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Acta Cryst. (2007). E63, m2010-m2011    [ doi:10.1107/S1600536807030826 ]

Bis{2-bromo-4-chloro-6-[(2-dimethylaminoethylimino)methyl]phenolato}cadmium(II) monohydrate

L.-Z. Li and L.-H. Wang

Abstract top

In the title compound, [Cd(C11H13BrClN2O)2]·H2O, both the mononuclear cadmium(II) complex and the solvent water molecule lie on a crystallographic twofold rotation axis, which passes through the metal centre and the O atom of the water molecule. The CdII atom is six-coordinated in a severely distorted octahedral geometry by two phenolate O, two imine N and two amine N atoms from two Schiff base ligands. The water molecule is linked to the CdII complex molecule through O-H...O hydrogen bonds.

Comment top

Cadmium complexes derived from Schiff bases have been widely studied for their structures and applications (Shashidhar et al., 2007; Keypour et al., 2007; Cao, 2007; Das et al., 2007; Chakraborty et al., 2007). Recently, we have reported a few transition metal complexes derived from Schiff bases (Li & Wang, 2007a,b; Li & You, 2007; Wang & Li, 2007). As a further investigation of the work on the structural characterization of such complexes, the title cadmium(II) complex, (I), is reported here.

The asymmetric unit of (I) contains one-half of the mononuclear cadmium(II) complex, with the other half related by a crystallographic twofold axis passing through the metal atom; the lattice water molecule also lies on the twofold axis (Fig. 1). The CdII atom is six-coordinated in an anti-trigonal bipyramidal geometry by two phenolate O, two imine N and two amine N atoms from two Schiff base ligands. The Cd—O and Cd—N bond lengths (Table 1) are comparable to the corresponding values observed in other Schiff base cadmium(II) complexes (Ghosh et al., 2007; Rahaman et al., 2006; You et al., 2006; Cai et al., 2006).

The water molecule is linked to the CdII complex molecule through O—H···O hydrogen bonds (Table 2).

Related literature top

For related literature, see: Cai et al. (2006); Cao (2007); Chakraborty et al. (2007); Das et al. (2007); Ghosh et al. (2007); Keypour et al. (2007); Li & Wang (2007a,b); Li & You (2007); Rahaman et al. (2006); Shashidhar et al. (2007); Wang & Li (2007); You et al. (2006).

Experimental top

3-Bromo-5-chlorosalicylaldehyde (0.2 mmol, 47.0 mg) and N,N-dimethyl-1,2-diaminoethane (0.2 mmol, 17.6 mg) were dissolved in a methanol solution (20 ml). The mixture was stirred at room temperature for 30 min, giving a clear yellow solution. To this solution was added an aqueous solution (2 ml) of Cd(NO3)2·4H2O (0.1 mmol, 30.8 mg) with stirring. The resulting mixture was stirred for a further 30 min at room temperature, giving a clear colourless solution. After allowing the solution to stand in air for a week, colourless block-shaped crystals were formed.

