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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): m964.
Published online 2009 July 22. doi:  10.1107/S1600536809028220
PMCID: PMC2977086

Dichlorido{2-[2-(dimethyl­ammonio)ethyl­imino­meth­yl]-6-methoxy­phenolato}zinc(II)

Abstract

The structure of the title complex, [ZnCl2(C12H18N2O2)], contains a zwitterionic Schiff base ligand. The complex adopts a distorted tetra­hedral coordination geometry around the metal centre with the Schiff base ligand coordinated in a bidentate fashion via the imine N and phenolate O atoms. In the crystal, inter­molecular N—H(...)O and C—H(...)Cl hydrogen bonds link the mol­ecules into chains parallel to the c-glide planes.

Related literature

For bidentate Schiff base–Zn(II) complexes, see: Qiu (2006 [triangle]); Wang & Qiu (2006 [triangle]); Ye & You (2008 [triangle]); You (2005a [triangle],b [triangle]); Zhu (2008 [triangle]).

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Object name is e-65-0m964-scheme1.jpg

Experimental

Crystal data

  • [ZnCl2(C12H18N2O2)]
  • M r = 358.55
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m964-efi1.jpg
  • a = 8.5621 (6) Å
  • b = 16.9642 (12) Å
  • c = 13.1106 (7) Å
  • β = 127.732 (3)°
  • V = 1506.08 (17) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.98 mm−1
  • T = 298 K
  • 0.32 × 0.25 × 0.22 mm

Data collection

  • Bruker SMART APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.552, T max = 0.649
  • 8355 measured reflections
  • 2960 independent reflections
  • 2439 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.028
  • wR(F 2) = 0.075
  • S = 1.01
  • 2960 reflections
  • 175 parameters
  • H-atom parameters constrained
  • Δρmax = 0.35 e Å−3
  • Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028220/bh2237sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028220/bh2237Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We are grateful to the National Science Council of Taiwan for financial support.

supplementary crystallographic information

Comment

The Schiff base 2-((2-(dimethylamino)ethylimino)methyl)-6-methoxyphenol reacts with zinc(II) chloride in methanol to form the title complex. It adopts tetrahedron coordination geometry with the Schiff base ligand coordinated via the imine N and the phenolate O atoms. A formal proton transfer of the phenolic hydrogen to the amine N atom occurred leading to the formation of the neutral O/N-bidentate ligand bearing a pendant ammonium group.

Bidentate Schiff base Zn(II) complexes similar to the title complex were reported in the literature (Qiu, 2006; Wang & Qiu, 2006; Ye & You, 2008; You, 2005a, b; Zhu, 2008).

Classical intermolecular H-bonds of the type N—H···O and non-classical H-bonds of the type C—H···Cl exist (Table 1). These H-bonds link the complex into one-dimensional hydrogen bonded chains.

Experimental

To an aqueous solution (20 ml) of zinc(II) chloride (0.136 g, 1.00 mmol), a methanolic solution of the Schiff base 2-((2-(dimethylamino)ethylimino)methyl)-6-methoxyphenol (1.00 mmol) was added. The resulting mixture was kept at room temperature yielding brown block-like crystals suitable for X-ray diffraction after few days. Crystals were isolated by filtration and were dried in the air.

Refinement

All the H atoms were positioned geometrically and refined as riding atoms, with Caryl—H = 0.93, Cmethyl—H = 0.96, Cmethylene—H = 0.97, and N—H = 0.91 Å, while Uiso(H) = 1.5Ueq(C) for the methyl H atoms and Uiso(H) = 1.2Ueq(C) for all the other H atoms.

Figures

Fig. 1.
The structure of the title complex, showing 50% displacement ellipsoids for non-H atoms. The H atoms are depicted by circles of arbitrary radius.
Fig. 2.
A packing diagram of the title compound showing the intermolecular hydrogen bonds (dashed lines).

