Dibromido{2-morpholino-N-[1-(2-pyrid­yl)ethyl­idene]ethanamine-κ3N,N′,N′′}zinc(II)

Ding, Y.-W.; Wang, X.-L.; Ni, L.-L.

doi:10.1107/S1600536811002753

metal-organic compounds

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Volume 67| Part 2| February 2011| Page m261

doi:10.1107/S1600536811002753

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Dibromido{2-morpholino-N-[1-(2-pyridyl)ethylidene]ethanamine-κ³N,N′,N′′}zinc(II)

Yan-Wei Ding,^a ^* Xiao-Ling Wang ^a and Li-Li Ni ^b

^aCollege of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, People's Republic of China, and ^bThe Miyun High School Attached to Capital Normal University, Beijing 101500, People's Republic of China
^*Correspondence e-mail: dingyanwei@sohu.com

(Received 17 January 2011; accepted 20 January 2011; online 26 January 2011)

In the title complex, [ZnBr₂(C₁₃H₁₉N₃O)], the Zn^II 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 ).

Experimental

Crystal data

[ZnBr₂(C₁₃H₁₉N₃O)]
M_r = 458.50
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.065
wR(F²) = 0.177
S = 1.05
3411 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 1.35 e Å⁻³
Δρ_min = −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 ).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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).

Experimental top

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.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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) and publCIF (Westrip, 2010).

Figures top

Fig. 1. Molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

Dibromido{2-morpholino-N-[1-(2-pyridyl)ethylidene]ethanamine- κ³N,N',N''}zinc(II) top

Crystal data top

[ZnBr₂(C₁₃H₁₉N₃O)]	F(000) = 904
M_r = 458.50	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	3411 independent reflections
Radiation source: fine-focus sealed tube	2159 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.108
ω scans	θ_max = 27.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
T_min = 0.209, T_max = 0.230	k = −17→17
12426 measured reflections	l = −15→15

Refinement top

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(F_o²) + (0.0584P)² + 5.9893P] where P = (F_o² + 2F_c²)/3
3411 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 1.35 e Å⁻³
0 restraints	Δρ_min = −1.26 e Å⁻³

Crystal data top

[ZnBr₂(C₁₃H₁₉N₃O)]	V = 1604.9 (11) Å³
M_r = 458.50	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.831 (4) Å	µ = 6.51 mm⁻¹
b = 13.985 (6) Å	T = 298 K
c = 12.183 (5) Å	0.35 × 0.32 × 0.32 mm
β = 106.626 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3411 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2159 reflections with I > 2σ(I)
T_min = 0.209, T_max = 0.230	R_int = 0.108
12426 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.177	H-atom parameters constrained
S = 1.05	Δρ_max = 1.35 e Å⁻³
3411 reflections	Δρ_min = −1.26 e Å⁻³
182 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Experimental details

Crystal data
Chemical formula	[ZnBr₂(C₁₃H₁₉N₃O)]
M_r	458.50
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.831 (4), 13.985 (6), 12.183 (5)
β (°)	106.626 (4)
V (Å³)	1604.9 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.51
Crystal size (mm)	0.35 × 0.32 × 0.32

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.209, 0.230
No. of measured, independent and observed [I > 2σ(I)] reflections	12426, 3411, 2159
R_int	0.108

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.177, 1.05
No. of reflections	3411
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.35, −1.26

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

References

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