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Acta Cryst. (2007). E63, m1629    [ doi:10.1107/S160053680702171X ]

Iodido(1,4,7,10-tetraazacyclododecane)zinc(II) triiodide

J. Du, M. Jia and Y.-Z. Li

Abstract top

The asymmetric unit of the title compound, [ZnI(C8H16N4)]I3, contains one iodido(1,4,7,10-tetraazacyclododecane)zinc(II) cation, with zinc in a slightly distorted square-pyramidal coordination geometry, and one triiodide counter-anion. The coordination number of zinc is five. In the cation, the iodine ion is located at the apex of the square pyramid and the zinc ion lies 0.846 (15) Å from the basal plane, which is made up of four N atoms. Weak intermolecular C-H...I interactions seem to be effective in stabilizing the crystal structure.

Comment top

The 1,4,7,10-tetraazacyclododecane (cyclen) is a multipotent ligand which has been used in chemistry, biology and many other fields not only due to its excellent coordination properties but also because of the interesting characteristics of its with metal complexes (Guo et al., 1999). Previously accumulated studies about the intrinsic chemical properties of Zn2+ can be finely tuned by complexation with macrocyclic polyamines such as 1,5,9-triazacyclododecane and 1,4,7,10-tetraazacyclododecane (Kimura et al., 2004). Kimura et al. and others also have investigated the coordination of imides and phosphates to Zn(II)-cyclen complexes in great detail (Kimura et al., 1993; Kimura et al.,1997).

In this paper, we report the crystal structure of a novel Zn(II)-cyclen complex composed of a iodo-(1,4,7,10-tetraazacyclododecane)-zinc(II) cation and a triiodine anion as the counter anion. The asymmetric unit of the title compound is presented in Figure 1. In the cation each zinc atom is coordinated by four nitrogen atoms of the cyclen and one iodo ligand (Fig.1). Weak intermolecular C—H···I interactions seem to be effective in the stabilization of the whole crystal structure in which two neighboring cations are linked into a dimeric unit (C4—H4b···I1i; i: 1 - x,1 - y,1 - z) (Fig. 2). Additional weak intermolecular C—H···I interactions (C7—H7a···I4; C5—H5b···I4ii; ii: -x,1 - y,-z) link all of the dimers into a linear one-dimensional supramolecular structure (Fig. 2).

Related literature top

For related literature, see: Kimura et al. (1997); Shionoya et al. (1993); Wang et al. (2003); Aoki & Kimura (2004).

Experimental top

The title complex was prepared by the direct combination of 1:1 molar equivalents of cyclen, Zn(NO3)2 and KI in ethanol at room temperature for two hours. Then the solution was filtered off and placed directly in the air to evapore the solvent. Single crystals of the title compound suitable for structure analysis were obtained fromn the solution after two weeks.

