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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1094–m1095.
Published online 2008 July 31. doi:  10.1107/S1600536808023660
PMCID: PMC2962000

Dibromido[N-propyl-N′-(2-pyridylmethyl­idene)ethane-1,2-diamine]zinc(II)

Abstract

The title complex, [ZnBr2(C11H17N3)], is a mononuclear zinc(II) compound derived from the Schiff base N-propyl-N′-(1-pyridin-2-ylmethyl­idene)ethane-1,2-diamine. The ZnII atom is five-coordinate, binding to the imine N, pyridine N, and amine N atoms of the Schiff base ligand and to two bromide anions in a distorted trigonal-bipyramidal coordination geometry. Adjacent mol­ecules are linked through inter­molecular N—H(...)Br hydrogen bonds, forming dimers.

Related literature

For background to the chemistry of Schiff base complexes, see: Ali et al. (2008 [triangle]); Biswas et al. (2008 [triangle]); Chen et al. (2008 [triangle]); Darensbourg & Frantz (2007 [triangle]); Habibi et al. (2007 [triangle]); Kawamoto et al. (2008 [triangle]); Lipscomb & Sträter (1996 [triangle]); Tomat et al. (2007 [triangle]); Wu et al. (2008 [triangle]); Yuan et al. (2007 [triangle]). For related structures, see: Dapporto et al. (2001 [triangle]); You & Zhu (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1094-scheme1.jpg

Experimental

Crystal data

  • [ZnBr2(C11H17N3)]
  • M r = 416.47
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1094-efi1.jpg
  • a = 8.252 (4) Å
  • b = 12.249 (5) Å
  • c = 14.726 (6) Å
  • β = 94.562 (7)°
  • V = 1483.8 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 7.02 mm−1
  • T = 298 (2) K
  • 0.32 × 0.30 × 0.30 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.212, T max = 0.227 (expected range = 0.114–0.122)
  • 12333 measured reflections
  • 3378 independent reflections
  • 2167 reflections with I > 2σ(I)
  • R int = 0.083

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.105
  • S = 1.01
  • 3378 reflections
  • 159 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.91 e Å−3
  • Δρmin = −0.80 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808023660/sj2523sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023660/sj2523Isup2.hkl

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

supplementary crystallographic information

Comment

Schiff bases have widely been used as versatile ligands in coordination chemistry (Biswas et al., 2008; Wu et al., 2008; Kawamoto et al., 2008; Ali et al., 2008; Habibi et al., 2007), and their metal complexes are of great interest in many fields (Chen et al., 2008; Yuan et al., 2007; Tomat et al., 2007; Darensbourg & Frantz, 2007). Zinc(II) is an important element in biological systems, functions as the active site of hydrolytic enzymes, such as carboxypeptidase and carbonic anhydrase where it is in a hard-donor coordination environment of nitrogen and oxygen ligands (Lipscomb & Sträter, 1996). In this paper, a new zinc(II) complex, (I), Fig. 1, with the Schiff base ligand N-propyl-N'-(1-pyridin-2-ylmethylidene)ethane-1,2-diamine has been synthesized and structurally characterized.

The ZnII atom in (I) is five-coordinated by one imine N, one pyridine N, and one amine N atoms of the Schiff base ligand, and by two Br- anions, in a distorted trigonal-bipyramidal coordination geometry. The coordinate bond lengths (Table 1) are typical and comparable to the corresponding values observed in similar zinc(II) Schiff base complexes (You & Zhu, 2006; Dapporto et al., 2001). The bond angle N1—Zn1—N3 in the complex is 149.43 (15)° indicating a significant distortion from trigonal-bipyramidal coordination.

In the crystal structure, adjacent molecules are linked through intermolecular N–H···Br hydrogen bonds (Table 2), forming dimers (Fig. 2).

Experimental

The Schiff base compound was prepared by the condensation of equimolar amounts of pyridine-2-carbaldehyde with N-propylethane-1,2-diamine in a methanol solution. The complex was prepared by the following method. To an anhydrous methanol solution (5 ml) of ZnBr2 (22.5 mg, 0.1 mmol) was added a methanol solution (10 ml) of the Schiff base compound (19.1 mg, 0.1 mmol) with stirring. The mixture was stirred for 30 min at room temperature and filtered. Upon keeping the filtrate in air for a few days, colorless block-shaped crystals formed at the bottom of the vessel on slow evaporation of the solvent.

Refinement

H3A attached to N3 was located from a difference Fourier map and refined isotropically, with the N–H distance restrained to 0.90 (1) Å, and with Uiso(H) fixed at 0.08 Å2. Other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C–H distances in the range 0.93–0.97Å and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I) with ellipsoids drawn at the 30% probability level.
Fig. 2.
The crystal packing of (I), viewed along the a axis.

