Tetraiodide von Tris(1,2-ethandiamin)komplexen der Metalle Zink und Nickel

The isotypic compounds tris(1,2-ethanedi­amine-N,N')­zinc(II) triiodide iodide, [Zn(C₂H₈N₂)₃](I₃)I, and tris(1,2-ethanedi­amine-N,N')­nickel(II) triiodide iodide, [Ni(C₂H₈N₂)₃](I₃)I, contain the octahedral [M(en)₃]²⁺ cation, with M = Zn and Ni, in both enantiomeric forms, an essentially linear triiodide anion and an iodide anion. The geometries of the complex ions are as expected, e.g. d(Ni-N) = 2.123 (5), 2.127 (6) and 2.134 (5) Å, and d(Zn-N) = 2.176 (4), 2.193 (4) and 2.210 (4) Å. The shortest contact between the triiodide and iodide ions is 3.979 (1) Å for the nickel compound and 4.013 (1) Å for the zinc compound.

Computing details

For both compounds, data collection: IPDS-Programmsystem (Stoe & Cie, 1996/97); cell refinement: IPDS-Programmsystem; data reduction: IPDS-Programmsystem; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: WinGX (Farrugia, 1998), PARST95 (Nardelli, 1995), PLATON96 (Spek, 1996), CIFEDIT (Wieczorrek, 1999).

(I) Tris(1,2-ethandiamin)zinktriiodid-iodid

Crystal data

[Zn(C2H8N2)3][I3]I	Dx = 2.588 Mg m^−3
Mr = 753.28	Melting point: 457 K
Tetragonal, I42d	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I -4 2bw	Cell parameters from 5000 reflections
a = 14.742 (1) Å	θ = 2.8–25.2°
c = 17.791 (1) Å	µ = 7.65 mm^−1
V = 3866.5 (3) Å^3	T = 293 K
Z = 8	Tetragonale Bipyramide nach <101>, clear dark red
F(000) = 2752	0.40 × 0.36 × 0.36 mm

Data collection

Stoe & Cie. IPDS diffractometer	1730 independent reflections
Radiation source: fine-focus sealed tube	1631 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.077
Detector resolution: 44.4 pixels mm^-1	θmax = 25.2°, θmin = 2.8°
oszillation scans	h = −17→17
Absorption correction: numerical Die Absorptionskorrektur wurde unter WINGX V1.61 nach den Pyramidenflächen <101> durchgeführt (Alcock 1970).	k = −17→17
Tmin = 0.174, Tmax = 0.232	l = −21→21
16727 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.020	w = 1/[σ^2(Fo^2) + 7.2246P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.042	(Δ/σ)max = 0.001
S = 1.09	Δρmax = 0.47 e Å^−3
1730 reflections	Δρmin = −0.48 e Å^−3
82 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00167 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.02 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
I1	0.5000	0.5000	0.37741 (3)	0.05352 (15)
I2	0.60152 (2)	0.67050 (2)	0.37813 (2)	0.05671 (12)
I3	0.60136 (3)	1.2500	0.1250	0.05170 (14)
Zn	0.7500	1.22777 (4)	0.3750	0.03157 (15)
N1	0.6774 (3)	1.1293 (2)	0.3066 (2)	0.0374 (9)
H1A	0.6789	1.1462	0.2580	0.070 (8)*
H1B	0.7039	1.0745	0.3107	0.070 (8)*
C2	0.5827 (3)	1.1242 (4)	0.3326 (3)	0.0511 (15)
H2A	0.5558	1.0674	0.3162	0.055 (7)*
H2B	0.5479	1.1735	0.3109	0.055 (7)*
C3	0.5793 (4)	1.1301 (4)	0.4172 (3)	0.0538 (15)
H3A	0.5167	1.1302	0.4340	0.055 (7)*
H3B	0.6095	1.0779	0.4390	0.055 (7)*
N4	0.6244 (3)	1.2135 (3)	0.4418 (2)	0.0429 (10)
H4A	0.6377	1.2102	0.4911	0.070 (8)*
H4B	0.5879	1.2616	0.4342	0.070 (8)*
N5	0.8016 (3)	1.3420 (3)	0.4414 (2)	0.0391 (9)
H5A	0.7912	1.3322	0.4906	0.070 (8)*
H5B	0.8618	1.3479	0.4345	0.070 (8)*
C6	0.7546 (5)	1.4251 (3)	0.4168 (2)	0.0401 (10)
H6A	0.7887	1.4780	0.4327	0.055 (7)*
H6B	0.6950	1.4280	0.4397	0.055 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0391 (2)	0.0808 (3)	0.0407 (2)	0.0155 (2)	0.000	0.000
I2	0.0615 (2)	0.0646 (2)	0.04400 (19)	0.00266 (16)	0.0059 (2)	−0.01274
I3	0.0348 (2)	0.0841 (3)	0.0363 (2)	0.000	0.000	0.0055 (3)
Zn	0.0348 (3)	0.0317 (3)	0.0282 (3)	0.000	−0.0011 (3)	0.000
N1	0.042 (2)	0.035 (2)	0.035 (2)	−0.0011 (18)	−0.0024 (17)	−0.0025 (15)
C2	0.045 (3)	0.050 (3)	0.059 (4)	−0.014 (3)	−0.010 (2)	−0.001 (3)
C3	0.051 (4)	0.063 (4)	0.048 (3)	−0.005 (3)	0.010 (2)	0.010 (3)
N4	0.040 (2)	0.053 (2)	0.036 (2)	0.0023 (17)	0.0024 (17)	0.0016 (17)
N5	0.044 (2)	0.043 (2)	0.031 (2)	−0.0016 (18)	−0.0027 (16)	−0.0017 (17)
C6	0.051 (3)	0.033 (2)	0.037 (2)	0.001 (3)	0.005 (2)	−0.0050 (17)

