Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106017720/gd3008sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106017720/gd3008Isup2.hkl |
CCDC reference: 616106
Zinc oxide (0.2 g, 0.0025 mol), CdI2 (0.455 g, 0.00125 mol), NH4I (0.72 g, 0.005 mol), dimethylformamide (20 ml) and ethylenediamine (0.5 ml, 0.0075 mol) were heated to 323–333 K and stirred magnetically for about 50 min. The solution was filtered and propan-2-ol (10 ml) was added to the resulting colourless solution. Colourless crystals of (I) suitable for single-crystal X-ray diffraction separated over one day; these were washed with dry propan-2-ol and dried in vacuo at room temperature (yield 1.32 g, 78%). An additional amount of product can be obtained from the filtrate. Analysis, calculated for C12H48CdZn2N12I6 (Mr = 1365.19): C 10.6, H 3.5, Cd 8.2, I 55.8, N 12.3, Zn 9.6%; found: C 10.6, H 3.7, Cd 8.3, I 55.4, N 12.5, Zn 9.6%.
All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.97 Å and N—H = 0.90 Å, and with Uiso(H) = 1.2Ueq(C,N). The absolute axis assignment (Jones, 1986) was established by means of the Flack parameter (Flack, 1983).
Data collection: P3 (Siemens, 1989); cell refinement: P3; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1991); software used to prepare material for publication: SHELXL97.
[Zn(C2H8N2)3][CdI4]I2 | Dx = 2.435 Mg m−3 |
Mr = 1365.16 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I42d | Cell parameters from 24 reflections |
Hall symbol: I -4 2bw | θ = 10–14° |
a = 14.803 (2) Å | µ = 6.84 mm−1 |
c = 16.991 (4) Å | T = 294 K |
V = 3723.2 (11) Å3 | Block, colourless |
Z = 4 | 0.4 × 0.2 × 0.2 mm |
F(000) = 2520 |
Siemens P3/PC diffractometer | 825 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 25.1°, θmin = 1.8° |
θ/2θ scans | h = 0→17 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→17 |
Tmin = 0.127, Tmax = 0.255 | l = 0→20 |
3556 measured reflections | 2 standard reflections every 95 reflections |
916 independent reflections | intensity decay: 5% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0332P)2 + 14.3589P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
916 reflections | Δρmax = 0.51 e Å−3 |
76 parameters | Δρmin = −0.62 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with how many Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.07 (7) |
[Zn(C2H8N2)3][CdI4]I2 | Z = 4 |
Mr = 1365.16 | Mo Kα radiation |
Tetragonal, I42d | µ = 6.84 mm−1 |
a = 14.803 (2) Å | T = 294 K |
c = 16.991 (4) Å | 0.4 × 0.2 × 0.2 mm |
V = 3723.2 (11) Å3 |
Siemens P3/PC diffractometer | 825 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.034 |
Tmin = 0.127, Tmax = 0.255 | 2 standard reflections every 95 reflections |
3556 measured reflections | intensity decay: 5% |
916 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0332P)2 + 14.3589P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | Δρmax = 0.51 e Å−3 |
