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Acta Cryst. (2009). E65, m358    [ doi:10.1107/S1600536809007028 ]

Diaquadibromidobis[3-dimethylamino-1-(4-pyridyl-[kappa]N)prop-2-en-1-one]cadmium(II)

H.-Z. Dong, Z.-L. Chu and N.-L. Hu

Abstract top

In the title compound, [CdBr2(C10H12N2O)2(H2O)2], the CdII ion is located on an inversion center and is six-coordinated by two N atoms [Cd-N = 2.377 (3) Å] from two different 3-dimethylamino-1-(4-pyridyl)prop-2-en-1-one ligands, two O atoms [Cd-O = 2.355 (2) Å] from two coordinated water molecules and two bromide anions [Cd-Br = 2.6855 (5) Å]. Intermolecular O-H...O hydrogen bonds link the molecules into layers parallel to the bc plane.

Comment top

In recent years, researchers showed considerable interest in the physical and chemical properties of mono- and polynuclear complexes of transition metals having the d10 electronic configuration (Bi et al., 2008; Dong et al., 2008). Ligands with pyridyl group have been used to generate various metal-organic architectures with cadmium salts (Hu et al., 2003; Ito et al., 1984). Here we report a new monomeric cadmium(II) complex, viz. the title compound, [Cd(C10H12N2O)2Br2(H2O)2].

The asymmetric unit of the title compound contains a half of centrosymmetric molecule, and the CdII ion lies on an inversion center. Each CdII ion exhibits an octahedral environment with two nitrogen atoms from the pyridyl groups of two ligands, two oxygen atoms from two coordinated water molecules, and two bromine anions (Fig. 1). Intermolecular O—H···O hydrogen bonds (Table 1) link the molecules into layers parallel to bc plane.

Related literature top

For general backgroud, see: Bi et al. (2008); Dong et al. (2008). For related structures, see: Hu et al. (2003); Ito et al. (1984). For details of the synthesis, see Sun et al. (2008).

Experimental top

All solvents and chemicals were of analytical grade and were used without further purification. Ligand was prepared by similar procedure reported in the literature (Sun et al., 2008). For the synthesis of title compoud, a solution of ligand (0.1 mmol), CdBr2 (0.1 mmol) in 30 ml me thanol was refluxed for 2 h, and then cooled to room temperature and filtered. Single crystals suitable for X-ray analysis were grown from the methanol solution by slow evaporation at room temperature in air. Anal. Calcd. for C20H28CdN4O4Br2: C, 36.36; H, 4.27; N, 8.48. Found: C, 36.38; H, 4.38; N, 8.32. Main FT—IR (KBr, cm-1): 3078(w), 1627(s), 1603(m), 1558(w),1498(s), 1437(m), 1384(m), 1329(w),1233(m),781(w).

