Dibromido{2-[1-(cyclo­propyl­imino)­eth­yl]pyridine}­zinc(II)

Yue, S.-Y.; Lu, J.-F.

doi:10.1107/S1600536810025201

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page m880

https://doi.org/10.1107/S1600536810025201

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Dibromido{2-[1-(cyclopropylimino)ethyl]pyridine}zinc(II)

Si-Yu Yue ^a and Jiu-Fu Lu ^a ^*

^aSchool of Chemistry and Environmental Science, Shaanxi University of Technology, Hanzhong 723000, People's Republic of China
^*Correspondence e-mail: jiufulu@163.com

(Received 25 June 2010; accepted 27 June 2010; online 3 July 2010)

In the title compound, [ZnBr₂(C₁₀H₁₂N₂)], the Zn²⁺ ion is coordinated by the N,N′-bidentate Schiff base ligand and two bromode ions in a distorted tetrahedral arrangement. The dihedral angle between the pyridine and the cyclopropyl rings is 95.4 (8)°.

Related literature

For background to Schiff bases as chelating ligands, see: Hamaker et al. (2010 ); Wang et al. (2010 ); Mirkhani et al. (2010 ); Liu & Yang (2009 ). For similar zinc complexes, see: Zakrzewski & Lingafelter (1970 ); Gourbatsis et al. (1999 ); Merino et al. (2001 ); Majumder et al. (2006 ).

Experimental

Crystal data

[ZnBr₂(C₁₀H₁₂N₂)]
M_r = 385.41
Monoclinic, P 2₁
a = 7.029 (3) Å
b = 14.090 (3) Å
c = 7.037 (2) Å
β = 111.820 (3)°
V = 647.0 (4) Å³
Z = 2
Mo Kα radiation
μ = 8.04 mm⁻¹
T = 298 K
0.23 × 0.23 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.259, T_max = 0.283
4060 measured reflections
2408 independent reflections
1708 reflections with I > 2σ(I)
R_int = 0.104

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.165
S = 0.95
2408 reflections
137 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.96 e Å⁻³
Δρ_min = −1.09 e Å⁻³
Absolute structure: Flack (1983 ), 957 Friedel pairs
Flack parameter: −0.05 (3)

Table 1
Selected bond lengths (Å)

Zn1—N1	2.041 (9)
Zn1—N2	2.073 (10)
Zn1—Br1	2.3488 (18)
Zn1—Br2	2.3616 (19)

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810025201/hb5526sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810025201/hb5526Isup2.hkl

checkCIF report

Comment top

Schiff bases have often been used as chelating ligands in coordination chemistry (Hamaker et al., 2010; Wang et al., 2010; Mirkhani et al., 2010; Liu & Yang, 2009). We report here the crystal structure of the title new zinc complex with the chelating Schiff base ligand cyclopropyl-(1-pyridin-2-ylethylidene)amine.

The Zn atom in the complex is four-coordinated by one pyridine N and one imine N atoms of the Schiff base ligand, and by two bromide atoms, forming a tetrahedral geometry (Fig. 1). The dihedral angle between the pyridine and the cyclopropyl rings is 95.4 (8)°. The bond lengths (Table 1) related to the Zn atom are comparable to those observed in similar zinc complexes (Zakrzewski & Lingafelter, 1970; Gourbatsis et al., 1999; Merino et al., 2001; Majumder et al., 2006).

Related literature top

For background to Schiff bases as chelating ligands, see: Hamaker et al. (2010); Wang et al. (2010); Mirkhani et al. (2010); Liu & Yang (2009). For similar zinc complexes, see: Zakrzewski & Lingafelter (1970); Gourbatsis et al. (1999); Merino et al. (2001); Majumder et al. (2006).

Experimental top

2-Acetylpyridine (0.1 mmol, 12.1 mg) and cyclopropylamine (0.1 mmol, 5.7 mg) were mixed and stirred in methanol (10 ml) for 30 min. Then a methanol solution (5 ml) of zinc bromide (0.1 mmol, 22.5 mg) was added to the mixture. The final mixture was stirred for another 30 min to give a colourless solution. Colourless blocks of (I) were obtained by slow evaporation of the solution at room temperature.

Structure description top

For background to Schiff bases as chelating ligands, see: Hamaker et al. (2010); Wang et al. (2010); Mirkhani et al. (2010); Liu & Yang (2009). For similar zinc complexes, see: Zakrzewski & Lingafelter (1970); Gourbatsis et al. (1999); Merino et al. (2001); Majumder et al. (2006).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title complex, showing 30% probability displacement ellipsoids.

