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Acta Cryst. (2008). E64, m762    [ doi:10.1107/S1600536808008040 ]

Bis(diethylenetriamine)cadmium(II) diiodide

B. Huang, Z. Liu and L. Wang

Abstract top

In the title compound, [Cd(dien)2]I2, where dien = diethylenetriamine (C4H13N3), the CdII ion is in a distorted octahedral coordination environment. In the crystal structure, intermolecular N-H...I hydrogen bonds link cations and anions into a three-dimensional network.

Comment top

The goal of our research has been to determine the capability of a number of linear multidentate ligands to induce extended structures in cadmium compounds. Previously, some ligands containing diethylenetriamine and their metal coordination compounds have been studied (Hines et al.,2006; Biagini & Cannas, 1970; Hynes, et al., 1996; Xiang, et al., 2006).

In the molecular structure, the CdII ion is coordinated by six N atoms from two diethylene triamine ligands, forming a distorted octahedral coordination geometry (Fig. 1). In the crystal structure, intermolecular N–H···I hydrogen bonds link the cations and anions into a three-dimensional network (Fig.2).

Related literature top

For related literature, see: Hynes et al. (1996); Biagini & Cannas (1970); Xiang et al. (2006); Hines et al. (2006).

Experimental top

Diethylenetriamine (0.21 g, 2.0 mmol) in 10 ml water was added slowly to a CdAc2.2H2O (0.27 g, 1.0 mmol) solution in 10 ml water and KI (0.33 g, 2.0 mmol) solution in 10 ml water. The mixture was stirred for 1 h. After filtration, the colourless solution was allowed to stand at room temperature. Colourless block-shaped crystals suitable for X-ray analysis were obtained in several days in 50% yield.

