Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059971/gk2101sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059971/gk2101Isup2.hkl |
CCDC reference: 672781
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (Wav) = 0.000 Å
- R factor = 0.017
- wR factor = 0.044
- Data-to-parameter ratio = 22.1
checkCIF/PLATON results
No syntax errors found
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.864 Tmax scaled 0.234 Tmin scaled 0.194 REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.35 From the CIF: _reflns_number_total 1771 Count of symmetry unique reflns 999 Completeness (_total/calc) 177.28% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 772 Fraction of Friedel pairs measured 0.773 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Bu et al. (2000); Jia et al. (2004); Pan et al. (2005); Stephan & Kanatzidis (1997); Vaqueiro (2006); Vaqueiro et al. (2004); Varand et al. (1967); Wang et al. (2003); Wieczorrek (2000); Yu et al. (2001, 2002).
CoCl2.6H2O (0.5 mmol, 119 mg), HI (25.6 mmol, 4 ml), ethylenediamine (15 mmol, 1 ml) and ethanol (2 ml) were heated at 453 K for two days under autogeneous pressure in a sealed 25 ml Teflon-lined stainless steel vessel, and then cooled down to room temperature within two days. Red crystals of the title compound were obtained with 25% yield (based on cobalt chloride).
All atoms were allowed to ride on their respective parent atoms with the C—H and N—H bond distances fixed at 0.97 and 0.90 Å, respectively. H atoms were included in the refinement process with isotropic displacement parameters Uiso(H) = 1.2Ueq(C,N). The deepest hole in the final difference map of -1.01 e Å-3 is in the vicinity of the Co atom. The crystal was refined as an inversion twin.
Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL (Siemens, 1994); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXTL (Siemens, 1994).
Fig. 1. ORTEP drawing of the title compond showing 30% probability displacement ellipsoids. Hydrogen atoms are omitted for clarity. | |
Fig. 2. Packing diagram viewed along the c direction. |
[Co(C2H8N2)3](I3)I | Dx = 2.561 Mg m−3 |
Mr = 746.84 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I42d | Cell parameters from 5670 reflections |
Hall symbol: I -4 2bw | θ = 3.0–27.5° |
a = 14.7850 (4) Å | µ = 7.26 mm−1 |
c = 17.7221 (9) Å | T = 293 K |
V = 3874.0 (2) Å3 | Prism, red |
Z = 8 | 0.30 × 0.20 × 0.20 mm |
F(000) = 2728 |
Rigaku Mercury CCD diffractometer | 1771 independent reflections |
Radiation source: rotating anode generator | 1766 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 25.4°, θmin = 3.3° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002) | h = −16→17 |
Tmin = 0.224, Tmax = 0.271 | k = −17→14 |
12658 measured reflections | l = −19→21 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.017 | H-atom parameters constrained |
wR(F2) = 0.044 | w = 1/[σ2(Fo2) + (0.0313P)2 + 5.16P] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max = 0.001 |
1771 reflections | Δρmax = 0.43 e Å−3 |