Geometric parameters (Å, º)

I1—I2	2.9254 (3)	Zn—N4	2.210 (4)
I1—I2^i	2.9254 (3)	N1—C2	1.472 (6)
Zn—N1	2.176 (4)	C2—C3	1.509 (7)
Zn—N1^ii	2.176 (4)	C3—N4	1.464 (7)
Zn—N5	2.193 (4)	N5—C6	1.474 (6)
Zn—N5^ii	2.193 (4)	C6—C6^ii	1.492 (8)
Zn—N4^ii	2.210 (4)
I2—I1—I2^i	179.50 (3)	N1—Zn—N4	79.89 (15)
N1—Zn—N1^ii	96.3 (2)	N1^ii—Zn—N4	92.76 (16)
N1—Zn—N5	169.78 (17)	N5—Zn—N4	94.26 (15)
N1^ii—Zn—N5	92.31 (13)	N5^ii—Zn—N4	94.14 (15)
N1—Zn—N5^ii	92.31 (13)	N4^ii—Zn—N4	169.1 (2)
N1^ii—Zn—N5^ii	169.78 (17)	C2—N1—Zn	109.0 (3)
N5—Zn—N5^ii	79.7 (2)	N1—C2—C3	109.9 (4)
N1—Zn—N4^ii	92.76 (16)	N4—C3—C2	109.4 (5)
N1^ii—Zn—N4^ii	79.89 (15)	C3—N4—Zn	107.4 (3)
N5—Zn—N4^ii	94.14 (15)	C6—N5—Zn	108.4 (3)
N5^ii—Zn—N4^ii	94.26 (15)	N5—C6—C6^ii	109.8 (3)

Symmetry codes: (i) −x+1, −y+1, z; (ii) −x+3/2, y, −z+3/4.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I3	0.90	3.04	3.855 (4)	151
N1—H1B···I3^iii	0.90	2.92	3.767 (4)	159
N4—H4A···I2^iv	0.90	2.96	3.765 (4)	150

Symmetry codes: (iii) y−1/2, −x+3/2, −z+1/2; (iv) y, x+1/2, z+1/4.

