Bis{4-bromo-2-[(2-hy­droxy­eth­yl)imino­meth­yl]phenolato-κ3O,N,O′}cadmium

Yu, J.

doi:10.1107/S1600536811025852

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page m1035

doi:10.1107/S1600536811025852

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Bis{4-bromo-2-[(2-hydroxyethyl)iminomethyl]phenolato-κ³O,N,O′}cadmium

Jing Yu ^a ^*

^aSchool of Biological and Chemical Engineering, Jiaxing University, Jiaxing Zhejiang 314001, People's Republic of China
^*Correspondence e-mail: jxxyyuj@yahoo.cn

(Received 25 June 2011; accepted 30 June 2011; online 6 July 2011)

The centrosymmetric title compound, [Cd(C₉H₉BrNO₂)₂], was obtained by the reaction of 5-bromosalicylaldehyde, 2-aminoethanol and cadmium nitrate in ethanol. The Cd atom, located on an inversion centre, is hexacoordinated by two Schiff base ligands in an octahedral coordination through the phenolate O atom, the imine N atom and the hydroxy O atoms. In the crystal, molecules are linked through intermolecular O—H⋯O hydrogen bonds, forming chains along the b axis.

Related literature

For the structures and properties of Schiff base Cd complexes, see: Sarkar et al. (2011 ); Das et al. (2010 ); Fang & Nie (2010 ); Niu et al. (2010 ); Keypour et al. (2009 ).

Experimental

Crystal data

[Cd(C₉H₉BrNO₂)₂]
M_r = 598.56
Monoclinic, P 2/n
a = 10.207 (4) Å
b = 5.3275 (19) Å
c = 18.656 (7) Å
β = 99.156 (4)°
V = 1001.5 (6) Å³
Z = 2
Mo Kα radiation
μ = 5.11 mm⁻¹
T = 298 K
0.23 × 0.20 × 0.20 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.386, T_max = 0.428
7794 measured reflections
2172 independent reflections
1524 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.126
S = 1.02
2172 reflections
126 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.41 e Å⁻³
Δρ_min = −1.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.85 (1)	1.75 (2)	2.599 (7)	173 (9)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-1, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025852/hg5060sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025852/hg5060Isup2.hkl

checkCIF report

Comment top

Schiff base cadmium(II) complexes have been received much attention due to their interesting structures and luminescent properties (Sarkar et al., 2011; Das et al., 2010; Fang & Nie, 2010; Niu et al., 2010; Keypour et al., 2009).

The molecule of the title complex, (I) (Fig. 1), is centrosymmetric, with the inversion center located at the Cd atom. The Cd atom is hexa-coordinated by two Schiff base ligands, forming an octahedral coordination. The Schiff base coordinates to the Co atom through the phenolate O atom, the imine N atom, and the hydroxy O atom. The bond lengths are within normal values. In the crystal, molecules are linked through intermolecular O—H···O hydrogen bonds (Table 1), to form chains along the b axis, Fig. 2.

Related literature top

For the structures and properties of Schiff base–cadmium(II) complexes, see: Sarkar et al. (2011); Das et al. (2010); Fang & Nie (2010); Niu et al. (2010); Keypour et al. (2009).

Experimental top

To a solution of 5-bromosalicylaldehyde (0.181 g, 1.0 mmol), 2-aminoethanol (0.061 g, 1.0 mmol) in 20 ml absolute ethanol was added slowly a solution of cadmium nitrate (0.154 g, 0.5 mmol) in ethanol. The mixture was stirred for 2 h at room temperature to give a colorless solution, which was filtered and the filtrate was left to stand at room temperature. Colorless block crystals suitable for X-ray diffraction were obtained by slow evaporation.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. Unlabelled atoms are at the symmetry position 1/2 - x, y, 1/2 - z.
	Fig. 2. The packing of (I), viewed down the c axis. Hydrogen bonds are drawn as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

Bis{4-bromo-2-[(2-hydroxyethyl)iminomethyl]phenolato- κ³O,N,O'}cadmium top

Crystal data top

[Cd(C₉H₉BrNO₂)₂]	F(000) = 580
M_r = 598.56	D_x = 1.985 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 1609 reflections
a = 10.207 (4) Å	θ = 2.5–24.4°
b = 5.3275 (19) Å	µ = 5.11 mm⁻¹
c = 18.656 (7) Å	T = 298 K
β = 99.156 (4)°	Block, colorless
V = 1001.5 (6) Å³	0.23 × 0.20 × 0.20 mm
Z = 2

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2172 independent reflections
Radiation source: fine-focus sealed tube	1524 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 27.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −13→12
T_min = 0.386, T_max = 0.428	k = −6→6
7794 measured reflections	l = −23→23