916 reflections | Δρmin = −0.62 e Å−3 |
76 parameters | Absolute structure: Flack (1983), with how many Friedel pairs |
0 restraints | Absolute structure parameter: −0.07 (7) |
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. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.0000 | 0.0000 | 0.0000 | 0.0372 (3) | |
I1 | 0.13938 (4) | −0.06598 (5) | 0.09476 (4) | 0.04409 (19) | |
Zn1 | −0.28000 (9) | −0.2500 | 0.1250 | 0.0302 (3) | |
N2 | −0.3762 (5) | −0.3284 (5) | 0.0570 (4) | 0.0388 (19) | |
H2C | −0.4313 | −0.3029 | 0.0600 | 0.047* | |
H2D | −0.3594 | −0.3295 | 0.0061 | 0.047* | |
N3 | −0.2971 (5) | −0.1311 (6) | 0.0459 (4) | 0.0417 (19) | |
H3C | −0.2479 | −0.0955 | 0.0479 | 0.050* | |
H3D | −0.3051 | −0.1493 | −0.0041 | 0.050* | |
N1 | −0.1666 (5) | −0.3072 (6) | 0.0593 (5) | 0.041 (2) | |
H1C | −0.1758 | −0.3666 | 0.0509 | 0.050* | |
H1D | −0.1615 | −0.2797 | 0.0123 | 0.050* | |
C2 | −0.3795 (8) | −0.4211 (7) | 0.0882 (7) | 0.056 (3) | |
H2A | −0.3286 | −0.4554 | 0.0685 | 0.068* | |
H2B | −0.4346 | −0.4505 | 0.0710 | 0.068* | |
I2 | −0.2500 | −0.39531 (6) | −0.1250 | 0.0500 (3) | |
C3 | −0.3767 (8) | −0.0817 (8) | 0.0736 (6) | 0.055 (3) | |
H3A | −0.4309 | −0.1107 | 0.0539 | 0.067* | |
H3B | −0.3752 | −0.0205 | 0.0532 | 0.067* | |
C1 | −0.0838 (6) | −0.2937 (7) | 0.1056 (6) | 0.043 (2) | |
H1A | −0.0790 | −0.3410 | 0.1449 | 0.051* | |
H1B | −0.0317 | −0.2980 | 0.0712 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0359 (4) | 0.0359 (4) | 0.0398 (7) | 0.000 | 0.000 | 0.000 |
I1 | 0.0394 (3) | 0.0501 (4) | 0.0428 (3) | 0.0006 (3) | −0.0038 (3) | 0.0087 (3) |
Zn1 | 0.0251 (7) | 0.0391 (8) | 0.0263 (6) | 0.000 | 0.000 | −0.0046 (6) |
N2 | 0.032 (4) | 0.056 (5) | 0.028 (4) | 0.000 (4) | 0.004 (3) | −0.013 (4) |
N3 | 0.042 (4) | 0.051 (5) | 0.032 (4) | −0.005 (4) | −0.007 (4) | 0.004 (4) |
N1 | 0.033 (4) | 0.055 (5) | 0.036 (4) | −0.006 (4) | 0.012 (3) | −0.012 (4) |
C2 | 0.046 (6) | 0.054 (7) | 0.069 (7) | −0.012 (5) | 0.003 (6) | −0.009 (6) |
I2 | 0.0875 (8) | 0.0365 (5) | 0.0261 (4) | 0.000 | 0.0032 (5) | 0.000 |
C3 | 0.054 (7) | 0.068 (8) | 0.044 (6) | 0.008 (6) | −0.002 (5) | 0.010 (5) |
C1 | 0.034 (5) | 0.061 (6) | 0.033 (5) | 0.016 (4) | −0.003 (4) | −0.005 (5) |
Cd1—I1 | 2.7934 (9) | N1—H1D | 0.9000 |
Zn1—N2 | 2.171 (8) | C2—C3i | 1.499 (15) |
Zn1—N1 | 2.186 (7) | C2—H2A | 0.9700 |
Zn1—N3 | 2.229 (8) | C2—H2B | 0.9700 |
N2—C2 | 1.472 (13) | I2—I2 | 0.0000 |
N2—H2C | 0.9000 | C3—C2i | 1.499 (15) |
N2—H2D | 0.9000 | C3—H3A | 0.9700 |
N3—C3 | 1.464 (13) | C3—H3B | 0.9700 |
N3—H3C | 0.9000 | C1—C1i | 1.45 (2) |
N3—H3D | 0.9000 | C1—H1A | 0.9700 |
N1—C1 | 1.470 (12) | C1—H1B | 0.9700 |
N1—H1C | 0.9000 | ||
I1ii—Cd1—I1 | 109.40 (2) | Zn1—N3—H3C | 110.3 |
I1ii—Cd1—I1iii | 109.40 (2) | C3—N3—H3D | 110.3 |
I1—Cd1—I1iii | 109.61 (3) | Zn1—N3—H3D | 110.3 |
I1ii—Cd1—I1iv | 109.61 (3) | H3C—N3—H3D | 108.6 |
I1—Cd1—I1iv | 109.40 (2) | C1—N1—Zn1 | 108.3 (5) |