Crystal data

[ZnCl2(C12H18N2O2)]F(000) = 736
Mr = 358.55Dx = 1.581 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4320 reflections
a = 8.5621 (6) Åθ = 2.4–26.0°
b = 16.9642 (12) ŵ = 1.98 mm1
c = 13.1106 (7) ÅT = 298 K
β = 127.732 (3)°Block, brown
V = 1506.08 (17) Å30.32 × 0.25 × 0.22 mm
Z = 4

Data collection

Bruker SMART APEXII diffractometer2960 independent reflections
Radiation source: fine-focus sealed tube2439 reflections with I > 2σ(I)
graphiteRint = 0.030
ω scansθmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)h = −10→9
Tmin = 0.552, Tmax = 0.649k = −20→20
8355 measured reflectionsl = −10→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0461P)2] where P = (Fo2 + 2Fc2)/3
2960 reflections(Δ/σ)max = 0.001
175 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = −0.34 e Å3
0 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Zn10.68123 (3)0.747503 (13)0.52685 (2)0.02988 (10)
Cl10.60094 (9)0.72171 (4)0.65804 (6)0.04492 (16)
Cl20.86631 (8)0.65127 (4)0.53283 (6)0.04647 (17)
O10.7870 (2)0.85437 (8)0.55417 (13)0.0336 (3)
O20.9469 (2)0.99419 (9)0.62283 (15)0.0432 (4)
N10.1190 (3)0.63462 (11)0.31873 (17)0.0357 (4)
H10.01100.62590.23580.043*
N20.4369 (2)0.76199 (10)0.34509 (17)0.0285 (4)
C10.1242 (4)0.57202 (15)0.4010 (2)0.0512 (6)
H1A0.00340.57320.39100.077*
H1B0.23360.58130.48970.077*
H1C0.13880.52140.37510.077*
C20.0953 (3)0.71360 (15)0.3580 (2)0.0442 (6)
H2A0.08000.75300.29990.066*
H2B0.21010.72530.44410.066*
H2C−0.01940.71330.35520.066*
C30.2983 (3)0.62794 (13)0.3237 (2)0.0364 (5)
H3A0.29120.57860.28370.044*
H3B0.41440.62580.41340.044*
C40.3242 (3)0.69479 (13)0.2580 (2)0.0354 (5)
H4A0.39210.67490.22530.043*
H4B0.19510.71320.18500.043*
C50.3886 (3)0.83097 (13)0.2944 (2)0.0324 (5)
H50.27680.83380.20870.039*
C60.4879 (3)0.90494 (12)0.35490 (19)0.0302 (5)
C70.3821 (3)0.97261 (14)0.2809 (2)0.0393 (5)
H70.25820.96660.20180.047*
C80.4579 (4)1.04639 (14)0.3232 (2)0.0432 (6)
H80.38411.09030.27500.052*
C90.6463 (3)1.05555 (13)0.4387 (2)0.0397 (5)
H90.69881.10590.46740.048*
C100.7563 (3)0.99069 (12)0.5115 (2)0.0321 (5)
C110.6771 (3)0.91289 (12)0.47493 (19)0.0280 (4)
C121.0452 (4)1.06907 (14)0.6573 (3)0.0537 (7)
H12A0.98711.10440.68280.081*
H12B1.03141.09070.58450.081*
H12C1.18271.06220.72760.081*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.02911 (15)0.02351 (15)0.03349 (16)−0.00104 (9)0.01735 (12)0.00050 (9)
Cl10.0429 (3)0.0566 (4)0.0423 (3)0.0001 (3)0.0297 (3)0.0034 (3)
Cl20.0428 (3)0.0418 (3)0.0553 (4)0.0101 (3)0.0303 (3)−0.0005 (3)
O10.0304 (7)0.0224 (8)0.0340 (8)−0.0004 (6)0.0126 (6)0.0016 (6)
O20.0423 (9)0.0256 (8)0.0426 (9)−0.0090 (7)0.0163 (8)−0.0024 (7)
N10.0308 (9)0.0373 (11)0.0342 (10)−0.0060 (8)0.0175 (8)−0.0036 (8)
N20.0267 (8)0.0282 (10)0.0314 (9)−0.0047 (7)0.0183 (8)−0.0039 (7)
C10.0598 (16)0.0482 (16)0.0506 (15)−0.0093 (12)0.0363 (14)0.0020 (12)
C20.0353 (12)0.0465 (15)0.0497 (14)0.0028 (11)0.0254 (11)−0.0053 (11)
C30.0323 (11)0.0282 (12)0.0454 (13)−0.0019 (9)0.0220 (10)−0.0063 (9)
C40.0360 (11)0.0366 (13)0.0353 (12)−0.0084 (9)0.0227 (10)−0.0113 (9)
C50.0286 (10)0.0379 (13)0.0312 (11)0.0001 (9)0.0186 (9)0.0028 (9)
C60.0325 (10)0.0273 (11)0.0343 (11)0.0011 (8)0.0222 (9)0.0028 (8)
C70.0364 (12)0.0376 (13)0.0380 (12)0.0038 (10)0.0197 (10)0.0080 (10)
C80.0462 (14)0.0292 (13)0.0490 (14)0.0094 (10)0.0264 (12)0.0145 (10)
C90.0508 (14)0.0250 (12)0.0480 (14)−0.0013 (10)0.0326 (12)0.0041 (10)
C100.0364 (12)0.0264 (11)0.0334 (11)−0.0013 (9)0.0214 (10)0.0004 (9)
C110.0317 (10)0.0260 (11)0.0315 (11)0.0007 (8)0.0219 (9)0.0027 (8)
C120.0561 (16)0.0275 (14)0.0609 (17)−0.0159 (11)0.0272 (14)−0.0082 (11)