Refinement top

H atoms were placed in calculated positions with C—H = 0.97 Å, N—H = 0.90Å (NH2) N—H = 0.91Å (NH) and Uiso=1.2Ueq(C,N).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure, showing 50% probability displacement ellipsoids and H atoms as small spheres.
[Figure 2] Fig. 2. Part of the crystal structure showing hydrogen bonds as dashed lines.
(I) top
Crystal data top
[Cd(C4H13N3)2]I2F000 = 1080
Mr = 572.55Dx = 2.071 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1123 reflections
a = 9.8842 (9) Åθ = 2.4–26.8º
b = 15.1947 (11) ŵ = 4.55 mm−1
c = 12.4209 (9) ÅT = 292 (2) K
β = 100.204 (6)ºBlock, colorless
V = 1836.0 (3) Å30.30 × 0.30 × 0.20 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		3991 independent reflections
Radiation source: fine focus sealed Siemens Mo tube3214 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 292(2) Kθmax = 27.0º
0.3° wide ω exposures scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→6
Tmin = 0.102, Tmax = 0.177k = −19→19
10779 measured reflectionsl = −15→15
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)] = 0.024H-atom parameters constrained
wR(F2) = 0.057  w = 1/[σ2(Fo2) + (0.0279P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
3991 reflectionsΔρmax = 0.73 e Å−3
154 parametersΔρmin = −0.64 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cd(C4H13N3)2]I2V = 1836.0 (3) Å3
Mr = 572.55Z = 4
Monoclinic, P21/cMo Kα
a = 9.8842 (9) ŵ = 4.55 mm−1
b = 15.1947 (11) ÅT = 292 (2) K
c = 12.4209 (9) Å0.30 × 0.30 × 0.20 mm
β = 100.204 (6)º
Data collection top
Bruker SMART APEX CCD
diffractometer		3991 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3214 reflections with I > 2σ(I)
Tmin = 0.102, Tmax = 0.177Rint = 0.021
10779 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024154 parameters
wR(F2) = 0.057H-atom parameters constrained
S = 1.08Δρmax = 0.73 e Å−3
3991 reflectionsΔρmin = −0.64 e Å−3
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
xyzUiso*/Ueq
Cd10.22542 (2)0.082844 (14)0.762034 (17)0.04124 (7)
C10.4649 (5)0.1808 (3)0.6705 (4)0.0826 (13)
H1A0.54850.21540.68640.099*
H1B0.41670.19720.59840.099*
C20.5008 (4)0.0855 (3)0.6713 (4)0.0794 (13)
H2A0.55770.07420.61670.095*
H2B0.55300.06970.74230.095*
C30.3956 (5)−0.0636 (3)0.6679 (4)0.0875 (14)
H3A0.4529−0.07340.73880.105*
H3B0.4414−0.08920.61240.105*
C40.2589 (5)−0.1067 (3)0.6646 (4)0.0842 (14)
H4A0.2022−0.09750.59330.101*
H4B0.2716−0.16960.67560.101*
C5−0.0645 (4)0.1671 (3)0.6612 (4)0.0790 (12)
H5A−0.15500.16240.61620.095*
H5B−0.03140.22670.65500.095*
C6−0.0731 (4)0.1480 (3)0.7764 (4)0.0792 (12)
H6A−0.13670.18870.80120.095*
H6B−0.10800.08880.78200.095*
C70.0734 (5)0.1198 (4)0.9566 (3)0.0876 (14)
H7A0.03900.05980.95250.105*
H7B0.01790.15440.99800.105*
C80.2183 (5)0.1208 (3)1.0127 (3)0.0856 (14)
H8A0.25120.18101.01880.103*
H8B0.22420.09751.08610.103*
I10.18377 (3)0.107898 (16)0.365025 (19)0.05948 (8)
I20.65646 (3)0.170576 (15)0.988829 (18)0.05505 (8)
N10.3786 (3)0.20013 (19)0.7513 (2)0.0624 (8)
H1C0.33070.24980.73240.075*
H1D0.43180.20870.81710.075*
N20.3770 (3)0.0320 (2)0.6482 (2)0.0651 (8)
H20.33680.04050.57720.078*
N30.1905 (3)−0.07111 (17)0.7482 (2)0.0589 (8)
H3C0.2237−0.09670.81280.071*
