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

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

doi:10.1107/S1600536809007028

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page m358

doi:10.1107/S1600536809007028

Open

access

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

Hua-Ze Dong,^a Zhao-Lian Chu ^b and Nai-Liang Hu ^c ^*

^aDepartment of Chemistry and Chemical Engineering, Hefei Teachers College, Hefei 230061, People's Republic of China, ^bInstitute of Molecular Engineering & Applied Chemistry, School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243002, People's Republic of China, and ^cSchool of Chemistry and Chemical Engineering, Anhui University, Hefei 230039, People's Republic of China
^*Correspondence e-mail: dapdong@163.com

(Received 20 February 2009; accepted 25 February 2009; online 6 March 2009)

In the title compound, [CdBr₂(C₁₀H₁₂N₂O)₂(H₂O)₂], the Cd^II 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.

Related literature

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

Crystal data

[CdBr₂(C₁₀H₁₂N₂O)₂(H₂O)₂]
M_r = 660.68
Monoclinic, C 2/c
a = 21.362 (3) Å
b = 8.4360 (9) Å
c = 14.6371 (16) Å
β = 114.456 (3)°
V = 2401.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 4.27 mm⁻¹
T = 273 K
0.2 × 0.2 × 0.2 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.407, T_max = 0.424
6227 measured reflections
2356 independent reflections
2085 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.090
S = 1.02
2356 reflections
144 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.93 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1ⁱ	0.85	2.02	2.770 (3)	147
O2—H2B⋯O1ⁱⁱ	0.85	2.31	2.751 (4)	113
Symmetry codes: (i) x, y-1, z; (ii) $[-x+1, y-1, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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 I, global. DOI: 10.1107/S1600536809007028/cv2525sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007028/cv2525Isup2.hkl

checkCIF report

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 Cd^II ion lies on an inversion center. Each Cd^II 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).

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

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
M_r = 660.68	D_x = 1.828 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3328 reflections
a = 21.362 (3) Å	θ = 2.6–27.8°
b = 8.4360 (9) Å	µ = 4.27 mm⁻¹
c = 14.6371 (16) Å	T = 273 K
β = 114.456 (3)°	Block, colourless
V = 2401.1 (5) Å³	0.2 × 0.2 × 0.2 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2356 independent reflections
Radiation source: fine-focus sealed tube	2085 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −26→25
T_min = 0.407, T_max = 0.424	k = −8→10
6227 measured reflections	l = −18→17

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0479P)²] where P = (F_o² + 2F_c²)/3
2356 reflections	(Δ/σ)_max < 0.001
144 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.93 e Å⁻³

Crystal data top

[CdBr₂(C₁₀H₁₂N₂O)₂(H₂O)₂]	V = 2401.1 (5) Å³
M_r = 660.68	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 21.362 (3) Å	µ = 4.27 mm⁻¹
b = 8.4360 (9) Å	T = 273 K
c = 14.6371 (16) Å	0.2 × 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)
T_min = 0.407, T_max = 0.424	R_int = 0.073
6227 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.02	Δρ_max = 0.62 e Å⁻³
2356 reflections	Δρ_min = −0.93 e Å⁻³
144 parameters