Geometric parameters (Å, °)

Zn1—O11.9590 (14)C3—C41.521 (3)
Zn1—N22.0034 (18)C3—H3A0.9700
Zn1—Cl22.2429 (6)C3—H3B0.9700
Zn1—Cl12.2516 (6)C4—H4A0.9700
O1—C111.324 (2)C4—H4B0.9700
O2—C101.372 (3)C5—C61.450 (3)
O2—C121.435 (3)C5—H50.9300
N1—C21.493 (3)C6—C111.414 (3)
N1—C11.495 (3)C6—C71.415 (3)
N1—C31.500 (3)C7—C81.362 (3)
N1—H10.9100C7—H70.9300
N2—C51.283 (3)C8—C91.389 (3)
N2—C41.479 (3)C8—H80.9300
C1—H1A0.9600C9—C101.381 (3)
C1—H1B0.9600C9—H90.9300
C1—H1C0.9600C10—C111.426 (3)
C2—H2A0.9600C12—H12A0.9600
C2—H2B0.9600C12—H12B0.9600
C2—H2C0.9600C12—H12C0.9600
O1—Zn1—N297.67 (6)H3A—C3—H3B107.5
O1—Zn1—Cl2115.44 (5)N2—C4—C3112.94 (18)
N2—Zn1—Cl2109.39 (5)N2—C4—H4A109.0
O1—Zn1—Cl1111.30 (5)C3—C4—H4A109.0
N2—Zn1—Cl1110.35 (5)N2—C4—H4B109.0
Cl2—Zn1—Cl1111.80 (3)C3—C4—H4B109.0
C11—O1—Zn1121.55 (13)H4A—C4—H4B107.8
C10—O2—C12117.37 (18)N2—C5—C6127.7 (2)
C2—N1—C1109.82 (19)N2—C5—H5116.2
C2—N1—C3113.83 (16)C6—C5—H5116.2
C1—N1—C3109.71 (18)C11—C6—C7120.1 (2)
C2—N1—H1107.8C11—C6—C5125.47 (19)
C1—N1—H1107.8C7—C6—C5114.34 (19)
C3—N1—H1107.8C8—C7—C6121.4 (2)
C5—N2—C4116.87 (19)C8—C7—H7119.3
C5—N2—Zn1119.94 (14)C6—C7—H7119.3
C4—N2—Zn1122.48 (14)C7—C8—C9119.5 (2)
N1—C1—H1A109.5C7—C8—H8120.2
N1—C1—H1B109.5C9—C8—H8120.2
H1A—C1—H1B109.5C10—C9—C8120.7 (2)
N1—C1—H1C109.5C10—C9—H9119.7
H1A—C1—H1C109.5C8—C9—H9119.7
H1B—C1—H1C109.5O2—C10—C9124.4 (2)
N1—C2—H2A109.5O2—C10—C11114.14 (18)
N1—C2—H2B109.5C9—C10—C11121.5 (2)
H2A—C2—H2B109.5O1—C11—C6125.57 (19)
N1—C2—H2C109.5O1—C11—C10117.83 (18)
H2A—C2—H2C109.5C6—C11—C10116.59 (18)
H2B—C2—H2C109.5O2—C12—H12A109.5
N1—C3—C4114.78 (18)O2—C12—H12B109.5
N1—C3—H3A108.6H12A—C12—H12B109.5
C4—C3—H3A108.6O2—C12—H12C109.5