Refinement top

All hydrogen atoms were geometrically positioned (C—H 0.93–0.97 Å, O–H 0.85 Å) and refined as riding, with Uiso(H)=1.2–1.5 Ueq of the parent atom.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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
[Figure 1] Fig. 1. Molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering [symmetry code: (A) 1 - x,1 - y,1 - z].
Diaquadibromidobis[3-dimethylamino-1-(4-pyridyl-κN)prop-2-en-1- one]cadmium(II) top
Crystal data top
[CdBr2(C10H12N2O)2(H2O)2]F(000) = 1304
Mr = 660.68Dx = 1.828 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3328 reflections
a = 21.362 (3) Åθ = 2.6–27.8°
b = 8.4360 (9) ŵ = 4.27 mm−1
c = 14.6371 (16) ÅT = 273 K
β = 114.456 (3)°Block, colourless
V = 2401.1 (5) Å30.2 × 0.2 × 0.2 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		2356 independent reflections
Radiation source: fine-focus sealed tube2085 reflections with I > 2σ(I)
graphiteRint = 0.073
φ and ω scansθmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −26→25
Tmin = 0.407, Tmax = 0.424k = −8→10
6227 measured reflectionsl = −18→17
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0479P)2]
where P = (Fo2 + 2Fc2)/3
2356 reflections(Δ/σ)max < 0.001
144 parametersΔρmax = 0.62 e Å−3
0 restraintsΔρmin = −0.93 e Å−3
Crystal data top
[CdBr2(C10H12N2O)2(H2O)2]V = 2401.1 (5) Å3
Mr = 660.68Z = 4
Monoclinic, C2/cMo Kα radiation
a = 21.362 (3) ŵ = 4.27 mm−1
b = 8.4360 (9) ÅT = 273 K
c = 14.6371 (16) Å0.2 × 0.2 × 0.2 mm
β = 114.456 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2356 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2085 reflections with I > 2σ(I)
Tmin = 0.407, Tmax = 0.424Rint = 0.073
6227 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.090Δρmax = 0.62 e Å−3
S = 1.01Δρmin = −0.93 e Å−3
2356 reflectionsAbsolute structure: ?
144 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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
xyzUiso*/Ueq
Cd10.50000.50000.50000.02740 (13)
Br10.626658 (19)0.61470 (5)0.54529 (3)0.04254 (15)
C10.44435 (18)0.8564 (4)0.4098 (2)0.0332 (8)
H10.45610.87600.47750.040*
C20.43309 (18)0.6830 (4)0.2848 (2)0.0350 (8)
H20.43680.58070.26390.042*
C30.42099 (19)0.9802 (4)0.3443 (2)0.0317 (8)
H30.41711.08100.36730.038*
C40.40298 (16)0.9534 (4)0.2423 (2)0.0270 (7)
C50.40919 (18)0.7997 (4)0.2139 (2)0.0341 (8)
H50.39710.77580.14670.041*
C60.33391 (18)1.0483 (5)0.0698 (2)0.0337 (8)
H60.31490.94720.05580.040*
C70.38011 (16)1.0865 (4)0.1687 (2)0.0276 (7)
C80.2340 (2)0.9862 (5)−0.1300 (3)0.0524 (11)
H8A0.26460.9016−0.12810.079*
H8B0.19900.9969−0.19700.079*
H8C0.21310.9631−0.08480.079*
C90.2647 (2)1.2464 (5)−0.1787 (3)0.0423 (9)
H9A0.28561.3452−0.14920.063*
H9B0.21671.2629−0.21960.063*
H9C0.28661.2058−0.21950.063*
C100.31637 (17)1.1583 (4)−0.0065 (2)0.0299 (7)
H100.33711.25750.00930.036*
N10.45139 (14)0.7084 (3)0.38242 (19)0.0311 (6)
N20.27261 (15)1.1335 (4)−0.1000 (2)0.0338 (7)
O10.40227 (12)1.2232 (3)0.19871 (16)0.0343 (5)
O20.50607 (12)0.3380 (3)0.37287 (16)0.0368 (6)
H2A0.46610.33440.32530.044*
H2B0.53230.38850.35250.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0341 (2)0.0237 (2)0.02374 (19)0.00164 (13)0.01137 (15)0.00238 (13)