H3D0.0998−0.08270.73160.071*
N40.0290 (3)0.1048 (2)0.6231 (2)0.0615 (8)
H4C0.05540.12570.56230.074*
H4D−0.01430.05310.60650.074*
N50.0621 (3)0.1560 (2)0.8462 (2)0.0604 (8)
H50.08480.21410.85200.073*
N60.3059 (3)0.06852 (19)0.9535 (2)0.0606 (8)
H6C0.30360.01160.97310.073*
H6D0.39340.08740.97020.073*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.03847 (13)0.04408 (13)0.04229 (12)0.00397 (10)0.01021 (10)−0.00010 (9)
C10.070 (3)0.110 (4)0.072 (3)−0.022 (3)0.024 (2)0.021 (2)
C20.048 (2)0.121 (4)0.074 (3)0.001 (2)0.025 (2)−0.007 (3)
C30.075 (3)0.082 (3)0.108 (4)0.028 (3)0.022 (3)−0.031 (3)
C40.101 (4)0.066 (3)0.081 (3)0.015 (3)0.003 (3)−0.024 (2)
C50.057 (2)0.077 (3)0.098 (3)0.023 (2)0.001 (2)0.009 (2)
C60.048 (2)0.099 (3)0.094 (3)0.017 (2)0.022 (2)−0.014 (3)
C70.091 (4)0.119 (4)0.063 (2)−0.002 (3)0.039 (3)−0.011 (2)
C80.117 (4)0.097 (3)0.044 (2)−0.010 (3)0.018 (2)−0.015 (2)
I10.05661 (15)0.05952 (15)0.06234 (15)−0.00248 (11)0.01062 (12)0.00141 (11)
I20.05468 (15)0.05668 (14)0.05193 (13)−0.00187 (11)0.00440 (11)0.00483 (9)
N10.0556 (18)0.0579 (17)0.0728 (19)−0.0036 (15)0.0085 (16)0.0135 (15)
N20.0564 (19)0.087 (2)0.0537 (16)0.0093 (18)0.0138 (15)−0.0073 (16)
N30.067 (2)0.0489 (16)0.0553 (16)−0.0018 (15)−0.0044 (15)−0.0007 (13)
N40.0578 (18)0.074 (2)0.0518 (16)0.0084 (16)0.0064 (15)0.0092 (14)
N50.064 (2)0.0563 (17)0.0658 (18)0.0051 (15)0.0250 (17)−0.0098 (14)
N60.074 (2)0.0551 (17)0.0481 (15)−0.0121 (15)−0.0012 (15)0.0081 (13)
Geometric parameters (Å, °) top
Cd1—N52.352 (3)C5—H5A0.9700
Cd1—N12.357 (3)C5—H5B0.9700
Cd1—N22.365 (3)C6—N51.463 (5)
Cd1—N32.366 (3)C6—H6A0.9700
Cd1—N62.380 (3)C6—H6B0.9700
Cd1—N42.381 (3)C7—N51.464 (5)
C1—N11.457 (5)C7—C81.478 (6)
C1—C21.490 (6)C7—H7A0.9700
C1—H1A0.9700C7—H7B0.9700
C1—H1B0.9700C8—N61.465 (5)
C2—N21.455 (5)C8—H8A0.9700
C2—H2A0.9700C8—H8B0.9700
C2—H2B0.9700I2—N13.685 (3)
C3—N21.478 (5)N1—H1C0.9000
C3—C41.497 (6)N1—H1D0.9000
C3—H3A0.9700N2—H20.9100
C3—H3B0.9700N3—H3C0.9000
C4—N31.441 (5)N3—H3D0.9000
C4—H4A0.9700N4—H4C0.9000
C4—H4B0.9700N4—H4D0.9000
C5—N41.460 (5)N5—H50.9100
C5—C61.478 (6)N6—H6C0.9000
C5—I14.854 (4)N6—H6D0.9000
N5—Cd1—N199.56 (11)H6A—C6—H6B108.1
N5—Cd1—N2167.86 (11)N5—C7—C8110.1 (4)
N1—Cd1—N274.45 (11)N5—C7—H7A109.6
N5—Cd1—N3113.37 (11)C8—C7—H7A109.6
N1—Cd1—N3146.11 (11)N5—C7—H7B109.6
N2—Cd1—N374.54 (11)C8—C7—H7B109.6
N5—Cd1—N674.53 (10)H7A—C7—H7B108.2
N1—Cd1—N691.23 (10)N6—C8—C7111.5 (3)
N2—Cd1—N6115.63 (11)N6—C8—H8A109.3
N3—Cd1—N690.05 (10)C7—C8—H8A109.3
N5—Cd1—N473.76 (10)N6—C8—H8B109.3
N1—Cd1—N4107.61 (11)C7—C8—H8B109.3
N2—Cd1—N497.70 (11)H8A—C8—H8B108.0
N3—Cd1—N489.76 (10)C1—N1—Cd1110.3 (2)
N6—Cd1—N4145.29 (10)C1—N1—I294.7 (2)
N1—C1—C2111.0 (3)Cd1—N1—I2104.93 (9)
N1—C1—H1A109.4C1—N1—H1C109.6
C2—C1—H1A109.4Cd1—N1—H1C109.6
N1—C1—H1B109.4I2—N1—H1C126.4
C2—C1—H1B109.4C1—N1—H1D109.6
H1A—C1—H1B108.0Cd1—N1—H1D109.6
N2—C2—C1110.6 (3)H1C—N1—H1D108.1
N2—C2—H2A109.5C2—N2—C3116.1 (3)
C1—C2—H2A109.5C2—N2—Cd1107.4 (2)
N2—C2—H2B109.5C3—N2—Cd1107.2 (2)
C1—C2—H2B109.5C2—N2—H2108.6
H2A—C2—H2B108.1C3—N2—H2108.6
N2—C3—C4109.9 (4)Cd1—N2—H2108.6
N2—C3—H3A109.7C4—N3—Cd1110.0 (2)
C4—C3—H3A109.7C4—N3—H3C109.7
N2—C3—H3B109.7Cd1—N3—H3C109.7
C4—C3—H3B109.7C4—N3—H3D109.7
H3A—C3—H3B108.2Cd1—N3—H3D109.7