Refinement top

H atoms were positioned geometrically and refined using a riding model with C—H = 0.97 Å, N—H = 0.91 Å, and with Uiso(H) = 1.2 times Ueq(C or N).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View of the title complex showing the labeling of the non-H atoms. Thermal ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. View of the linear one-dimensional supramolecular structure down the b axis. Symmetry codes: (i) 1 - x, 1 - y, 1 - z (ii) -x, 1 - y, -z.
Iodido(1,4,7,10-tetraazacyclododecane)zinc(II) triiodide top
Crystal data top
[ZnI(C8H16N4)]I3V = 931.5 (2) Å3
Mr = 745.25Z = 2
Triclinic, P1F(000) = 676
Hall symbol: -P 1Dx = 2.657 Mg m−3
a = 8.596 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.120 (1) ÅCell parameters from 1388 reflections
c = 12.342 (2) Åθ = 2.6–22.2°
α = 94.894 (2)°µ = 7.94 mm−1
β = 104.707 (2)°T = 298 K
γ = 91.295 (2)°0.26 × 0.24 × 0.22 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3575 independent reflections
Radiation source: sealed tube2260 reflections with I > 2σ(I)
graphiteRint = 0.030
phi and ω scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −10→10
Tmin = 0.15, Tmax = 0.17k = −11→8
5025 measured reflectionsl = −15→14
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)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0612P)2 + 1.99P]
where P = (Fo2 + 2Fc2)/3
3575 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 1.65 e Å−3
0 restraintsΔρmin = −1.68 e Å−3
Crystal data top
[ZnI(C8H16N4)]I3γ = 91.295 (2)°
Mr = 745.25V = 931.5 (2) Å3
Triclinic, P1Z = 2
a = 8.596 (1) ÅMo Kα radiation
b = 9.120 (1) ŵ = 7.94 mm−1
c = 12.342 (2) ÅT = 298 K
α = 94.894 (2)°0.26 × 0.24 × 0.22 mm
β = 104.707 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3575 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2260 reflections with I > 2σ(I)
Tmin = 0.15, Tmax = 0.17Rint = 0.030
5025 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.063H-atom parameters constrained
wR(F2) = 0.141Δρmax = 1.65 e Å−3
S = 1.07Δρmin = −1.68 e Å−3
3575 reflectionsAbsolute structure: ?
154 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
C10.1065 (17)0.9305 (16)0.3598 (12)0.060 (4)
H1A0.02780.88830.29270.072*
H1B0.07281.02590.38380.072*
C20.1345 (16)0.8207 (17)0.4595 (11)0.058 (4)
H2A0.03320.79840.47690.070*
H2B0.20870.86770.52700.070*
C30.0937 (17)0.5709 (16)0.3631 (12)0.061 (4)
H3A0.01080.61770.31030.073*
H3B0.04550.52440.41530.073*
C40.1799 (16)0.4582 (15)0.3013 (12)0.056 (3)
H4A0.10210.38340.25720.067*
H4B0.25890.41010.35600.067*
C50.1637 (15)0.5576 (14)0.1195 (10)0.052 (3)
H5A0.06710.60340.12980.062*
H5B0.13330.46500.07310.062*
C60.264 (2)0.6633 (15)0.0640 (12)0.067 (4)
H6A0.36020.61680.05400.080*
H6B0.19970.6859−0.00890.080*
C70.1895 (17)0.9072 (14)0.1314 (12)0.056 (3)
H7A0.08690.85790.12800.067*
H7B0.18070.95160.06160.067*
C80.2340 (15)1.0297 (14)0.2343 (13)0.061 (4)
H8A0.15181.10190.22780.073*
H8B0.33661.07970.23880.073*
I10.64993 (10)0.75291 (11)0.42815 (8)0.0584 (3)
I2−0.33154 (12)1.35959 (11)0.26103 (8)0.0616 (3)
I3−0.30693 (10)1.06260 (10)0.16838 (7)0.0498 (2)
I4−0.28278 (12)0.75799 (11)0.07214 (8)0.0637 (3)
N10.2439 (14)0.9392 (12)0.3441 (9)0.060 (3)
H10.30930.99260.40490.072*
N20.2099 (14)0.6659 (12)0.4164 (10)0.062 (3)
H20.27300.62630.47670.074*
N30.2664 (12)0.5358 (11)0.2213 (8)0.047 (3)
H30.34970.48180.21020.056*
N40.3093 (13)0.8072 (13)0.1461 (10)0.060 (3)
H40.40020.85070.13590.072*
Zn10.35735 (17)0.74403 (17)0.31372 (12)0.0475 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.048 (8)0.060 (9)0.059 (9)0.016 (6)−0.006 (6)−0.011 (7)
