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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2011 Jan 26;67(Pt 2):m261. doi: 10.1107/S1600536811002753

Dibromido{2-morpholino-N-[1-(2-pyrid­yl)ethyl­idene]ethanamine-κ3 N,N′,N′′}zinc(II)

Yan-Wei Ding a,*, Xiao-Ling Wang a, Li-Li Ni b
PMCID: PMC3051576  PMID: 21522912

Abstract

In the title complex, [ZnBr2(C13H19N3O)], the ZnII atom is five-coordinated by the three N-donor atoms of the Schiff base ligand and by two Br atoms in a distorted square-pyramidal geometry. The morpholine ring adopts a chair conformation.

Related literature

For background to Schiff base complexes, see: Dhar & Chakravarty (2003 ▶); Das et al. (2006 ▶); Nayak et al. (2006 ▶). For the crystal structures of similar Schiff base–zinc(II) complexes, see: Wang (2010 ▶); Zhu et al. (2007 ▶); Li & Zhang (2004 ▶); Zhu & Yang (2008 ▶).graphic file with name e-67-0m261-scheme1.jpg

Experimental

Crystal data

  • [ZnBr2(C13H19N3O)]

  • M r = 458.50

  • Monoclinic, Inline graphic

  • a = 9.831 (4) Å

  • b = 13.985 (6) Å

  • c = 12.183 (5) Å

  • β = 106.626 (4)°

  • V = 1604.9 (11) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 6.51 mm−1

  • T = 298 K

  • 0.35 × 0.32 × 0.32 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.209, T max = 0.230

  • 12426 measured reflections

  • 3411 independent reflections

  • 2159 reflections with I > 2σ(I)

  • R int = 0.108

Refinement

  • R[F 2 > 2σ(F 2)] = 0.065

  • wR(F 2) = 0.177

  • S = 1.05

  • 3411 reflections

  • 182 parameters

  • H-atom parameters constrained

  • Δρmax = 1.35 e Å−3

  • Δρmin = −1.26 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811002753/su2250sup1.cif

e-67-0m261-sup1.cif (17KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002753/su2250Isup2.hkl

e-67-0m261-Isup2.hkl (167.3KB, hkl)

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

supplementary crystallographic information

Comment

In the last few years, considerable attention has focused on the preparation and properties of Schiff base complexes (Dhar & Chakravarty, 2003; Das et al., 2006; Nayak et al., 2006). Herein we report on the crystal structure of a new Schiff base zinc(II) complex.

The molecular structure of the title mononuclear zinc(II) complex is shown in Fig. 1. The Zn atom is five-coordinated by the three N-donor atoms of the Schiff base ligand, and by two Br atoms in a distorted square-pyramidal geometry. All the coordinate bond lengths are within normal values and are comparable to those in similar zinc(II) complexes with Schiff bases (Wang, 2010; Zhu et al., 2007; Li & Zhang, 2004; Zhu & Yang, 2008). As expected, the morpholine ring adopts a chair conformation.

Experimental

The title complex was prepared by the reaction of 2-acetylpyridine (0.20 g, 1.65 mmol), 4-(2-aminoethyl)morpholine (0.21 g, 1.65 mmol), and zinc bromide (0.37 g, 1.65 mmol) in methanol at ambient temperature. Colourless block-like single crytals were formed by slow evaporation of the solution in air.

Refinement

The C-bound H-atoms were included in calculated positions and treated as riding atoms: C-H = 0.93, 0.97 and 0.96 Å for CH, CH2 and CH3 H-atoms, respectively, with Uiso(H) = k × Ueq(C), where k = 1.2 for CH and CH2 H-atoms, and 1.5 for CH3 H-atoms. The highest residual density peak, 1.35 e Å-2, is 0.58 Å from atom Zn1, while the deepest residual density hole, -1.26 e Å-2, is 0.62 Å from atom Br1.

Figures

Fig. 1.

Fig. 1.