N3—C4—C3110.6 (3)H3C—N3—H3D108.2
N3—C4—H4A109.5C5—N4—Cd1109.7 (2)
C3—C4—H4A109.5C5—N4—H4C109.7
N3—C4—H4B109.5Cd1—N4—H4C109.7
C3—C4—H4B109.5C5—N4—H4D109.7
H4A—C4—H4B108.1Cd1—N4—H4D109.7
N4—C5—C6109.5 (3)H4C—N4—H4D108.2
C6—C5—I1145.2 (2)C6—N5—C7115.7 (3)
N4—C5—H5A109.8C6—N5—Cd1108.9 (2)
C6—C5—H5A109.8C7—N5—Cd1107.1 (3)
I1—C5—H5A95.1C6—N5—H5108.3
N4—C5—H5B109.8C7—N5—H5108.3
C6—C5—H5B109.8Cd1—N5—H5108.3
I1—C5—H5B83.7C8—N6—Cd1109.2 (2)
H5A—C5—H5B108.2C8—N6—H6C109.8
N5—C6—C5110.7 (3)Cd1—N6—H6C109.8
N5—C6—H6A109.5C8—N6—H6D109.8
C5—C6—H6A109.5Cd1—N6—H6D109.8
N5—C6—H6B109.5H6C—N6—H6D108.3
C5—C6—H6B109.5
N1—C1—C2—N258.9 (5)N5—Cd1—N3—C4159.6 (3)
N2—C3—C4—N3−60.7 (5)N1—Cd1—N3—C4−35.0 (3)
N4—C5—C6—N560.3 (5)N2—Cd1—N3—C4−10.6 (3)
I1—C5—C6—N547.9 (7)N6—Cd1—N3—C4−127.3 (3)
N5—C7—C8—N6−59.8 (5)N4—Cd1—N3—C487.5 (3)
C2—C1—N1—Cd1−36.4 (4)C6—C5—N4—Cd1−41.6 (4)
C2—C1—N1—I271.5 (3)I1—C5—N4—Cd1126.6 (3)
N5—Cd1—N1—C1−161.1 (3)N5—Cd1—N4—C513.1 (2)
N2—Cd1—N1—C18.0 (3)N1—Cd1—N4—C5−82.0 (3)
N3—Cd1—N1—C132.4 (3)N2—Cd1—N4—C5−158.1 (3)
N6—Cd1—N1—C1124.3 (3)N3—Cd1—N4—C5127.6 (3)
N4—Cd1—N1—C1−85.3 (3)N6—Cd1—N4—C537.8 (3)
N5—Cd1—N1—I297.95 (10)C5—C6—N5—C7−166.7 (4)
N2—Cd1—N1—I2−92.87 (11)C5—C6—N5—Cd1−46.1 (4)
N3—Cd1—N1—I2−68.49 (19)C8—C7—N5—C6172.1 (4)
N6—Cd1—N1—I223.43 (10)C8—C7—N5—Cd150.5 (4)
N4—Cd1—N1—I2173.83 (9)N1—Cd1—N5—C6122.7 (3)
C1—C2—N2—C3−168.3 (3)N2—Cd1—N5—C663.4 (6)
C1—C2—N2—Cd1−48.4 (4)N3—Cd1—N5—C6−65.5 (3)
C4—C3—N2—C2167.6 (3)N6—Cd1—N5—C6−148.7 (3)
C4—C3—N2—Cd147.6 (4)N4—Cd1—N5—C617.0 (3)
N5—Cd1—N2—C282.9 (6)N1—Cd1—N5—C7−111.5 (3)
N1—Cd1—N2—C221.2 (3)N2—Cd1—N5—C7−170.9 (5)
N3—Cd1—N2—C2−145.0 (3)N3—Cd1—N5—C760.3 (3)
N6—Cd1—N2—C2−62.6 (3)N6—Cd1—N5—C7−22.9 (3)
N4—Cd1—N2—C2127.4 (3)N4—Cd1—N5—C7142.8 (3)
N5—Cd1—N2—C3−151.7 (5)C7—C8—N6—Cd135.5 (4)
N1—Cd1—N2—C3146.6 (3)N5—Cd1—N6—C8−6.3 (3)
N3—Cd1—N2—C3−19.6 (3)N1—Cd1—N6—C893.3 (3)
N6—Cd1—N2—C362.9 (3)N2—Cd1—N6—C8166.6 (3)
N4—Cd1—N2—C3−107.2 (3)N3—Cd1—N6—C8−120.6 (3)
C3—C4—N3—Cd139.8 (4)N4—Cd1—N6—C8−30.9 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3C···I2i0.902.773.673 (3)176
N6—H6C···I2i0.902.823.709 (3)168
N3—H3D···I1ii0.902.873.759 (3)168
N4—H4D···I1ii0.903.023.873 (3)159
N5—H5···I1iii0.912.873.778 (3)174
N1—H1D···I20.902.853.685 (3)155
N2—H2···I10.912.983.869 (3)167
N4—H4C···I10.902.963.789 (3)153
N6—H6D···I20.902.863.751 (3)169
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y, −z+1; (iii) x, −y+1/2, z+1/2.
Table 1
Selected geometric parameters (Å) top
Cd1—N52.352 (3)Cd1—N32.366 (3)
Cd1—N12.357 (3)Cd1—N62.380 (3)
Cd1—N22.365 (3)Cd1—N42.381 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3C···I2i0.902.773.673 (3)176
N6—H6C···I2i0.902.823.709 (3)168
N3—H3D···I1ii0.902.873.759 (3)168
N4—H4D···I1ii0.903.023.873 (3)159
N5—H5···I1iii0.912.873.778 (3)174
N1—H1D···I20.902.853.685 (3)155
N2—H2···I10.912.983.869 (3)167
N4—H4C···I10.902.963.789 (3)153
N6—H6D···I20.902.863.751 (3)169
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y, −z+1; (iii) x, −y+1/2, z+1/2.
Acknowledgements top

This work is supported by the National 863 High Technology Research and Development Program of China (No.2002 A A214011).

references
References top

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