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.034P)² + 5.8476P] where P = (F_o² + 2F_c²)/3
2172 reflections	(Δ/σ)_max < 0.001
126 parameters	Δρ_max = 1.41 e Å⁻³
1 restraint	Δρ_min = −1.55 e Å⁻³

Crystal data top

[Cd(C₉H₉BrNO₂)₂]	V = 1001.5 (6) Å³
M_r = 598.56	Z = 2
Monoclinic, P2/n	Mo Kα radiation
a = 10.207 (4) Å	µ = 5.11 mm⁻¹
b = 5.3275 (19) Å	T = 298 K
c = 18.656 (7) Å	0.23 × 0.20 × 0.20 mm
β = 99.156 (4)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2172 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1524 reflections with I > 2σ(I)
T_min = 0.386, T_max = 0.428	R_int = 0.039
7794 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	1 restraint
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 1.41 e Å⁻³
2172 reflections	Δρ_min = −1.55 e Å⁻³
126 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
Cd1	0.2500	0.38621 (12)	0.2500	0.0491 (2)
Br1	0.21431 (12)	0.4350 (3)	0.64964 (5)	0.1157 (5)
N1	0.4104 (7)	0.2594 (14)	0.3415 (3)	0.0705 (19)
O1	0.2194 (5)	0.6681 (8)	0.3344 (2)	0.0577 (13)
O2	0.3921 (6)	0.0979 (9)	0.2021 (3)	0.0676 (14)
C1	0.3083 (7)	0.4314 (13)	0.4410 (3)	0.0529 (17)
C2	0.2245 (7)	0.6144 (12)	0.4037 (3)	0.0476 (15)
C3	0.1433 (9)	0.7475 (15)	0.4453 (4)	0.073 (2)
H3	0.0893	0.8751	0.4231	0.087*
C4	0.1407 (9)	0.6964 (18)	0.5174 (4)	0.081 (3)
H4	0.0842	0.7849	0.5428	0.097*
C5	0.2219 (9)	0.5144 (17)	0.5511 (4)	0.069 (2)
C6	0.3057 (8)	0.3868 (16)	0.5151 (4)	0.067 (2)
H6	0.3625	0.2677	0.5397	0.080*
C7	0.4004 (8)	0.2792 (17)	0.4087 (4)	0.073 (2)
H7	0.4597	0.1840	0.4407	0.088*
C8	0.5021 (11)	0.066 (2)	0.3211 (5)	0.112 (4)
H8A	0.5895	0.0913	0.3493	0.134*
H8B	0.4712	−0.0987	0.3329	0.134*
C9	0.5113 (10)	0.075 (2)	0.2490 (6)	0.113 (4)
H9A	0.5551	−0.0772	0.2366	0.136*
H9B	0.5676	0.2151	0.2409	0.136*
H2	0.358 (8)	−0.047 (7)	0.194 (5)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0826 (6)	0.0363 (3)	0.0287 (3)	0.000	0.0101 (3)	0.000
Br1	0.1431 (11)	0.1725 (13)	0.0387 (5)	0.0486 (9)	0.0363 (6)	0.0257 (6)
N1	0.082 (5)	0.092 (5)	0.038 (3)	0.029 (4)	0.011 (3)	−0.004 (3)
O1	0.107 (4)	0.038 (2)	0.030 (2)	0.007 (2)	0.018 (2)	0.0017 (18)
O2	0.084 (4)	0.056 (3)	0.064 (3)	−0.005 (3)	0.016 (3)	−0.026 (3)
C1	0.067 (5)	0.060 (4)	0.032 (3)	0.008 (3)	0.008 (3)	0.000 (3)
C2	0.074 (5)	0.037 (3)	0.033 (3)	−0.004 (3)	0.013 (3)	−0.002 (3)
C3	0.114 (7)	0.062 (5)	0.044 (4)	0.024 (5)	0.021 (4)	0.003 (4)
C4	0.111 (7)	0.095 (6)	0.042 (4)	0.033 (6)	0.030 (4)	0.000 (4)
C5	0.089 (6)	0.086 (5)	0.032 (4)	0.017 (5)	0.014 (4)	0.004 (4)
C6	0.083 (6)	0.081 (5)	0.036 (4)	0.021 (5)	0.006 (4)	0.004 (4)
C7	0.088 (6)	0.095 (6)	0.037 (4)	0.035 (5)	0.011 (4)	0.007 (4)
C8	0.112 (8)	0.166 (11)	0.059 (5)	0.078 (8)	0.020 (5)	0.005 (6)
C9	0.084 (7)	0.157 (11)	0.094 (7)	0.031 (7)	0.002 (6)	−0.069 (7)

