 0.0170 (3) 0.0042 (2) O1 0.0462 (10) 0.0313 (8) 0.0386 (9) 0.0002 (7) 0.0068 (7) −0.0054 (6) O2 0.0914 (17) 0.0473 (12) 0.0731 (15) 0.0155 (11) 0.0006 (12) 0.0077 (11) O3 0.0891 (17) 0.0796 (15) 0.0575 (13) 0.0162 (13) −0.0167 (12) 0.0106 (11) N1 0.0362 (10) 0.0272 (9) 0.0301 (9) −0.0017 (7) 0.0100 (8) −0.0008 (7) N2 0.0358 (10) 0.0355 (10) 0.0356 (10) 0.0025 (8) 0.0058 (8) −0.0001 (8) N3 0.0549 (14) 0.0527 (14) 0.0512 (14) 0.0048 (11) 0.0047 (11) 0.0141 (11) C1 0.0323 (11) 0.0306 (11) 0.0339 (11) −0.0032 (9) 0.0095 (9) 0.0002 (9) C2 0.0324 (11) 0.0332 (11) 0.0360 (11) −0.0065 (9) 0.0133 (9) −0.0004 (9) C3 0.0393 (13) 0.0416 (13) 0.0345 (12) −0.0079 (10) 0.0108 (10) −0.0057 (10) C4 0.0395 (13) 0.0555 (15) 0.0337 (12) −0.0096 (11) 0.0056 (10) 0.0030 (11) C5 0.0383 (13) 0.0414 (13) 0.0431 (13) −0.0020 (10) 0.0077 (10) 0.0079 (11) C6 0.0400 (13) 0.0340 (12) 0.0422 (13) −0.0023 (10) 0.0106 (10) −0.0009 (10) C7 0.0385 (12) 0.0282 (10) 0.0345 (11) −0.0041 (9) 0.0153 (9) −0.0030 (9) C8 0.0441 (13) 0.0353 (12) 0.0288 (11) −0.0004 (9) 0.0135 (10) −0.0012 (9) C9 0.0455 (13) 0.0327 (11) 0.0271 (11) 0.0029 (9) 0.0072 (9) −0.0001 (9) C10 0.0353 (13) 0.0456 (14) 0.0556 (15) 0.0067 (10) 0.0097 (11) −0.0039 (12) C11 0.0423 (16) 0.094 (2) 0.101 (3) 0.0079 (16) 0.0333 (17) 0.021 (2) C12 0.0423 (15) 0.075 (2) 0.0678 (19) 0.0019 (14) −0.0035 (14) −0.0131 (16)

Geometric parameters (Å, º)

O1—Zn1—N1 97.09 (7) C5—C6—H6 119.7 O1—Zn1—Cl2 108.72 (6) C1—C6—H6 119.7 N1—Zn1—Cl2 109.73 (6) N1—C7—C1 127.2 (2) O1—Zn1—Cl1 110.24 (6) N1—C7—H7 116.4 N1—Zn1—Cl1 111.17 (5) C1—C7—H7 116.4 Cl2—Zn1—Cl1 117.88 (3) N1—C8—C9 112.25 (17) C2—O1—Zn1 122.88 (13) N1—C8—H8A 109.2 C7—N1—C8 118.21 (18) C9—C8—H8A 109.2 C7—N1—Zn1 120.27 (14) N1—C8—H8B 109.2 C8—N1—Zn1 121.51 (13) C9—C8—H8B 109.2 C9—N2—C10 116.16 (18) H8A—C8—H8B 107.9 C9—N2—H2A 108.2 N2—C9—C8 111.83 (17) C10—N2—H2A 108.2 N2—C9—H9A 109.3 C9—N2—H2B 108.2 C8—C9—H9A 109.3 C10—N2—H2B 108.2 N2—C9—H9B 109.3 H2A—N2—H2B 107.4 C8—C9—H9B 109.3 O3—N3—O2 123.0 (2) H9A—C9—H9B 107.9 O3—N3—C5 118.3 (2) C12—C10—C11 112.3 (3) O2—N3—C5 118.7 (2) C12—C10—N2 110.2 (2) C6—C1—C2 119.5 (2) C11—C10—N2 107.4 (2) C6—C1—C7 114.31 (19) C12—C10—H10 109.0 C2—C1—C7 126.19 (19) C11—C10—H10 109.0 O1—C2—C3 118.52 (19) N2—C10—H10 109.0 O1—C2—C1 123.96 (19) C10—C11—H11A 109.5 C3—C2—C1 117.52 (19) C10—C11—H11B 109.5 C4—C3—C2 121.9 (2) H11A—C11—H11B 109.5 C4—C3—H3 119.0 C10—C11—H11C 109.5 C2—C3—H3 119.0 H11A—C11—H11C 109.5 C3—C4—C5 119.4 (2) H11B—C11—H11C 109.5 C3—C4—H4 120.3 C10—C12—H12A 109.5 C5—C4—H4 120.3 C10—C12—H12B 109.5 C6—C5—C4 121.0 (2) H12A—C12—H12B 109.5 C6—C5—N3 119.0 (2) C10—C12—H12C 109.5 C4—C5—N3 119.9 (2) H12A—C12—H12C 109.5 C5—C6—C1 120.6 (2) H12B—C12—H12C 109.5

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N2—H2A···Cl2i _{0.90 2.44 3.231 (2) 146}

N2—H2B···O1i _{0.90 2.08 2.922 (3) 154}

C7—H7···Cl1i _{0.93 2.75 3.600 (3) 153}

C8—H8B···Cl2ii _{0.97 2.80 3.581 (3) 138}

C9—H9B···Cl1iii _{0.97 2.74 3.551 (3) 141}