Dibromido{2-[1-(cyclopropylimino)ethyl]pyridine}zinc(II) top

Crystal data top

[ZnBr₂(C₁₀H₁₂N₂)]	F(000) = 372
M_r = 385.41	D_x = 1.978 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.029 (3) Å	Cell parameters from 1405 reflections
b = 14.090 (3) Å	θ = 2.8–25.0°
c = 7.037 (2) Å	µ = 8.04 mm⁻¹
β = 111.820 (3)°	T = 298 K
V = 647.0 (4) Å³	Block, colourless
Z = 2	0.23 × 0.23 × 0.21 mm

Data collection top

Bruker APEXII CCD diffractometer	2408 independent reflections
Radiation source: fine-focus sealed tube	1708 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.104
ω scans	θ_max = 27.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −8→8
T_min = 0.259, T_max = 0.283	k = −18→17
4060 measured reflections	l = −8→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.165	w = 1/[σ²(F_o²) + (0.0966P)²] where P = (F_o² + 2F_c²)/3
S = 0.95	(Δ/σ)_max < 0.001
2408 reflections	Δρ_max = 0.96 e Å⁻³
137 parameters	Δρ_min = −1.09 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 957 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (3)

Crystal data top

[ZnBr₂(C₁₀H₁₂N₂)]	V = 647.0 (4) Å³
M_r = 385.41	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.029 (3) Å	µ = 8.04 mm⁻¹
b = 14.090 (3) Å	T = 298 K
c = 7.037 (2) Å	0.23 × 0.23 × 0.21 mm
β = 111.820 (3)°

Data collection top

Bruker APEXII CCD diffractometer	2408 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1708 reflections with I > 2σ(I)
T_min = 0.259, T_max = 0.283	R_int = 0.104
4060 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.165	Δρ_max = 0.96 e Å⁻³
S = 0.95	Δρ_min = −1.09 e Å⁻³
2408 reflections	Absolute structure: Flack (1983), 957 Friedel pairs
137 parameters	Absolute structure parameter: −0.05 (3)
1 restraint

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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) top

	x	y	z	U_iso*/U_eq
Zn1	0.01583 (18)	0.10050 (8)	0.5412 (2)	0.0380 (3)
Br1	−0.0650 (2)	−0.05302 (9)	0.6175 (2)	0.0601 (4)
Br2	0.0576 (2)	0.12235 (9)	0.2262 (2)	0.0559 (4)
N1	−0.1663 (14)	0.2047 (7)	0.5832 (15)	0.040 (2)
N2	0.2313 (14)	0.1748 (7)	0.7783 (14)	0.036 (2)
C1	−0.3710 (18)	0.2147 (10)	0.491 (2)	0.050 (3)
H1	−0.4447	0.1674	0.4022	0.060*
C2	−0.477 (2)	0.2918 (10)	0.524 (2)	0.053 (3)
H2	−0.6184	0.2965	0.4582	0.064*
C3	−0.369 (2)	0.3597 (10)	0.652 (2)	0.057 (4)
H3	−0.4351	0.4134	0.6742	0.069*
C4	−0.158 (2)	0.3503 (9)	0.753 (2)	0.047 (3)
H4	−0.0833	0.3966	0.8450	0.056*
C5	−0.0622 (16)	0.2727 (8)	0.7166 (16)	0.034 (2)
C6	0.1628 (17)	0.2531 (8)	0.8195 (16)	0.036 (2)
C7	0.288 (2)	0.3276 (9)	0.968 (2)	0.058 (4)
H7A	0.2300	0.3390	1.0702	0.087*
H7B	0.2870	0.3854	0.8960	0.087*
H7C	0.4265	0.3057	1.0337	0.087*
C8	0.4414 (17)	0.1441 (9)	0.8788 (19)	0.044 (3)
H8	0.5438	0.1939	0.9385	0.053*
C9	0.471 (2)	0.0526 (10)	0.995 (2)	0.051 (3)
H9A	0.3501	0.0188	0.9917	0.061*
H9B	0.5889	0.0474	1.1220	0.061*
C10	0.511 (2)	0.0589 (11)	0.799 (2)	0.058 (4)
H10A	0.6518	0.0572	0.8084	0.070*
H10B	0.4131	0.0285	0.6781	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0393 (6)	0.0335 (7)	0.0441 (7)	−0.0027 (6)	0.0189 (5)	−0.0084 (6)
Br1	0.0749 (9)	0.0420 (7)	0.0784 (10)	−0.0192 (7)	0.0460 (8)	−0.0117 (7)
Br2	0.0672 (8)	0.0607 (9)	0.0464 (7)	−0.0071 (6)	0.0287 (7)	−0.0038 (6)
N1	0.039 (5)	0.039 (6)	0.039 (5)	0.000 (4)	0.010 (4)	−0.005 (4)
N2	0.040 (5)	0.037 (5)	0.029 (5)	0.004 (4)	0.011 (4)	0.009 (4)
C1	0.043 (7)	0.061 (8)	0.045 (7)	0.001 (6)	0.016 (6)	0.001 (6)
C2	0.056 (8)	0.056 (8)	0.056 (8)	0.029 (7)	0.030 (7)	0.009 (7)
C3	0.069 (9)	0.045 (8)	0.066 (9)	0.028 (7)	0.035 (8)	0.013 (7)
C4	0.066 (8)	0.034 (6)	0.045 (7)	0.006 (6)	0.026 (7)	0.001 (5)
C5	0.035 (6)	0.038 (6)	0.028 (5)	0.003 (5)	0.009 (5)	0.009 (5)
C6	0.051 (7)	0.031 (6)	0.030 (6)	−0.002 (5)	0.020 (5)	0.001 (4)
C7	0.065 (9)	0.041 (8)	0.061 (9)	−0.007 (6)	0.016 (8)	−0.014 (6)
C8	0.032 (6)	0.043 (7)	0.052 (7)	0.002 (5)	0.009 (5)	0.001 (6)
C9	0.052 (8)	0.047 (7)	0.054 (7)	0.012 (6)	0.019 (7)	0.015 (6)
C10	0.046 (7)	0.079 (10)	0.047 (7)	0.018 (7)	0.015 (6)	0.007 (7)