Br10.0377 (2)0.0426 (3)0.0455 (2)−0.00547 (16)0.01541 (19)0.00457 (17)
C10.043 (2)0.031 (2)0.0228 (15)−0.0064 (15)0.0108 (14)0.0005 (14)
C20.043 (2)0.0280 (19)0.0297 (16)0.0049 (15)0.0112 (15)0.0012 (15)
C30.043 (2)0.0242 (19)0.0264 (16)−0.0044 (14)0.0129 (15)−0.0006 (13)
C40.0252 (17)0.0282 (17)0.0270 (15)−0.0016 (13)0.0102 (13)0.0032 (14)
C50.042 (2)0.036 (2)0.0241 (15)0.0019 (15)0.0131 (15)−0.0017 (15)
C60.037 (2)0.0299 (19)0.0284 (16)−0.0003 (15)0.0076 (15)0.0022 (15)
C70.0299 (18)0.029 (2)0.0260 (16)0.0017 (14)0.0132 (14)0.0028 (14)
C80.058 (3)0.049 (3)0.037 (2)−0.0098 (19)0.006 (2)−0.0102 (18)
C90.044 (2)0.051 (2)0.0299 (17)0.0098 (18)0.0135 (16)0.0129 (17)
C100.0322 (18)0.0291 (18)0.0275 (15)0.0002 (14)0.0115 (14)−0.0019 (14)
N10.0342 (16)0.0294 (17)0.0295 (14)−0.0007 (12)0.0129 (12)0.0049 (12)
N20.0338 (16)0.0398 (18)0.0251 (13)0.0008 (12)0.0094 (12)0.0021 (13)
O10.0407 (14)0.0288 (14)0.0293 (11)−0.0061 (10)0.0105 (11)0.0017 (10)
O20.0361 (13)0.0434 (15)0.0304 (12)−0.0041 (11)0.0132 (10)−0.0094 (11)
Geometric parameters (Å, °) top
Cd1—O2i2.355 (2)C6—C101.379 (5)
Cd1—O22.355 (2)C6—C71.411 (4)
Cd1—N1i2.377 (3)C6—H60.9300
Cd1—N12.377 (3)C7—O11.255 (4)
Cd1—Br1i2.6855 (5)C8—N21.455 (5)
Cd1—Br12.6855 (5)C8—H8A0.9600
C1—N11.339 (4)C8—H8B0.9600
C1—C31.365 (5)C8—H8C0.9600
C1—H10.9300C9—N21.449 (4)
C2—N11.333 (4)C9—H9A0.9600
C2—C51.366 (5)C9—H9B0.9600
C2—H20.9300C9—H9C0.9600
C3—C41.398 (4)C10—N21.316 (4)
C3—H30.9300C10—H100.9300
C4—C51.385 (5)O2—H2A0.8500
C4—C71.491 (4)O2—H2B0.8501
C5—H50.9300
O2i—Cd1—O2180.0C10—C6—C7121.2 (3)
O2i—Cd1—N1i90.43 (9)C10—C6—H6119.4
O2—Cd1—N1i89.57 (9)C7—C6—H6119.4
O2i—Cd1—N189.57 (9)O1—C7—C6124.8 (3)
O2—Cd1—N190.43 (9)O1—C7—C4118.4 (3)
N1i—Cd1—N1180.00 (11)C6—C7—C4116.8 (3)
O2i—Cd1—Br1i91.41 (6)N2—C8—H8A109.5
O2—Cd1—Br1i88.59 (6)N2—C8—H8B109.5
N1i—Cd1—Br1i90.33 (7)H8A—C8—H8B109.5
N1—Cd1—Br1i89.67 (7)N2—C8—H8C109.5
O2i—Cd1—Br188.59 (6)H8A—C8—H8C109.5
O2—Cd1—Br191.41 (6)H8B—C8—H8C109.5
N1i—Cd1—Br189.67 (7)N2—C9—H9A109.5
N1—Cd1—Br190.33 (7)N2—C9—H9B109.5
Br1i—Cd1—Br1180.000 (15)H9A—C9—H9B109.5
N1—C1—C3123.8 (3)N2—C9—H9C109.5
N1—C1—H1118.1H9A—C9—H9C109.5
C3—C1—H1118.1H9B—C9—H9C109.5
N1—C2—C5123.3 (3)N2—C10—C6125.0 (3)
N1—C2—H2118.3N2—C10—H10117.5
C5—C2—H2118.3C6—C10—H10117.5
C1—C3—C4119.1 (3)C2—N1—C1116.8 (3)
C1—C3—H3120.5C2—N1—Cd1120.2 (2)
C4—C3—H3120.5C1—N1—Cd1122.8 (2)
C5—C4—C3117.0 (3)C10—N2—C9121.4 (3)
C5—C4—C7122.1 (3)C10—N2—C8121.3 (3)
C3—C4—C7120.9 (3)C9—N2—C8117.2 (3)
C2—C5—C4119.9 (3)Cd1—O2—H2A107.7
C2—C5—H5120.0Cd1—O2—H2B104.3
C4—C5—H5120.0H2A—O2—H2B108.3
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O1ii0.852.022.770 (3)147
O2—H2B···O1iii0.852.312.751 (4)113
Symmetry codes: (ii) x, y−1, z; (iii) −x+1, y−1, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O1i0.852.022.770 (3)147
O2—H2B···O1ii0.852.312.751 (4)113
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1, −z+1/2.
Acknowledgements top

The authors are indebted to Anhui Provincial Natural Science Research Project (KJ2009B240Z) and the National Natural Science Foundation of China (No.20871039) for financial support.

references
References top

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