80 parameters | Δρmin = −1.02 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 772 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.0 (5) |
[Co(C2H8N2)3](I3)I | Z = 8 |
Mr = 746.84 | Mo Kα radiation |
Tetragonal, I42d | µ = 7.26 mm−1 |
a = 14.7850 (4) Å | T = 293 K |
c = 17.7221 (9) Å | 0.30 × 0.20 × 0.20 mm |
V = 3874.0 (2) Å3 |
Rigaku Mercury CCD diffractometer | 1771 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002) | 1766 reflections with I > 2σ(I) |
Tmin = 0.224, Tmax = 0.271 | Rint = 0.032 |
12658 measured reflections |
R[F2 > 2σ(F2)] = 0.017 | H-atom parameters constrained |
wR(F2) = 0.044 | Δρmax = 0.43 e Å−3 |
S = 0.98 | Δρmin = −1.02 e Å−3 |
1771 reflections | Absolute structure: Flack (1983), with 772 Friedel pairs |
80 parameters | Absolute structure parameter: 0.0 (5) |
0 restraints |
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. Crystal refined as inversion twin with BASF 0.5 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 | ||
I1 | 1.101498 (17) | 0.7500 | 0.1250 | 0.01992 (6) | |
I2 | 0.329735 (14) | 0.898314 (14) | 0.128322 (12) | 0.02335 (5) | |
I3 | 0.5000 | 1.0000 | 0.12773 (2) | 0.02203 (7) | |
Co1 | 0.77236 (4) | 0.7500 | 0.1250 | 0.01965 (13) | |
N11 | 0.7898 (2) | 0.61932 (19) | 0.05720 (15) | 0.0196 (7) | |
H11E | 0.7419 | 0.5828 | 0.0644 | 0.024* | |
H11F | 0.7938 | 0.6320 | 0.0076 | 0.024* | |
N12 | 0.87417 (19) | 0.8274 (2) | 0.05429 (15) | 0.0173 (6) | |
H12E | 0.9293 | 0.8021 | 0.0587 | 0.021* | |
H12F | 0.8579 | 0.8261 | 0.0054 | 0.021* | |
N13 | 0.6522 (2) | 0.8038 (2) | 0.05786 (15) | 0.0177 (7) | |
H13E | 0.6458 | 0.8636 | 0.0659 | 0.021* | |
H13F | 0.6613 | 0.7948 | 0.0082 | 0.021* | |
C11 | 0.8727 (3) | 0.5747 (2) | 0.0830 (2) | 0.0238 (9) | |
H11A | 0.9251 | 0.6053 | 0.0620 | 0.029* | |
H11B | 0.8735 | 0.5124 | 0.0657 | 0.029* | |
C12 | 0.8767 (3) | 0.9226 (2) | 0.0817 (2) | 0.0244 (9) | |
H12A | 0.8258 | 0.9558 | 0.0610 | 0.029* | |
H12B | 0.9319 | 0.9515 | 0.0645 | 0.029* | |
C13 | 0.5697 (2) | 0.7554 (3) | 0.08248 (15) | 0.0176 (7) | |
H13A | 0.5675 | 0.6964 | 0.0587 | 0.021* | |
H13B | 0.5166 | 0.7891 | 0.0670 | 0.021* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.01401 (12) | 0.03132 (15) | 0.01442 (12) | 0.000 | 0.000 | 0.00234 (13) |
I2 | 0.02650 (11) | 0.02545 (11) | 0.01809 (9) | 0.00195 (8) | 0.00569 (11) | −0.00330 (10) |
I3 | 0.03353 (15) | 0.01645 (14) | 0.01612 (13) | 0.00729 (11) | 0.000 | 0.000 |
Co1 | 0.0191 (3) | 0.0207 (3) | 0.0192 (3) | 0.000 | 0.000 | 0.0004 (3) |
N11 | 0.0280 (15) | 0.0192 (15) | 0.0118 (13) | −0.0022 (12) | 0.0005 (11) | 0.0009 (11) |
N12 | 0.0169 (14) | 0.0197 (14) | 0.0153 (12) | −0.0011 (12) | 0.0015 (11) | −0.0015 (11) |
N13 | 0.0216 (15) | 0.0195 (16) | 0.0119 (12) | −0.0010 (12) | −0.0003 (11) | 0.0021 (10) |
C11 | 0.029 (2) | 0.0205 (18) | 0.0216 (18) | 0.0043 (16) | 0.0055 (15) | −0.0063 (13) |
C12 | 0.023 (2) | 0.0227 (19) | 0.0275 (19) | −0.0115 (16) | 0.0013 (15) | 0.0020 (14) |
C13 | 0.0163 (14) | 0.0227 (16) | 0.0139 (15) | 0.0052 (18) | −0.0012 (11) | −0.0017 (15) |