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Molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

Crystal data

[ZnBr2(C13H19N3O)] F(000) = 904
Mr = 458.50 Dx = 1.898 Mg m−3
Monoclinic, P21/n Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn Cell parameters from 1887 reflections
a = 9.831 (4) Å θ = 2.3–25.1°
b = 13.985 (6) Å µ = 6.51 mm−1
c = 12.183 (5) Å T = 298 K
β = 106.626 (4)° Block, colourless
V = 1604.9 (11) Å3 0.35 × 0.32 × 0.32 mm
Z = 4
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Data collection

Bruker SMART CCD area-detector diffractometer 3411 independent reflections
Radiation source: fine-focus sealed tube 2159 reflections with I > 2σ(I)
graphite Rint = 0.108
ω scans θmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001) h = −12→12
Tmin = 0.209, Tmax = 0.230 k = −17→17
12426 measured reflections l = −15→15
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Refinement

Refinement on F2 Primary atom site location: structure-invariant direct methods
Least-squares matrix: full Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065 Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177 H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0584P)2 + 5.9893P] where P = (Fo2 + 2Fc2)/3
3411 reflections (Δ/σ)max < 0.001
182 parameters Δρmax = 1.35 e Å−3
0 restraints Δρmin = −1.26 e Å−3
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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 covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) 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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
Zn1 0.27265 (9) 0.91109 (6) 0.83908 (8) 0.0207 (3)
Br1 0.45896 (10) 0.79761 (8) 0.87089 (9) 0.0448 (3)
Br2 0.04314 (10) 0.86043 (7) 0.72941 (9) 0.0418 (3)
O1 0.3163 (7) 0.9365 (6) 0.4853 (6) 0.0490 (19)
N1 0.2385 (7) 0.8835 (5) 1.0100 (6) 0.0247 (16)
N2 0.2537 (7) 1.0444 (5) 0.9095 (6) 0.0252 (16)
N3 0.3418 (6) 1.0118 (5) 0.7105 (5) 0.0227 (15)
C1 0.1995 (7) 0.9617 (6) 1.0565 (6) 0.0210 (18)
C2 0.1623 (9) 0.9559 (7) 1.1573 (7) 0.033 (2)
H2 0.1349 1.0105 1.1889 0.040*
C3 0.1660 (11) 0.8680 (8) 1.2116 (8) 0.044 (3)
H3 0.1394 0.8630 1.2788 0.053*
C4 0.2089 (10) 0.7900 (8) 1.1649 (8) 0.042 (3)
H4 0.2155 0.7307 1.2006 0.051*
C5 0.2422 (10) 0.8003 (7) 1.0642 (8) 0.036 (2)
H5 0.2690 0.7460 1.0314 0.043*
C6 0.2071 (8) 1.0522 (6) 0.9937 (7) 0.0251 (19)
C7 0.1620 (9) 1.1447 (6) 1.0362 (8) 0.036 (2)
H7A 0.2439 1.1770 1.0840 0.054*
H7B 0.0967 1.1315 1.0797 0.054*
H7C 0.1167 1.1847 0.9721 0.054*
C8 0.2824 (10) 1.1260 (6) 0.8452 (8) 0.036 (2)
H8A 0.3204 1.1785 0.8969 0.043*
H8B 0.1954 1.1472 0.7902 0.043*
C9 0.3870 (10) 1.0959 (6) 0.7849 (8) 0.037 (2)
H9A 0.4031 1.1489 0.7388 0.045*
H9B 0.4764 1.0815 0.8414 0.045*
C10 0.4615 (9) 0.9792 (7) 0.6732 (8) 0.038 (2)
H10A 0.5339 0.9538 0.7384 0.045*
H10B 0.5020 1.0331 0.6434 0.045*
C11 0.4195 (12) 0.9037 (7) 0.5826 (9) 0.046 (3)
H11A 0.5026 0.8835 0.5610 0.055*
H11B 0.3829 0.8487 0.6135 0.055*
C12 0.1956 (11) 0.9629 (8) 0.5184 (8) 0.048 (3)
H12A 0.1594 0.9073 0.5485 0.057*
H12B 0.1223 0.9850 0.4516 0.057*
C13 0.2283 (9) 1.0409 (7) 0.6081 (8) 0.036 (2)
H13A 0.2573 1.0982 0.5759 0.043*
H13B 0.1432 1.0558 0.6298 0.043*
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
Zn1 0.0158 (5) 0.0246 (5) 0.0212 (5) −0.0006 (4) 0.0046 (4) −0.0044 (4)
Br1 0.0322 (6) 0.0540 (7) 0.0475 (7) 0.0094 (5) 0.0102 (5) 0.0007 (5)
Br2 0.0264 (5) 0.0500 (6) 0.0486 (7) −0.0049 (4) 0.0101 (4) −0.0081 (5)
O1 0.038 (4) 0.083 (5) 0.030 (4) 0.004 (4) 0.016 (3) −0.002 (4)
N1 0.022 (4) 0.032 (4) 0.019 (4) 0.004 (3) 0.004 (3) −0.001 (3)
N2 0.024 (4) 0.027 (4) 0.022 (4) 0.000 (3) 0.001 (3) −0.004 (3)
N3 0.018 (3) 0.028 (4) 0.020 (4) −0.003 (3) 0.004 (3) 0.005 (3)
C1 0.007 (4) 0.037 (5) 0.015 (4) 0.000 (3) −0.003 (3) −0.005 (3)
C2 0.025 (5) 0.049 (6) 0.027 (5) −0.005 (4) 0.007 (4) −0.015 (4)
C3 0.046 (6) 0.070 (8) 0.014 (5) −0.009 (5) 0.006 (4) 0.002 (5)
C4 0.052 (6) 0.049 (6) 0.025 (5) −0.006 (5) 0.010 (5) 0.009 (5)
C5 0.035 (5) 0.034 (5) 0.036 (6) 0.006 (4) 0.007 (4) 0.000 (4)
C6 0.021 (4) 0.028 (4) 0.023 (5) −0.003 (3) 0.002 (4) −0.010 (4)
C7 0.028 (5) 0.034 (5) 0.047 (6) 0.010 (4) 0.014 (4) −0.012 (4)
C8 0.051 (6) 0.026 (5) 0.031 (5) −0.008 (4) 0.012 (5) −0.006 (4)
C9 0.040 (6) 0.032 (5) 0.037 (6) −0.023 (4) 0.006 (4) −0.002 (4)
C10 0.020 (5) 0.055 (6) 0.041 (6) −0.003 (4) 0.011 (4) 0.008 (5)
C11 0.051 (6) 0.055 (7) 0.041 (6) 0.007 (5) 0.027 (5) −0.003 (5)
C12 0.043 (6) 0.072 (8) 0.023 (5) −0.005 (5) 0.002 (5) −0.003 (5)
C13 0.030 (5) 0.042 (6) 0.035 (5) 0.002 (4) 0.007 (4) 0.008 (4)
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Geometric parameters (Å, °)