Refinement top

Atom H2 was located from a difference Fourier map and its positional parameters were refined, with thw O—H distance restrained to 0.85 (1) Å. Other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. unlabelled atoms are related to labelled atoms by the symmetry operation (−x, y, 1/2 − z).
Bis{2-bromo-4-chloro-6-[(2-dimethylaminoethylimino)methyl]phenolato}cadmium(II) monohydrate top
Crystal data top
[Cd(C11H13BrClN2O)2]·H2OF000 = 1456
Mr = 739.60Dx = 1.826 Mg m−3
Orthorhombic, PbcnMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 2827 reflections
a = 12.4517 (18) Åθ = 2.5–24.3º
b = 9.2937 (14) ŵ = 4.01 mm−1
c = 23.254 (4) ÅT = 298 (2) K
V = 2691.1 (7) Å3Block, colourless
Z = 40.32 × 0.30 × 0.27 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3076 independent reflections
Radiation source: fine-focus sealed tube2184 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.067
T = 298(2) Kθmax = 27.5º
ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→16
Tmin = 0.293, Tmax = 0.331k = −11→11
21549 measured reflectionsl = −30→29
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.087  w = 1/[σ2(Fo2) + (0.0149P)2 + 3.7768P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
3076 reflectionsΔρmax = 0.62 e Å−3
160 parametersΔρmin = −0.58 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Cd(C11H13BrClN2O)2]·H2OV = 2691.1 (7) Å3
Mr = 739.60Z = 4
Orthorhombic, PbcnMo Kα
a = 12.4517 (18) ŵ = 4.01 mm−1
b = 9.2937 (14) ÅT = 298 (2) K
c = 23.254 (4) Å0.32 × 0.30 × 0.27 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3076 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2184 reflections with I > 2σ(I)
Tmin = 0.293, Tmax = 0.331Rint = 0.067
21549 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0391 restraint
wR(F2) = 0.087H atoms treated by a mixture of
independent and constrained refinement
S = 1.02Δρmax = 0.62 e Å−3
3076 reflectionsΔρmin = −0.58 e Å−3
160 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 > 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
xyzUiso*/Ueq
Cd10.00000.16643 (4)0.25000.03424 (12)
Br1−0.05873 (5)−0.18375 (6)0.41005 (2)0.07325 (19)
Cl10.31949 (15)−0.02044 (18)0.51342 (6)0.1009 (6)
O10.0340 (2)−0.0093 (3)0.31307 (11)0.0424 (7)
O20.00000.7240 (5)0.25000.0646 (12)
N10.1798 (3)0.2104 (4)0.26903 (15)0.0417 (8)
N20.0692 (3)0.3193 (4)0.17098 (15)0.0447 (8)
C10.1937 (3)0.0785 (4)0.35954 (17)0.0406 (9)
C20.0964 (3)−0.0023 (4)0.35705 (17)0.0394 (9)
C30.0726 (4)−0.0801 (4)0.40812 (18)0.0477 (11)
C40.1371 (5)−0.0844 (5)0.45538 (18)0.0585 (13)
H40.1171−0.13670.48780.070*
C50.2326 (4)−0.0096 (6)0.45414 (19)0.0593 (13)
C60.2605 (4)0.0715 (5)0.40785 (19)0.0545 (12)
H60.32460.12280.40830.065*
C70.2305 (3)0.1734 (4)0.31383 (18)0.0455 (10)
H70.29920.21120.31800.055*
C80.2352 (4)0.3090 (5)0.2292 (2)0.0542 (12)
H8A0.27600.25350.20140.065*
H8B0.28520.36870.25050.065*
C90.1559 (4)0.4034 (5)0.1981 (2)0.0549 (12)
H9A0.12490.47110.22510.066*
H9B0.19330.45810.16880.066*
C100.1122 (4)0.2283 (6)0.1254 (2)0.0680 (15)
H10A0.05410.18720.10380.102*
H10B0.15460.15260.14200.102*
H10C0.15640.28510.10030.102*
C11−0.0104 (4)0.4182 (6)0.1473 (2)0.0741 (16)
H11A0.02250.47710.11830.111*
H11B−0.03790.47840.17750.111*
H11C−0.06830.36430.13060.111*
H20.002 (5)0.783 (4)0.2779 (15)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0320 (2)0.0349 (2)0.0359 (2)0.000−0.00174 (18)0.000
Br10.0855 (4)0.0647 (3)0.0695 (4)−0.0195 (3)0.0068 (3)0.0153 (3)
Cl10.1271 (14)0.1097 (13)0.0658 (9)0.0133 (11)−0.0591 (9)0.0031 (8)