Geometric parameters (Å, º) top

Zn1—N1	2.041 (9)	C4—H4	0.9300
Zn1—N2	2.073 (10)	C5—C6	1.500 (15)
Zn1—Br1	2.3488 (18)	C6—C7	1.514 (16)
Zn1—Br2	2.3616 (19)	C7—H7A	0.9600
N1—C1	1.348 (15)	C7—H7B	0.9600
N1—C5	1.350 (15)	C7—H7C	0.9600
N2—C6	1.279 (15)	C8—C10	1.48 (2)
N2—C8	1.446 (14)	C8—C9	1.498 (18)
C1—C2	1.383 (18)	C8—H8	0.9800
C1—H1	0.9300	C9—C10	1.506 (19)
C2—C3	1.34 (2)	C9—H9A	0.9700
C2—H2	0.9300	C9—H9B	0.9700
C3—C4	1.392 (19)	C10—H10A	0.9700
C3—H3	0.9300	C10—H10B	0.9700
C4—C5	1.358 (17)

N1—Zn1—N2	80.2 (4)	N2—C6—C5	117.9 (10)
N1—Zn1—Br1	114.3 (3)	N2—C6—C7	125.7 (11)
N2—Zn1—Br1	116.6 (3)	C5—C6—C7	116.4 (10)
N1—Zn1—Br2	110.2 (3)	C6—C7—H7A	109.5
N2—Zn1—Br2	112.4 (3)	C6—C7—H7B	109.5
Br1—Zn1—Br2	117.36 (7)	H7A—C7—H7B	109.5
C1—N1—C5	117.7 (10)	C6—C7—H7C	109.5
C1—N1—Zn1	128.4 (8)	H7A—C7—H7C	109.5
C5—N1—Zn1	113.8 (7)	H7B—C7—H7C	109.5
C6—N2—C8	123.3 (11)	N2—C8—C10	118.4 (11)
C6—N2—Zn1	113.2 (7)	N2—C8—C9	115.8 (10)
C8—N2—Zn1	123.4 (8)	C10—C8—C9	60.7 (9)
N1—C1—C2	123.2 (13)	N2—C8—H8	116.7
N1—C1—H1	118.4	C10—C8—H8	116.7
C2—C1—H1	118.4	C9—C8—H8	116.7
C3—C2—C1	117.8 (12)	C8—C9—C10	59.1 (9)
C3—C2—H2	121.1	C8—C9—H9A	117.9
C1—C2—H2	121.1	C10—C9—H9A	117.9
C2—C3—C4	120.3 (12)	C8—C9—H9B	117.9
C2—C3—H3	119.8	C10—C9—H9B	117.9
C4—C3—H3	119.8	H9A—C9—H9B	115.0
C5—C4—C3	119.3 (12)	C8—C10—C9	60.2 (8)
C5—C4—H4	120.4	C8—C10—H10A	117.8
C3—C4—H4	120.4	C9—C10—H10A	117.8
N1—C5—C4	121.6 (10)	C8—C10—H10B	117.8
N1—C5—C6	114.0 (10)	C9—C10—H10B	117.8
C4—C5—C6	124.3 (11)	H10A—C10—H10B	114.9

Experimental details

Crystal data
Chemical formula	[ZnBr₂(C₁₀H₁₂N₂)]
M_r	385.41
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	7.029 (3), 14.090 (3), 7.037 (2)
β (°)	111.820 (3)
V (Å³)	647.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	8.04
Crystal size (mm)	0.23 × 0.23 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.259, 0.283
No. of measured, independent and observed [I > 2σ(I)] reflections	4060, 2408, 1708
R_int	0.104
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.165, 0.95
No. of reflections	2408
No. of parameters	137
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.96, −1.09
Absolute structure	Flack (1983), 957 Friedel pairs
Absolute structure parameter	−0.05 (3)

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—N1	2.041 (9)	Zn1—Br1	2.3488 (18)
Zn1—N2	2.073 (10)	Zn1—Br2	2.3616 (19)

Acknowledgements

The authors thank the Scientific Research Foundation of Shaanxi University of Technology (project No. SLGQD0708) for financial support.

References

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