Zn1—N2 2.083 (7) C4—H4 0.9300
Zn1—N1 2.235 (7) C5—H5 0.9300
Zn1—N3 2.347 (6) C6—C7 1.507 (11)
Zn1—Br1 2.3701 (15) C7—H7A 0.9600
Zn1—Br2 2.3775 (15) C7—H7B 0.9600
O1—C11 1.398 (12) C7—H7C 0.9600
O1—C12 1.407 (12) C8—C9 1.485 (13)
N1—C5 1.334 (11) C8—H8A 0.9700
N1—C1 1.337 (10) C8—H8B 0.9700
N2—C6 1.241 (11) C9—H9A 0.9700
N2—C8 1.457 (11) C9—H9B 0.9700
N3—C10 1.451 (11) C10—C11 1.496 (13)
N3—C13 1.474 (10) C10—H10A 0.9700
N3—C9 1.474 (10) C10—H10B 0.9700
C1—C2 1.380 (12) C11—H11A 0.9700
C1—C6 1.492 (11) C11—H11B 0.9700
C2—C3 1.391 (14) C12—C13 1.512 (13)
C2—H2 0.9300 C12—H12A 0.9700
C3—C4 1.352 (14) C12—H12B 0.9700
C3—H3 0.9300 C13—H13A 0.9700
C4—C5 1.365 (13) C13—H13B 0.9700
N2—Zn1—N1 73.5 (3) C6—C7—H7B 109.5
N2—Zn1—N3 79.4 (3) H7A—C7—H7B 109.5
N1—Zn1—N3 151.0 (2) C6—C7—H7C 109.5
N2—Zn1—Br1 133.48 (18) H7A—C7—H7C 109.5
N1—Zn1—Br1 92.70 (17) H7B—C7—H7C 109.5
N3—Zn1—Br1 98.80 (16) N2—C8—C9 108.2 (7)
N2—Zn1—Br2 108.40 (19) N2—C8—H8A 110.1
N1—Zn1—Br2 95.80 (18) C9—C8—H8A 110.1
N3—Zn1—Br2 102.32 (16) N2—C8—H8B 110.1
Br1—Zn1—Br2 117.20 (6) C9—C8—H8B 110.1
C11—O1—C12 108.1 (7) H8A—C8—H8B 108.4
C5—N1—C1 118.3 (8) N3—C9—C8 113.6 (7)
C5—N1—Zn1 128.4 (6) N3—C9—H9A 108.8
C1—N1—Zn1 113.1 (5) C8—C9—H9A 108.8
C6—N2—C8 123.3 (7) N3—C9—H9B 108.8
C6—N2—Zn1 121.2 (6) C8—C9—H9B 108.8
C8—N2—Zn1 115.2 (5) H9A—C9—H9B 107.7
C10—N3—C13 107.9 (7) N3—C10—C11 112.0 (7)
C10—N3—C9 108.4 (7) N3—C10—H10A 109.2
C13—N3—C9 108.8 (7) C11—C10—H10A 109.2
C10—N3—Zn1 115.9 (5) N3—C10—H10B 109.2
C13—N3—Zn1 115.9 (5) C11—C10—H10B 109.2
C9—N3—Zn1 99.3 (5) H10A—C10—H10B 107.9
N1—C1—C2 120.6 (8) O1—C11—C10 112.0 (8)
N1—C1—C6 114.4 (7) O1—C11—H11A 109.2
C2—C1—C6 124.9 (8) C10—C11—H11A 109.2
C1—C2—C3 119.9 (9) O1—C11—H11B 109.2
C1—C2—H2 120.1 C10—C11—H11B 109.2
C3—C2—H2 120.1 H11A—C11—H11B 107.9
C4—C3—C2 118.7 (9) O1—C12—C13 112.0 (8)
C4—C3—H3 120.6 O1—C12—H12A 109.2
C2—C3—H3 120.6 C13—C12—H12A 109.2
C3—C4—C5 118.5 (9) O1—C12—H12B 109.2
C3—C4—H4 120.7 C13—C12—H12B 109.2
C5—C4—H4 120.7 H12A—C12—H12B 107.9
N1—C5—C4 123.9 (9) N3—C13—C12 111.5 (8)
N1—C5—H5 118.1 N3—C13—H13A 109.3
C4—C5—H5 118.1 C12—C13—H13A 109.3
N2—C6—C1 115.7 (7) N3—C13—H13B 109.3
N2—C6—C7 125.1 (8) C12—C13—H13B 109.3
C1—C6—C7 119.3 (8) H13A—C13—H13B 108.0
C6—C7—H7A 109.5
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2250).