N1—C3—H3B108.6H12A—C12—H12C109.5
C4—C3—H3B108.6H12B—C12—H12C109.5
N2—Zn1—O1—C1114.33 (16)C11—C6—C7—C8−0.5 (3)
Cl2—Zn1—O1—C11130.12 (14)C5—C6—C7—C8−178.3 (2)
Cl1—Zn1—O1—C11−101.07 (15)C6—C7—C8—C92.7 (4)
O1—Zn1—N2—C5−8.41 (17)C7—C8—C9—C10−0.6 (4)
Cl2—Zn1—N2—C5−128.86 (16)C12—O2—C10—C9−7.6 (3)
Cl1—Zn1—N2—C5107.74 (16)C12—O2—C10—C11172.5 (2)
O1—Zn1—N2—C4161.59 (15)C8—C9—C10—O2176.4 (2)
Cl2—Zn1—N2—C441.14 (16)C8—C9—C10—C11−3.7 (3)
Cl1—Zn1—N2—C4−82.26 (15)Zn1—O1—C11—C6−9.9 (3)
C2—N1—C3—C4−48.9 (2)Zn1—O1—C11—C10171.41 (14)
C1—N1—C3—C4−172.44 (19)C7—C6—C11—O1177.8 (2)
C5—N2—C4—C3−146.55 (19)C5—C6—C11—O1−4.7 (3)
Zn1—N2—C4—C343.2 (2)C7—C6—C11—C10−3.5 (3)
N1—C3—C4—N288.5 (2)C5—C6—C11—C10174.0 (2)
C4—N2—C5—C6−173.07 (19)O2—C10—C11—O14.4 (3)
Zn1—N2—C5—C6−2.5 (3)C9—C10—C11—O1−175.5 (2)
N2—C5—C6—C1112.0 (4)O2—C10—C11—C6−174.43 (18)
N2—C5—C6—C7−170.4 (2)C9—C10—C11—C65.6 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.911.972.842 (2)161
N1—H1···O2i0.912.382.985 (2)124
C5—H5···Cl2i0.932.803.617 (2)148

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2237).

References

  • Bruker (2004). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Qiu, X.-Y. (2006). Acta Cryst. E62, m2173–m2174.
  • Sheldrick, G. M. (2003). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, Q. & Qiu, X.-Y. (2006). Acta Cryst. E62, m3002–m3003.
  • Ye, L.-J. & You, Z. (2008). Acta Cryst. E64, m869. [PMC free article] [PubMed]
  • You, Z.-L. (2005a). Acta Cryst. E61, m2416–m2418.
  • You, Z.-L. (2005b). Acta Cryst. C61, m383–m385. [PubMed]
  • Zhu, X.-W. (2008). Acta Cryst. E64, m1456–m1457. [PMC free article] [PubMed]

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