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

	x	y	z	U_iso*/U_eq
Cd1	0.5000	0.5000	0.5000	0.02740 (13)
Br1	0.626658 (19)	0.61470 (5)	0.54529 (3)	0.04254 (15)
C1	0.44435 (18)	0.8564 (4)	0.4098 (2)	0.0332 (8)
H1	0.4561	0.8760	0.4775	0.040*
C2	0.43309 (18)	0.6830 (4)	0.2848 (2)	0.0350 (8)
H2	0.4368	0.5807	0.2639	0.042*
C3	0.42099 (19)	0.9802 (4)	0.3443 (2)	0.0317 (8)
H3	0.4171	1.0810	0.3673	0.038*
C4	0.40298 (16)	0.9534 (4)	0.2423 (2)	0.0270 (7)
C5	0.40919 (18)	0.7997 (4)	0.2139 (2)	0.0341 (8)
H5	0.3971	0.7758	0.1467	0.041*
C6	0.33391 (18)	1.0483 (5)	0.0698 (2)	0.0337 (8)
H6	0.3149	0.9472	0.0558	0.040*
C7	0.38011 (16)	1.0865 (4)	0.1687 (2)	0.0276 (7)
C8	0.2340 (2)	0.9862 (5)	−0.1300 (3)	0.0524 (11)
H8A	0.2646	0.9016	−0.1281	0.079*
H8B	0.1990	0.9969	−0.1970	0.079*
H8C	0.2131	0.9631	−0.0848	0.079*
C9	0.2647 (2)	1.2464 (5)	−0.1787 (3)	0.0423 (9)
H9A	0.2856	1.3452	−0.1492	0.063*
H9B	0.2167	1.2629	−0.2196	0.063*
H9C	0.2866	1.2058	−0.2195	0.063*
C10	0.31637 (17)	1.1583 (4)	−0.0065 (2)	0.0299 (7)
H10	0.3371	1.2575	0.0093	0.036*
N1	0.45139 (14)	0.7084 (3)	0.38242 (19)	0.0311 (6)
N2	0.27261 (15)	1.1335 (4)	−0.1000 (2)	0.0338 (7)
O1	0.40227 (12)	1.2232 (3)	0.19871 (16)	0.0343 (5)
O2	0.50607 (12)	0.3380 (3)	0.37287 (16)	0.0368 (6)
H2A	0.4661	0.3344	0.3253	0.044*
H2B	0.5323	0.3885	0.3525	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0341 (2)	0.0237 (2)	0.02374 (19)	0.00164 (13)	0.01137 (15)	0.00238 (13)
Br1	0.0377 (2)	0.0426 (3)	0.0455 (2)	−0.00547 (16)	0.01541 (19)	0.00457 (17)
C1	0.043 (2)	0.031 (2)	0.0228 (15)	−0.0064 (15)	0.0108 (14)	0.0005 (14)
C2	0.043 (2)	0.0280 (19)	0.0297 (16)	0.0049 (15)	0.0112 (15)	0.0012 (15)
C3	0.043 (2)	0.0242 (19)	0.0264 (16)	−0.0044 (14)	0.0129 (15)	−0.0006 (13)
C4	0.0252 (17)	0.0282 (17)	0.0270 (15)	−0.0016 (13)	0.0102 (13)	0.0032 (14)
C5	0.042 (2)	0.036 (2)	0.0241 (15)	0.0019 (15)	0.0131 (15)	−0.0017 (15)
C6	0.037 (2)	0.0299 (19)	0.0284 (16)	−0.0003 (15)	0.0076 (15)	0.0022 (15)
C7	0.0299 (18)	0.029 (2)	0.0260 (16)	0.0017 (14)	0.0132 (14)	0.0028 (14)
C8	0.058 (3)	0.049 (3)	0.037 (2)	−0.0098 (19)	0.006 (2)	−0.0102 (18)
C9	0.044 (2)	0.051 (2)	0.0299 (17)	0.0098 (18)	0.0135 (16)	0.0129 (17)
C10	0.0322 (18)	0.0291 (18)	0.0275 (15)	0.0002 (14)	0.0115 (14)	−0.0019 (14)
N1	0.0342 (16)	0.0294 (17)	0.0295 (14)	−0.0007 (12)	0.0129 (12)	0.0049 (12)
N2	0.0338 (16)	0.0398 (18)	0.0251 (13)	0.0008 (12)	0.0094 (12)	0.0021 (13)
O1	0.0407 (14)	0.0288 (14)	0.0293 (11)	−0.0061 (10)	0.0105 (11)	0.0017 (10)
O2	0.0361 (13)	0.0434 (15)	0.0304 (12)	−0.0041 (11)	0.0132 (10)	−0.0094 (11)

Geometric parameters (Å, º) top

Cd1—O2ⁱ	2.355 (2)	C6—C10	1.379 (5)
Cd1—O2	2.355 (2)	C6—C7	1.411 (4)
Cd1—N1ⁱ	2.377 (3)	C6—H6	0.9300
Cd1—N1	2.377 (3)	C7—O1	1.255 (4)
Cd1—Br1ⁱ	2.6855 (5)	C8—N2	1.455 (5)
Cd1—Br1	2.6855 (5)	C8—H8A	0.9600
C1—N1	1.339 (4)	C8—H8B	0.9600
C1—C3	1.365 (5)	C8—H8C	0.9600
C1—H1	0.9300	C9—N2	1.449 (4)
C2—N1	1.333 (4)	C9—H9A	0.9600
C2—C5	1.366 (5)	C9—H9B	0.9600
C2—H2	0.9300	C9—H9C	0.9600
C3—C4	1.398 (4)	C10—N2	1.316 (4)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.385 (5)	O2—H2A	0.8500
C4—C7	1.491 (4)	O2—H2B	0.8501
C5—H5	0.9300