I1iii—Cd1—I1iv | 109.40 (2) | C1—N1—H1C | 110.0 |
N2—Zn1—N2i | 98.0 (4) | Zn1—N1—H1C | 110.0 |
N2—Zn1—N1i | 169.3 (3) | C1—N1—H1D | 110.0 |
N2i—Zn1—N1i | 91.4 (3) | Zn1—N1—H1D | 110.0 |
N2—Zn1—N1 | 91.4 (3) | H1C—N1—H1D | 108.4 |
N2i—Zn1—N1 | 169.3 (3) | N2—C2—C3i | 109.6 (9) |
N1i—Zn1—N1 | 79.7 (4) | N2—C2—H2A | 109.8 |
N2—Zn1—N3i | 79.9 (3) | C3i—C2—H2A | 109.8 |
N2i—Zn1—N3i | 91.5 (3) | N2—C2—H2B | 109.8 |
N1i—Zn1—N3i | 94.9 (3) | C3i—C2—H2B | 109.8 |
N1—Zn1—N3i | 95.1 (3) | H2A—C2—H2B | 108.2 |
N2—Zn1—N3 | 91.5 (3) | N3—C3—C2i | 110.9 (9) |
N2i—Zn1—N3 | 79.9 (3) | N3—C3—H3A | 109.5 |
N1i—Zn1—N3 | 95.1 (3) | C2i—C3—H3A | 109.5 |
N1—Zn1—N3 | 94.9 (3) | N3—C3—H3B | 109.5 |
N3i—Zn1—N3 | 166.9 (4) | C2i—C3—H3B | 109.5 |
C2—N2—Zn1 | 109.2 (6) | H3A—C3—H3B | 108.0 |
C2—N2—H2C | 109.8 | C1i—C1—N1 | 111.4 (7) |
Zn1—N2—H2C | 109.8 | C1i—C1—H1A | 109.4 |
C2—N2—H2D | 109.8 | N1—C1—H1A | 109.4 |
Zn1—N2—H2D | 109.8 | C1i—C1—H1B | 109.4 |
H2C—N2—H2D | 108.3 | N1—C1—H1B | 109.4 |
C3—N3—Zn1 | 107.0 (6) | H1A—C1—H1B | 108.0 |
C3—N3—H3C | 110.3 | ||
N2i—Zn1—N2—C2 | −104.8 (7) | N3i—Zn1—N3—C3 | 35.7 (15) |
N1i—Zn1—N2—C2 | 46.6 (19) | N2—Zn1—N1—C1 | −160.9 (7) |
N1—Zn1—N2—C2 | 80.3 (7) | N2i—Zn1—N1—C1 | 47 (2) |
N3i—Zn1—N2—C2 | −14.6 (6) | N1i—Zn1—N1—C1 | 13.1 (5) |
N3—Zn1—N2—C2 | 175.2 (6) | N3i—Zn1—N1—C1 | −81.0 (7) |
N2—Zn1—N3—C3 | 84.1 (7) | N3—Zn1—N1—C1 | 107.4 (7) |
N2i—Zn1—N3—C3 | −13.7 (7) | Zn1—N2—C2—C3i | 40.7 (11) |
N1i—Zn1—N3—C3 | −104.2 (7) | Zn1—N3—C3—C2i | 40.2 (11) |
N1—Zn1—N3—C3 | 175.7 (7) | Zn1—N1—C1—C1i | −38.6 (11) |
Symmetry codes: (i) x, −y−1/2, −z+1/4; (ii) y, −x, −z; (iii) −x, −y, z; (iv) −y, x, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···I2v | 0.90 | 2.90 | 3.758 (8) | 160 |
N2—H2D···I2 | 0.90 | 2.92 | 3.746 (7) | 153 |
N1—H1D···I1ii | 0.90 | 3.09 | 3.904 (9) | 150 |
N3—H3C···I1iii | 0.90 | 2.99 | 3.827 (8) | 156 |
Symmetry codes: (ii) y, −x, −z; (iii) −x, −y, z; (v) −y−1, x, −z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C2H8N2)3][CdI4]I2 |
Mr | 1365.16 |
Crystal system, space group | Tetragonal, I42d |
Temperature (K) | 294 |
a, c (Å) | 14.803 (2), 16.991 (4) |
V (Å3) | 3723.2 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.84 |
Crystal size (mm) | 0.4 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Siemens P3/PC diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.127, 0.255 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3556, 916, 825 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.062, 1.07 |
No. of reflections | 916 |
No. of parameters | 76 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0332P)2 + 14.3589P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.51, −0.62 |
Absolute structure | Flack (1983), with how many Friedel pairs |
Absolute structure parameter | −0.07 (7) |
Computer programs: P3 (Siemens, 1989), P3, XDISK (Siemens, 1991), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1991), SHELXL97.