O10.0469 (16)0.0394 (15)0.0407 (16)−0.0071 (13)−0.0115 (13)0.0045 (12)
O20.065 (3)0.052 (3)0.077 (4)0.000−0.003 (3)0.000
N10.0326 (18)0.045 (2)0.048 (2)−0.0032 (15)0.0034 (15)0.0044 (15)
N20.046 (2)0.043 (2)0.046 (2)−0.0001 (17)0.0015 (16)0.0080 (16)
C10.043 (2)0.037 (2)0.042 (2)0.0086 (19)−0.0100 (19)−0.0043 (18)
C20.043 (2)0.032 (2)0.043 (2)0.0052 (18)−0.0038 (18)−0.0039 (18)
C30.063 (3)0.035 (2)0.045 (2)0.002 (2)−0.001 (2)0.0033 (19)
C40.091 (4)0.052 (3)0.032 (2)0.011 (3)−0.006 (2)0.005 (2)
C50.079 (4)0.056 (3)0.042 (3)0.018 (3)−0.024 (2)−0.007 (2)
C60.055 (3)0.049 (3)0.059 (3)0.011 (2)−0.019 (2)−0.009 (2)
C70.033 (2)0.044 (2)0.059 (3)−0.0027 (19)−0.005 (2)−0.010 (2)
C80.042 (3)0.061 (3)0.059 (3)−0.010 (2)0.003 (2)0.009 (2)
C90.057 (3)0.047 (3)0.061 (3)−0.009 (2)0.007 (2)0.007 (2)
C100.089 (4)0.066 (3)0.049 (3)−0.017 (3)0.014 (3)0.001 (2)
C110.059 (3)0.078 (4)0.085 (4)0.007 (3)0.002 (3)0.043 (3)
Geometric parameters (Å, °) top
Cd1—O1i2.236 (3)C2—C31.421 (6)
Cd1—O12.236 (3)C3—C41.361 (6)
Cd1—N12.319 (3)C4—C51.378 (7)
Cd1—N1i2.319 (3)C4—H40.93
Cd1—N2i2.477 (3)C5—C61.359 (7)
Cd1—N22.477 (3)C6—H60.93
Br1—C31.899 (5)C7—H70.93
Cl1—C51.756 (4)C8—C91.505 (6)
O1—C21.286 (4)C8—H8A0.97
O2—H20.85 (4)C8—H8B0.97
N1—C71.266 (5)C9—H9A0.97
N1—C81.475 (5)C9—H9B0.97
N2—C101.459 (6)C10—H10A0.96
N2—C111.459 (6)C10—H10B0.96
N2—C91.475 (5)C10—H10C0.96
C1—C61.400 (5)C11—H11A0.96
C1—C21.426 (6)C11—H11B0.96
C1—C71.455 (6)C11—H11C0.96
O1i—Cd1—O186.12 (14)C3—C4—H4120.8
O1i—Cd1—N1115.90 (11)C5—C4—H4120.8
O1—Cd1—N179.68 (10)C6—C5—C4121.2 (4)
O1i—Cd1—N1i79.68 (10)C6—C5—Cl1119.7 (4)
O1—Cd1—N1i115.90 (11)C4—C5—Cl1119.1 (4)
N1—Cd1—N1i159.69 (16)C5—C6—C1120.6 (5)
O1i—Cd1—N2i147.12 (11)C5—C6—H6119.7
O1—Cd1—N2i89.90 (11)C1—C6—H6119.7
N1—Cd1—N2i95.34 (12)N1—C7—C1127.5 (4)
N1i—Cd1—N2i72.83 (11)N1—C7—H7116.3
O1i—Cd1—N289.90 (11)C1—C7—H7116.3
O1—Cd1—N2147.12 (11)N1—C8—C9110.9 (4)
N1—Cd1—N272.83 (11)N1—C8—H8A109.5
N1i—Cd1—N295.34 (12)C9—C8—H8A109.5
N2i—Cd1—N2110.01 (16)N1—C8—H8B109.5
C2—O1—Cd1126.8 (2)C9—C8—H8B109.5
C7—N1—C8116.9 (4)H8A—C8—H8B108.0
C7—N1—Cd1126.2 (3)N2—C9—C8112.1 (4)
C8—N1—Cd1116.2 (3)N2—C9—H9A109.2
C10—N2—C11109.9 (4)C8—C9—H9A109.2
C10—N2—C9110.4 (4)N2—C9—H9B109.2
C11—N2—C9108.9 (4)C8—C9—H9B109.2
C10—N2—Cd1109.6 (3)H9A—C9—H9B107.9
C11—N2—Cd1113.9 (3)N2—C10—H10A109.5
C9—N2—Cd1104.0 (2)N2—C10—H10B109.5
C6—C1—C2120.9 (4)H10A—C10—H10B109.5
C6—C1—C7115.3 (4)N2—C10—H10C109.5
C2—C1—C7123.9 (4)H10A—C10—H10C109.5
O1—C2—C3120.8 (4)H10B—C10—H10C109.5
O1—C2—C1124.9 (4)N2—C11—H11A109.5
C3—C2—C1114.3 (4)N2—C11—H11B109.5
C4—C3—C2124.5 (4)H11A—C11—H11B109.5
C4—C3—Br1118.3 (4)N2—C11—H11C109.5
C2—C3—Br1117.2 (3)H11A—C11—H11C109.5
C3—C4—C5118.5 (4)H11B—C11—H11C109.5
Symmetry codes: (i) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1ii0.85 (4)2.14 (3)2.911 (5)152 (5)
Symmetry codes: (ii) x, y+1, z.
Selected geometric parameters (Å, °) top
Cd1—O12.236 (3)Cd1—N22.477 (3)
Cd1—N12.319 (3)
O1i—Cd1—O186.12 (14)N1—Cd1—N2i95.34 (12)
O1—Cd1—N179.68 (10)O1—Cd1—N2147.12 (11)
O1—Cd1—N1i115.90 (11)N1—Cd1—N272.83 (11)
N1—Cd1—N1i159.69 (16)N2i—Cd1—N2110.01 (16)
O1—Cd1—N2i89.90 (11)
Symmetry codes: (i) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1ii0.85 (4)2.14 (3)2.911 (5)152 (5)
Symmetry codes: (ii) x, y+1, z.
Acknowledgements top

This work was supported by the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry (No. BZY 07002).

references
References top

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