(II) Tris(1,2-diaminoethan)nickeltriiodid-iodid

Crystal data

[Ni(C2H8N)3][I3]I	Dx = 2.596 Mg m^−3
Mr = 746.62	Melting point: 547 K
Tetragonal, I42d	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I -4 2bw	Cell parameters from 5000 reflections
a = 14.670 (1) Å	θ = 2.8–26.1°
c = 17.754 (2) Å	µ = 7.47 mm^−1
V = 3820.8 (6) Å^3	T = 293 K
Z = 8	Tetragonale Bipyramide nach <101>, clear dark red
F(000) = 2736	0.35 × 0.28 × 0.28 mm

Data collection

IPDS (Stoe & Cie) diffractometer	1886 independent reflections
Radiation source: fine-focus sealed tube	1477 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.080
Detector resolution: 44.4 pixels mm^-1	θmax = 26.1°, θmin = 2.8°
oscillation scans	h = −18→18
Absorption correction: numerical Die Absorptionskorrektur wurde unter WINGX V1.61 nach den Pyramidenflächen [101] durchgeführt (Alcock 1970).	k = −17→17
Tmin = 0.241, Tmax = 0.350	l = −21→21
10875 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.028	w = 1/[σ^2(Fo^2) + (0.0191P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.052	(Δ/σ)max < 0.001
S = 0.91	Δρmax = 0.74 e Å^−3
1886 reflections	Δρmin = −0.64 e Å^−3
82 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00019 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.09 (6)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
I1	0.5000	0.5000	−0.37720 (5)	0.04811 (19)
I2	0.32889 (3)	0.39777 (3)	−0.37798 (4)	0.05060 (15)
I3	0.2500	0.60145 (4)	−0.1250	0.04860 (18)
Ni	0.22909 (6)	0.7500	−0.3750	0.0260 (2)
N1	0.1311 (4)	0.6813 (4)	−0.3077 (3)	0.0337 (14)
H1A	0.1474	0.6841	−0.2589	0.052 (9)*
H1B	0.0763	0.7082	−0.3128	0.052 (9)*
C2	0.1257 (5)	0.5856 (5)	−0.3321 (5)	0.044 (2)
H2C	0.0681	0.5594	−0.3163	0.043 (9)*
H2D	0.1745	0.5507	−0.3091	0.043 (9)*
C3	0.1339 (6)	0.5815 (5)	−0.4177 (5)	0.043 (2)
H3C	0.1357	0.5185	−0.4342	0.043 (9)*
H3D	0.0815	0.6107	−0.4407	0.043 (9)*
N4	0.2178 (4)	0.6284 (4)	−0.4403 (3)	0.0388 (15)
H4A	0.2156	0.6422	−0.4897	0.052 (9)*
H4B	0.2663	0.5922	−0.4322	0.052 (9)*
N5	0.3389 (4)	0.8025 (4)	−0.4401 (3)	0.0363 (14)
H5A	0.3286	0.7927	−0.4894	0.052 (9)*
H5B	0.3444	0.8629	−0.4326	0.052 (9)*
C6	0.4233 (4)	0.7550 (6)	−0.4161 (3)	0.0360 (15)
H6C	0.4263	0.6954	−0.4396	0.043 (9)*
H6D	0.4762	0.7897	−0.4318	0.043 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0749 (5)	0.0355 (3)	0.0340 (3)	0.0133 (3)	0.000	0.000
I2	0.0600 (3)	0.0567 (3)	0.0351 (2)	0.0006 (2)	−0.0110 (3)	0.0047 (3)
I3	0.0844 (5)	0.0323 (3)	0.0291 (3)	0.000	−0.0046 (5)	0.000
Ni	0.0290 (6)	0.0303 (5)	0.0186 (5)	0.000	0.000	0.0018 (5)
N1	0.038 (3)	0.035 (3)	0.028 (3)	−0.001 (3)	0.004 (2)	0.000 (3)
C2	0.046 (5)	0.045 (5)	0.040 (5)	−0.020 (4)	0.001 (4)	0.009 (4)
C3	0.057 (5)	0.039 (5)	0.032 (5)	−0.007 (4)	−0.006 (4)	−0.007 (3)
N4	0.052 (4)	0.039 (3)	0.025 (3)	0.004 (2)	−0.003 (2)	0.001 (3)
N5	0.042 (3)	0.042 (3)	0.025 (3)	−0.003 (3)	−0.001 (3)	0.009 (3)
C6	0.035 (3)	0.041 (4)	0.032 (4)	−0.002 (4)	0.004 (3)	−0.007 (4)