C20.041 (7)0.086 (11)0.043 (7)0.008 (7)0.004 (6)−0.003 (7)
C30.057 (8)0.070 (9)0.052 (8)−0.030 (7)0.007 (6)0.018 (7)
C40.052 (8)0.043 (7)0.064 (9)0.002 (6)0.000 (7)−0.001 (6)
C50.047 (7)0.056 (8)0.044 (7)−0.010 (6)0.007 (6)−0.025 (6)
C60.105 (13)0.050 (8)0.052 (8)0.018 (8)0.028 (8)0.014 (7)
C70.056 (8)0.048 (8)0.063 (9)0.016 (6)0.010 (6)0.019 (6)
C80.033 (6)0.041 (7)0.092 (11)−0.002 (5)−0.010 (6)−0.005 (7)
I10.0407 (5)0.0647 (6)0.0574 (6)0.0038 (4)−0.0045 (4)−0.0113 (4)
I20.0593 (6)0.0559 (6)0.0614 (6)0.0094 (4)0.0034 (4)−0.0046 (4)
I30.0421 (4)0.0550 (5)0.0523 (5)0.0052 (3)0.0100 (4)0.0096 (4)
I40.0624 (6)0.0585 (6)0.0646 (6)0.0078 (4)0.0107 (5)−0.0099 (5)
N10.056 (7)0.056 (7)0.047 (6)0.007 (5)−0.012 (5)−0.032 (5)
N20.058 (7)0.049 (7)0.072 (8)0.002 (5)0.003 (6)0.017 (6)
N30.038 (5)0.048 (6)0.043 (6)0.011 (4)−0.007 (4)−0.007 (5)
N40.040 (6)0.066 (8)0.076 (8)−0.011 (5)0.012 (5)0.023 (6)
Zn10.0400 (8)0.0514 (8)0.0455 (8)0.0024 (6)0.0036 (6)−0.0050 (6)
Geometric parameters (Å, °) top
C1—N11.246 (18)C7—N41.379 (16)
C1—C21.63 (2)C7—C81.581 (19)
C1—H1A0.9700C7—I44.115 (15)
C1—H1B0.9700C7—H7A0.9700
C2—N21.669 (18)C7—H7B0.9700
C2—H2A0.9700C8—N11.632 (19)
C2—H2B0.9700C8—H8A0.9700
C3—N21.308 (16)C8—H8B0.9700
C3—C41.54 (2)I1—Zn12.5483 (16)
C3—H3A0.9700I2—I32.8826 (13)
C3—H3B0.9700I3—I42.9599 (14)
C4—N31.581 (18)I4—H7A3.1705
C4—H4A0.9700N1—Zn12.100 (11)
C4—H4B0.9700N1—H10.9100
C5—N31.373 (16)N2—Zn12.156 (12)
C5—C61.59 (2)N2—H20.9100
C5—H5A0.9700N3—Zn12.151 (10)
C5—H5B0.9700N3—H30.9100
C6—N41.565 (18)N4—Zn12.136 (12)
C6—H6A0.9700N4—H40.9100
C6—H6B0.9700
N1—C1—C2101.0 (11)H7A—C7—H7B108.4
N1—C1—H1A111.6C7—C8—N1104.3 (10)
C2—C1—H1A111.6C7—C8—H8A110.9
N1—C1—H1B111.6N1—C8—H8A110.9
C2—C1—H1B111.6C7—C8—H8B110.9
H1A—C1—H1B109.4N1—C8—H8B110.9
C1—C2—N2108.7 (10)H8A—C8—H8B108.9
C1—C2—H2A110.0I2—I3—I4179.70 (5)
N2—C2—H2A110.0I3—I4—H7A81.9
C1—C2—H2B110.0I3—I4—C780.26 (18)
N2—C2—H2B110.0C1—N1—C8108.1 (11)
H2A—C2—H2B108.3C1—N1—Zn1118.8 (10)
N2—C3—C4103.2 (12)C8—N1—Zn1105.5 (7)
N2—C3—H3A111.1C1—N1—H1108.0
C4—C3—H3A111.1C8—N1—H1108.0
N2—C3—H3B111.1Zn1—N1—H1108.0
C4—C3—H3B111.1C3—N2—C2110.4 (12)
H3A—C3—H3B109.1C3—N2—Zn1114.6 (10)
C3—C4—N3111.0 (10)C2—N2—Zn1102.5 (7)
C3—C4—H4A109.4C3—N2—H2109.7
N3—C4—H4A109.4C2—N2—H2109.7
C3—C4—H4B109.4Zn1—N2—H2109.7
N3—C4—H4B109.4C5—N3—C4112.9 (10)
H4A—C4—H4B108.0C5—N3—Zn1110.3 (8)
N3—C5—C6104.4 (10)C4—N3—Zn1104.0 (7)
N3—C5—H5A110.9C5—N3—H3109.8
C6—C5—H5A110.9C4—N3—H3109.8
N3—C5—H5B110.9Zn1—N3—H3109.8
C6—C5—H5B110.9C7—N4—C6113.4 (11)
H5A—C5—H5B108.9C7—N4—Zn1109.0 (10)
N4—C6—C5106.7 (10)C6—N4—Zn1107.4 (7)
N4—C6—H6A110.4C7—N4—H4109.0
C5—C6—H6A110.4C6—N4—H4109.0
N4—C6—H6B110.4Zn1—N4—H4109.0
C5—C6—H6B110.4N1—Zn1—N483.6 (5)
H6A—C6—H6B108.6N1—Zn1—N3132.1 (4)
N4—C7—C8108.2 (11)N4—Zn1—N380.3 (4)
N4—C7—I4119.4 (8)N1—Zn1—N280.5 (5)
C8—C7—I4110.6 (8)N4—Zn1—N2134.3 (4)
N4—C7—H7A110.1N3—Zn1—N279.4 (4)
C8—C7—H7A110.1N1—Zn1—I1111.8 (3)
N4—C7—H7B110.1N4—Zn1—I1117.7 (3)
C8—C7—H7B110.1N3—Zn1—I1115.7 (3)
I4—C7—H7B98.0N2—Zn1—I1107.9 (3)
Acknowledgements top

Financial support from the National Natural Science Foundation of China (No. 30370351) and the Natural Science Foundation of Jiangsu province (No. BK 2005209) is gratefully acknowledged.

references
References top

Aoki, S. & Kimura, E. (2004). Chem. Rev. pp. 769–787.

Bruker (2000). SMART (Version 5.0), SAINT (Version 6), SHELXTL (Version 6.1) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.

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Shionoya, M., Kimura, E. & Shiro, M. (1993). J. Am. Chem. Soc. 115, 6730–6737.

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