Cd1—I1 | 2.7934 (9) | Zn1—N1 | 2.186 (7) |
Zn1—N2 | 2.171 (8) | Zn1—N3 | 2.229 (8) |
I1i—Cd1—I1 | 109.40 (2) | N2—Zn1—N3iii | 79.9 (3) |
I1—Cd1—I1ii | 109.61 (3) | N1—Zn1—N3iii | 95.1 (3) |
N2—Zn1—N2iii | 98.0 (4) | N2—Zn1—N3 | 91.5 (3) |
N2—Zn1—N1iii | 169.3 (3) | N1—Zn1—N3 | 94.9 (3) |
N2—Zn1—N1 | 91.4 (3) | N3iii—Zn1—N3 | 166.9 (4) |
N1iii—Zn1—N1 | 79.7 (4) |
Symmetry codes: (i) y, −x, −z; (ii) −x, −y, z; (iii) x, −y−1/2, −z+1/4. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···I2iv | 0.90 | 2.90 | 3.758 (8) | 159.5 |
N2—H2D···I2 | 0.90 | 2.92 | 3.746 (7) | 153.1 |
N1—H1D···I1i | 0.90 | 3.09 | 3.904 (9) | 149.6 |
N3—H3C···I1ii | 0.90 | 2.99 | 3.827 (8) | 156.0 |
Symmetry codes: (i) y, −x, −z; (ii) −x, −y, z; (iv) −y−1, x, −z. |
It has been shown that the preparation of complexes from zero-valent metals or metal oxides is a fascinating and promising means to the production of heterometallic compounds of unusual stoichiometry and structure (Pryma et al., 2003; Nesterova et al., 2005). The reaction of zinc oxide with cadmium iodide and ammonium iodide in a dimethylformamide solution of ethylenediamine (en) in the open air, using a molar ratio of ZnO:CdI2:NH4I:en of 2:1:4:6, gives colourless crystals of the title compound, [Zn(en)3]2[CdI4]I2, (I).
Single-crystal structural analysis confirms that (I) is an ionic compound and is built of discrete octahedral [Zn(en)3]2+ cations and tetrahedral [CdI4]2− and I− anions, forming a three-dimensional framework by means of weak hydrogen bonds. The Cd atom lies on a 4 axis, while the cation and the free I− ion both lie on twofold rotation axes. In the selected asymmetric unit (Fig. 1), the cation has a Δ configuration.
The ZnII atom in [Zn(en)3]2+ is coordinated by six N atoms from three bidentate en ligands, with Zn—N distances ranging from 2.171 (8) to 2.229 (8) Å (Table 1). The coordination environment of the complex cation is distorted octahedral, as can be seen from the trans N—Zn—N angles, which vary from 166.9 (4) to 169.3 (3)°, and the cis N—Zn—N angles, which vary from 79.7 (4) to 95.1 (3)°. The observed bond distances and angles are in accordance with those found for the similar zinc(II) complexes [Zn(en)3][Ni(C4N2S2)2], [Zn(en)3][Te3](0.5en) and [Zn(en)3](NO3)2 (Fu et al., 2004; Shreeve-Keyer et al., 1997; Neill et al., 1997). The CdII coordination environment has approximate tetrahedral symmetry. The [Mean?] Cd—I bond length in the [CdI4]2− anion is approximately equal to the sum of the covalent radii for the atoms of Cd (1.51 Å) and I (1.33 Å) (Batsanov, 1991) and is typical of its type (Bailey & Pennington, 1995; Nieuwenhuyzen et al., 1992; Kallel et al., 1981).
A complex system of hydrogen bonds links the ions of (I) into a three-dimensional framework. Each I− anion is hydrogen bonded to three different [Zn(en)3]2+ units (Fig. 2), while each [CdI4]2− unit is hydrogen bonded to four different [Zn(en)3]2+ cations (Fig. 3). The non-coordinated atom I2 takes part in hydrogen bonding with the NH2 groups of en in the cations, being four-coordinated by H(N) atoms (Table 2). All four I atoms in the [CdI4]2− anion are two-coordinated by H(N) atoms, forming eight hydrogen bonds to [Zn(en)3]2+ cations. The hydrogen bonds interlink the [Zn(en)3]2+ and [CdI4]2− building blocks and I− anions into a three-dimensional framework. The nearest I1···I2vii distance is 4.695 (5) Å [symmetry code: (vii) −y, x, −z], indicating no specific interaction between I atoms.
The title salt represents a suitable system for a comparison of the strengths of two types of N—H···I hydrogen bonds. Thus, the bonds involving the free I− anions are ca 0.11 Å shorter than those involving the I atoms in the [CdI4]2− anion. Moreover, the mean value of all hydrogen bonds observed in [Zn(en)3]2[CdI4]I2 (3.81 Å), compared with the mean value found in [Cd(en)3]2[CdI4]I2 (3.76 Å) (Wieczorrek & Tebbe, 1998), indicates donor properties for the NH2 group somewhat stronger in [Cd(en)3]2+ than in [Zn(en)3]2+.