Geometric parameters (Å, º)

I3—I2^i	3.9793 (7)	Ni—N5	2.127 (6)
I3—I2^ii	3.9793 (7)	Ni—N4^v	2.134 (5)
I1—I2^iii	2.9241 (5)	Ni—N4	2.134 (5)
I1—I2	2.9241 (5)	N1—C2	1.472 (9)
I2—I3^iv	3.9793 (7)	C2—C3	1.526 (9)
Ni—N1^v	2.123 (5)	C3—N4	1.466 (9)
Ni—N1	2.123 (5)	N5—C6	1.483 (8)
Ni—N5^v	2.127 (6)	C6—C6^v	1.467 (12)
I2^i—I3—I2^ii	66.042 (16)	N5—Ni—N4^v	93.0 (2)
I2^iii—I1—I2	179.45 (4)	N1^v—Ni—N4	92.2 (2)
I1—I2—I3^iv	177.606 (19)	N1—Ni—N4	81.7 (2)
N1^v—Ni—N1	94.8 (3)	N5^v—Ni—N4	93.0 (2)
N1^v—Ni—N5^v	172.0 (2)	N5—Ni—N4	93.8 (2)
N1—Ni—N5^v	92.02 (19)	N4^v—Ni—N4	171.1 (3)
N1^v—Ni—N5	92.02 (19)	C2—N1—Ni	108.9 (4)
N1—Ni—N5	172.0 (2)	N1—C2—C3	109.0 (6)
N5^v—Ni—N5	81.6 (3)	N4—C3—C2	108.7 (7)
N1^v—Ni—N4^v	81.7 (2)	C3—N4—Ni	108.0 (4)
N1—Ni—N4^v	92.2 (2)	C6—N5—Ni	107.8 (4)
N5^v—Ni—N4^v	93.8 (2)	C6^v—C6—N5	109.4 (5)
I2^iii—I1—I2—I3^iv	115.6 (7)	N1—Ni—N4—C3	16.8 (4)
N1^v—Ni—N1—C2	103.8 (5)	N5^v—Ni—N4—C3	108.4 (4)
N5^v—Ni—N1—C2	−80.5 (4)	N5—Ni—N4—C3	−169.8 (4)
N5—Ni—N1—C2	−44.2 (19)	N4^v—Ni—N4—C3	−30.7 (4)
N4^v—Ni—N1—C2	−174.3 (4)	N1^v—Ni—N5—C6	−170.7 (5)
N4—Ni—N1—C2	12.2 (4)	N1—Ni—N5—C6	−23 (2)
Ni—N1—C2—C3	−38.5 (8)	N5^v—Ni—N5—C6	14.1 (3)
N1—C2—C3—N4	54.7 (9)	N4^v—Ni—N5—C6	107.5 (5)
C2—C3—N4—Ni	−42.2 (7)	N4—Ni—N5—C6	−78.4 (5)
N1^v—Ni—N4—C3	−77.7 (5)	Ni—N5—C6—C6^v	−40.9 (9)

Symmetry codes: (i) y, x+1/2, z+1/4; (ii) −y+1/2, x+1/2, −z−1/2; (iii) −x+1, −y+1, z; (iv) y−1/2, x, z−1/4; (v) x, −y+3/2, −z−3/4.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···I3^vi	0.90	2.90	3.753 (6)	159
N4—H4A···I2^vi	0.90	3.00	3.791 (5)	148

Symmetry code: (vi) −y+1/2, −x+1, z−1/4.