Crystal data

[ZnBr2(C11H17N3)]F000 = 816
Mr = 416.47Dx = 1.864 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1994 reflections
a = 8.252 (4) Åθ = 2.2–25.3º
b = 12.249 (5) ŵ = 7.02 mm1
c = 14.726 (6) ÅT = 298 (2) K
β = 94.562 (7)ºBlock, colorless
V = 1483.8 (11) Å30.32 × 0.30 × 0.30 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer3378 independent reflections
Radiation source: fine-focus sealed tube2167 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.083
T = 298(2) Kθmax = 27.5º
ω scansθmin = 2.2º
Absorption correction: multi-scan(SADABS; Sheldrick, 2004)h = −10→10
Tmin = 0.212, Tmax = 0.227k = −15→15
12333 measured reflectionsl = −18→19

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105  w = 1/[σ2(Fo2) + (0.0211P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
3378 reflectionsΔρmax = 0.91 e Å3
159 parametersΔρmin = −0.80 e Å3
1 restraintExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0140 (7)

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.

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

xyzUiso*/Ueq
Zn10.04170 (7)0.30316 (4)0.86078 (4)0.02971 (19)
Br1−0.19476 (6)0.34399 (5)0.94074 (4)0.0454 (2)
Br20.00560 (8)0.29983 (5)0.69779 (4)0.0524 (2)
N10.0385 (5)0.1154 (3)0.8679 (3)0.0359 (10)
N20.2385 (5)0.2563 (3)0.9510 (3)0.0338 (10)
N30.1741 (5)0.4581 (3)0.8836 (3)0.0296 (9)
C10.1561 (6)0.0745 (4)0.9254 (3)0.0351 (12)
C20.1774 (8)−0.0353 (4)0.9398 (4)0.0495 (15)
H20.2599−0.06110.98100.059*
C30.0742 (9)−0.1061 (5)0.8922 (5)0.0606 (18)
H30.0849−0.18110.90090.073*
C4−0.0449 (8)−0.0652 (5)0.8318 (5)0.0575 (17)
H4−0.1150−0.11170.79780.069*
C5−0.0591 (7)0.0466 (5)0.8222 (4)0.0489 (15)
H5−0.14120.07430.78180.059*
C60.2635 (6)0.1575 (4)0.9712 (4)0.0367 (12)
H60.34740.13731.01380.044*
C70.3456 (6)0.3442 (4)0.9865 (4)0.0396 (13)
H7A0.45530.31721.00030.048*
H7B0.30680.37451.04170.048*
C80.3422 (6)0.4295 (4)0.9126 (4)0.0375 (13)
H8A0.40040.49410.93520.045*
H8B0.39580.40160.86110.045*
C90.1638 (6)0.5399 (4)0.8098 (4)0.0400 (13)
H9A0.19390.50610.75400.048*
H9B0.24040.59840.82520.048*
C10−0.0046 (6)0.5869 (4)0.7943 (4)0.0426 (14)
H10A−0.08250.52780.78570.051*
H10B−0.02980.62770.84780.051*
C11−0.0207 (7)0.6607 (5)0.7126 (4)0.0641 (19)
H11A0.06630.71290.71670.096*
H11B−0.12300.69830.71080.096*
H11C−0.01580.61800.65820.096*
H3A0.130 (7)0.491 (4)0.930 (3)0.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0321 (3)0.0296 (3)0.0266 (3)0.0004 (2)−0.0029 (2)−0.0032 (3)
Br10.0399 (3)0.0451 (4)0.0526 (4)−0.0043 (2)0.0125 (3)−0.0179 (3)
Br20.0811 (5)0.0481 (4)0.0263 (3)0.0018 (3)−0.0070 (3)−0.0066 (3)
N10.043 (3)0.033 (2)0.031 (3)−0.003 (2)0.002 (2)−0.001 (2)
N20.039 (3)0.032 (2)0.029 (2)0.000 (2)−0.003 (2)0.001 (2)
N30.036 (2)0.027 (2)0.026 (2)−0.0041 (17)0.0009 (19)−0.0019 (18)
C10.046 (3)0.031 (3)0.029 (3)0.002 (2)0.010 (2)0.005 (2)
C20.065 (4)0.035 (3)0.050 (4)0.007 (3)0.013 (3)0.009 (3)
C30.087 (5)0.028 (3)0.071 (5)0.002 (3)0.032 (4)0.004 (3)
C40.070 (4)0.037 (4)0.067 (5)−0.010 (3)0.019 (4)−0.010 (3)
C50.044 (3)0.047 (4)0.056 (4)−0.006 (3)0.000 (3)−0.011 (3)
C60.041 (3)0.038 (3)0.030 (3)0.008 (2)−0.002 (2)0.000 (2)
C70.042 (3)0.040 (3)0.035 (3)−0.001 (2)−0.011 (3)−0.002 (3)
C80.037 (3)0.033 (3)0.041 (3)−0.008 (2)−0.002 (2)−0.003 (3)
C90.046 (3)0.033 (3)0.041 (3)−0.009 (2)0.005 (3)0.004 (3)
C100.044 (3)0.032 (3)0.052 (4)0.002 (2)0.003 (3)0.007 (3)
C110.065 (4)0.054 (4)0.071 (5)0.004 (3)−0.004 (4)0.030 (3)