References

  1. Bruker (2001). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  2. Bruker (2007). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  3. Das, S., Nag, A., Goswami, D. & Bharadwaj, P. K. (2006). J. Am. Chem. Soc. 128, 402–403. [DOI] [PubMed]
  4. Dhar, S. & Chakravarty, A. R. (2003). Inorg. Chem. 42, 2483–2485. [DOI] [PubMed]
  5. Li, Z.-X. & Zhang, X.-L. (2004). Acta Cryst. E60, m1017–m1019.
  6. Nayak, M., Koner, R., Lin, H.-H., Flörke, U., Wei, H.-H. & Mohanta, S. (2006). Inorg. Chem. 45, 10764–10773. [DOI] [PubMed]
  7. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
  8. Wang, F.-M. (2010). Acta Cryst. E66, m778–m779. [DOI] [PMC free article] [PubMed]
  9. Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
  10. Zhu, Q.-Y., Wei, Y.-J. & Wang, F.-W. (2007). Acta Cryst. E63, m1431–m1432.
  11. Zhu, X.-W. & Yang, X.-Z. (2008). Acta Cryst. E64, m1094–m1095. [DOI] [PMC free article] [PubMed]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811002753/su2250sup1.cif

e-67-0m261-sup1.cif (17KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002753/su2250Isup2.hkl

e-67-0m261-Isup2.hkl (167.3KB, hkl)

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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