O2ⁱ—Cd1—O2	180.0	C10—C6—C7	121.2 (3)
O2ⁱ—Cd1—N1ⁱ	90.43 (9)	C10—C6—H6	119.4
O2—Cd1—N1ⁱ	89.57 (9)	C7—C6—H6	119.4
O2ⁱ—Cd1—N1	89.57 (9)	O1—C7—C6	124.8 (3)
O2—Cd1—N1	90.43 (9)	O1—C7—C4	118.4 (3)
N1ⁱ—Cd1—N1	180.00 (11)	C6—C7—C4	116.8 (3)
O2ⁱ—Cd1—Br1ⁱ	91.41 (6)	N2—C8—H8A	109.5
O2—Cd1—Br1ⁱ	88.59 (6)	N2—C8—H8B	109.5
N1ⁱ—Cd1—Br1ⁱ	90.33 (7)	H8A—C8—H8B	109.5
N1—Cd1—Br1ⁱ	89.67 (7)	N2—C8—H8C	109.5
O2ⁱ—Cd1—Br1	88.59 (6)	H8A—C8—H8C	109.5
O2—Cd1—Br1	91.41 (6)	H8B—C8—H8C	109.5
N1ⁱ—Cd1—Br1	89.67 (7)	N2—C9—H9A	109.5
N1—Cd1—Br1	90.33 (7)	N2—C9—H9B	109.5
Br1ⁱ—Cd1—Br1	180.000 (15)	H9A—C9—H9B	109.5
N1—C1—C3	123.8 (3)	N2—C9—H9C	109.5
N1—C1—H1	118.1	H9A—C9—H9C	109.5
C3—C1—H1	118.1	H9B—C9—H9C	109.5
N1—C2—C5	123.3 (3)	N2—C10—C6	125.0 (3)
N1—C2—H2	118.3	N2—C10—H10	117.5
C5—C2—H2	118.3	C6—C10—H10	117.5
C1—C3—C4	119.1 (3)	C2—N1—C1	116.8 (3)
C1—C3—H3	120.5	C2—N1—Cd1	120.2 (2)
C4—C3—H3	120.5	C1—N1—Cd1	122.8 (2)
C5—C4—C3	117.0 (3)	C10—N2—C9	121.4 (3)
C5—C4—C7	122.1 (3)	C10—N2—C8	121.3 (3)
C3—C4—C7	120.9 (3)	C9—N2—C8	117.2 (3)
C2—C5—C4	119.9 (3)	Cd1—O2—H2A	107.7
C2—C5—H5	120.0	Cd1—O2—H2B	104.3
C4—C5—H5	120.0	H2A—O2—H2B	108.3

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱⁱ	0.85	2.02	2.770 (3)	147
O2—H2B···O1ⁱⁱⁱ	0.85	2.31	2.751 (4)	113

Symmetry codes: (ii) x, y−1, z; (iii) −x+1, y−1, −z+1/2.

Experimental details

Crystal data
Chemical formula	[CdBr₂(C₁₀H₁₂N₂O)₂(H₂O)₂]
M_r	660.68
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	273
a, b, c (Å)	21.362 (3), 8.4360 (9), 14.6371 (16)
β (°)	114.456 (3)
V (Å³)	2401.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.27
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.407, 0.424
No. of measured, independent and observed [I > 2σ(I)] reflections	6227, 2356, 2085
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.090, 1.02
No. of reflections	2356
No. of parameters	144
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.93

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱ	0.85	2.02	2.770 (3)	147.0
O2—H2B···O1ⁱⁱ	0.85	2.31	2.751 (4)	113.0

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1, −z+1/2.

Acknowledgements

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

Bi, J. H., Kong, L. T., Huang, Z. X. & Liu, J. H. (2008). Inorg. Chem. 47, 4564–4569. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dong, H. Z., Yang, J., Liu, X. & Gou, S. H. (2008). Inorg. Chem. 47, 2913–2915. Web of Science CSD CrossRef PubMed CAS Google Scholar
Hu, C. H., Li, Q. & Englert, U. (2003). CrystEngComm, 5, 519–529. Web of Science CSD CrossRef CAS Google Scholar
Ito, M., Shibata, T. & Saito, Y. (1984). Acta Cryst. C40, 2041–2043. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, Y.-Y., Dong, H.-Z. & Cheng, L. (2008). Acta Cryst. E64, o901. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page m358

doi:10.1107/S1600536809007028

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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