Geometric parameters (Å, °)

Zn1—N22.095 (4)C4—C51.380 (8)
Zn1—N32.202 (4)C4—H40.9300
Zn1—N12.303 (4)C5—H50.9300
Zn1—Br22.3954 (13)C6—H60.9300
Zn1—Br12.4102 (11)C7—C81.508 (7)
N1—C51.313 (6)C7—H7A0.9700
N1—C11.334 (6)C7—H7B0.9700
N2—C61.259 (6)C8—H8A0.9700
N2—C71.463 (6)C8—H8B0.9700
N3—C81.461 (6)C9—C101.505 (7)
N3—C91.477 (6)C9—H9A0.9700
N3—H3A0.90 (5)C9—H9B0.9700
C1—C21.371 (7)C10—C111.501 (7)
C1—C61.475 (7)C10—H10A0.9700
C2—C31.369 (8)C10—H10B0.9700
C2—H20.9300C11—H11A0.9600
C3—C41.367 (8)C11—H11B0.9600
C3—H30.9300C11—H11C0.9600
N2—Zn1—N377.83 (16)N1—C5—H5118.7
N2—Zn1—N173.04 (15)C4—C5—H5118.7
N3—Zn1—N1149.43 (15)N2—C6—C1118.2 (5)
N2—Zn1—Br2131.24 (11)N2—C6—H6120.9
N3—Zn1—Br2100.86 (11)C1—C6—H6120.9
N1—Zn1—Br291.57 (11)N2—C7—C8106.0 (4)
N2—Zn1—Br1111.33 (12)N2—C7—H7A110.5
N3—Zn1—Br199.08 (11)C8—C7—H7A110.5
N1—Zn1—Br199.94 (11)N2—C7—H7B110.5
Br2—Zn1—Br1116.88 (4)C8—C7—H7B110.5
C5—N1—C1118.1 (5)H7A—C7—H7B108.7
C5—N1—Zn1128.8 (4)N3—C8—C7109.8 (4)
C1—N1—Zn1113.1 (3)N3—C8—H8A109.7
C6—N2—C7122.7 (4)C7—C8—H8A109.7
C6—N2—Zn1121.2 (3)N3—C8—H8B109.7
C7—N2—Zn1116.1 (3)C7—C8—H8B109.7
C8—N3—C9112.0 (4)H8A—C8—H8B108.2
C8—N3—Zn1106.6 (3)N3—C9—C10111.7 (4)
C9—N3—Zn1118.3 (3)N3—C9—H9A109.3
C8—N3—H3A109 (4)C10—C9—H9A109.3
C9—N3—H3A105 (4)N3—C9—H9B109.3
Zn1—N3—H3A106 (4)C10—C9—H9B109.3
N1—C1—C2122.9 (5)H9A—C9—H9B107.9
N1—C1—C6114.3 (4)C11—C10—C9111.9 (5)
C2—C1—C6122.7 (5)C11—C10—H10A109.2
C3—C2—C1118.4 (6)C9—C10—H10A109.2
C3—C2—H2120.8C11—C10—H10B109.2
C1—C2—H2120.8C9—C10—H10B109.2
C4—C3—C2119.1 (6)H10A—C10—H10B107.9
C4—C3—H3120.5C10—C11—H11A109.5
C2—C3—H3120.5C10—C11—H11B109.5
C3—C4—C5118.8 (6)H11A—C11—H11B109.5
C3—C4—H4120.6C10—C11—H11C109.5
C5—C4—H4120.6H11A—C11—H11C109.5
N1—C5—C4122.7 (6)H11B—C11—H11C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3A···Br1i0.90 (5)2.80 (4)3.539 (4)141 (5)

Symmetry codes: (i) −x, −y+1, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2523).

References

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