Geometric parameters (Å, º) top

Cd1—O1	2.233 (4)	C1—C7	1.443 (10)
Cd1—O1ⁱ	2.233 (4)	C2—C3	1.413 (10)
Cd1—N1	2.272 (6)	C3—C4	1.376 (10)
Cd1—N1ⁱ	2.272 (6)	C3—H3	0.9300
Cd1—O2ⁱ	2.382 (5)	C4—C5	1.363 (11)
Cd1—O2	2.382 (5)	C4—H4	0.9300
Br1—C5	1.900 (7)	C5—C6	1.352 (11)
N1—C7	1.278 (8)	C6—H6	0.9300
N1—C8	1.482 (10)	C7—H7	0.9300
O1—C2	1.318 (7)	C8—C9	1.364 (13)
O2—C9	1.387 (11)	C8—H8A	0.9700
O2—H2	0.850 (10)	C8—H8B	0.9700
C1—C2	1.405 (9)	C9—H9A	0.9700
C1—C6	1.407 (9)	C9—H9B	0.9700

O1—Cd1—O1ⁱ	95.5 (2)	C4—C3—C2	122.8 (7)
O1—Cd1—N1	80.5 (2)	C4—C3—H3	118.6
O1ⁱ—Cd1—N1	124.4 (2)	C2—C3—H3	118.6
O1—Cd1—N1ⁱ	124.4 (2)	C5—C4—C3	119.1 (7)
O1ⁱ—Cd1—N1ⁱ	80.5 (2)	C5—C4—H4	120.4
N1—Cd1—N1ⁱ	145.4 (4)	C3—C4—H4	120.4
O1—Cd1—O2ⁱ	90.41 (19)	C6—C5—C4	121.0 (7)
O1ⁱ—Cd1—O2ⁱ	149.32 (19)	C6—C5—Br1	119.7 (6)
N1—Cd1—O2ⁱ	86.3 (2)	C4—C5—Br1	119.3 (6)
N1ⁱ—Cd1—O2ⁱ	71.4 (2)	C5—C6—C1	121.1 (7)
O1—Cd1—O2	149.32 (19)	C5—C6—H6	119.5
O1ⁱ—Cd1—O2	90.41 (19)	C1—C6—H6	119.5
N1—Cd1—O2	71.4 (2)	N1—C7—C1	127.9 (7)
N1ⁱ—Cd1—O2	86.3 (2)	N1—C7—H7	116.1
O2ⁱ—Cd1—O2	99.7 (3)	C1—C7—H7	116.1
C7—N1—C8	117.5 (7)	C9—C8—N1	112.1 (8)
C7—N1—Cd1	123.5 (5)	C9—C8—H8A	109.2
C8—N1—Cd1	115.0 (5)	N1—C8—H8A	109.2
C2—O1—Cd1	123.9 (4)	C9—C8—H8B	109.2
C9—O2—Cd1	110.2 (5)	N1—C8—H8B	109.2
C9—O2—H2	109 (6)	H8A—C8—H8B	107.9
Cd1—O2—H2	113 (6)	C8—C9—O2	115.7 (9)
C2—C1—C6	119.8 (6)	C8—C9—H9A	108.3
C2—C1—C7	124.7 (6)	O2—C9—H9A	108.3
C6—C1—C7	115.5 (6)	C8—C9—H9B	108.3
O1—C2—C1	124.2 (6)	O2—C9—H9B	108.3
O1—C2—C3	119.7 (6)	H9A—C9—H9B	107.4
C1—C2—C3	116.2 (6)

Symmetry code: (i) −x+1/2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱⁱ	0.85 (1)	1.75 (2)	2.599 (7)	173 (9)

Symmetry code: (ii) −x+1/2, y−1, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Cd(C₉H₉BrNO₂)₂]
M_r	598.56
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	298
a, b, c (Å)	10.207 (4), 5.3275 (19), 18.656 (7)
β (°)	99.156 (4)
V (Å³)	1001.5 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.11
Crystal size (mm)	0.23 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.386, 0.428
No. of measured, independent and observed [I > 2σ(I)] reflections	7794, 2172, 1524
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.126, 1.02
No. of reflections	2172
No. of parameters	126
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.41, −1.55

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008) and local programs.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.850 (10)	1.754 (17)	2.599 (7)	173 (9)

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

Acknowledgements

The School of Biological and Chemical Engineering at Jiaxing University is acknowledged for the provision of facilities to prepare and crystallize the compound. Dr Yu-Xi Sun of Qufu Normal University is acknowledged for the data collection.

References

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