I2—I3 | 2.9322 (2) | N13—C13 | 1.479 (4) |
Co1—N12 | 2.269 (3) | N13—H13E | 0.9000 |
Co1—N13 | 2.282 (3) | N13—H13F | 0.9000 |
Co1—N11 | 2.290 (3) | C11—H11A | 0.9700 |
N11—C11 | 1.465 (5) | C11—H11B | 0.9700 |
N11—H11E | 0.9000 | C12—H12A | 0.9700 |
N11—H11F | 0.9000 | C12—H12B | 0.9700 |
N12—C12 | 1.489 (5) | C13—H13A | 0.9700 |
N12—H12E | 0.9000 | C13—H13B | 0.9700 |
N12—H12F | 0.9000 | ||
I2i—I3—I2 | 179.587 (17) | C13—N13—Co1 | 108.63 (19) |
N12—Co1—N13 | 93.02 (9) | C13—N13—H13E | 110.0 |
N12—Co1—N11 | 93.51 (11) | Co1—N13—H13E | 110.0 |
N13—Co1—N11 | 96.22 (10) | C13—N13—H13F | 110.0 |
C11—N11—Co1 | 108.1 (2) | Co1—N13—H13F | 110.0 |
C11—N11—H11E | 110.1 | H13E—N13—H13F | 108.3 |
Co1—N11—H11E | 110.1 | N11—C11—H11A | 109.8 |
C11—N11—H11F | 110.1 | N11—C11—H11B | 109.8 |
Co1—N11—H11F | 110.1 | H11A—C11—H11B | 108.2 |
H11E—N11—H11F | 108.4 | N12—C12—H12A | 109.6 |
C12—N12—Co1 | 108.2 (2) | N12—C12—H12B | 109.6 |
C12—N12—H12E | 110.0 | H12A—C12—H12B | 108.1 |
Co1—N12—H12E | 110.0 | N13—C13—H13A | 109.6 |
C12—N12—H12F | 110.0 | N13—C13—H13B | 109.6 |
Co1—N12—H12F | 110.0 | H13A—C13—H13B | 108.1 |
H12E—N12—H12F | 108.4 |
Symmetry code: (i) −x+1, −y+2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N12—H12E···I1 | 0.90 | 2.91 | 3.765 (3) | 160 |
N12—H12F···I1ii | 0.90 | 3.00 | 3.817 (3) | 151 |
N13—H13E···I3 | 0.90 | 3.15 | 3.874 (3) | 139 |
N13—H13F···I2iii | 0.90 | 3.08 | 3.818 (3) | 141 |
N13—H13F···I1ii | 0.90 | 3.10 | 3.815 (3) | 137 |
N11—H11E···I2iv | 0.90 | 3.10 | 3.887 (3) | 148 |
N11—H11F···I2v | 0.90 | 2.92 | 3.735 (3) | 152 |
Symmetry codes: (ii) y, −x+2, −z; (iii) −y+3/2, −x+1, z−1/4; (iv) −x+1, y−1/2, −z+1/4; (v) y, −x+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Co(C2H8N2)3](I3)I |
Mr | 746.84 |
Crystal system, space group | Tetragonal, I42d |
Temperature (K) | 293 |
a, c (Å) | 14.7850 (4), 17.7221 (9) |
V (Å3) | 3874.0 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 7.26 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku Mercury CCD diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2002) |
Tmin, Tmax | 0.224, 0.271 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12658, 1771, 1766 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.044, 0.98 |
No. of reflections | 1771 |
No. of parameters | 80 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −1.02 |
Absolute structure | Flack (1983), with 772 Friedel pairs |
Absolute structure parameter | 0.0 (5) |
Computer programs: CrystalClear (Rigaku, 2002), SHELXTL (Siemens, 1994).
I2—I3 | 2.9322 (2) | Co1—N13 | 2.282 (3) |
Co1—N12 | 2.269 (3) | Co1—N11 | 2.290 (3) |
I2i—I3—I2 | 179.587 (17) |
Symmetry code: (i) −x+1, −y+2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N12—H12E···I1 | 0.90 | 2.91 | 3.765 (3) | 160 |
N12—H12F···I1ii | 0.90 | 3.00 | 3.817 (3) | 151 |
N13—H13E···I3 | 0.90 | 3.15 | 3.874 (3) | 139 |
N13—H13F···I2iii | 0.90 | 3.08 | 3.818 (3) | 141 |
N13—H13F···I1ii | 0.90 | 3.10 | 3.815 (3) | 137 |
N11—H11E···I2iv | 0.90 | 3.10 | 3.887 (3) | 148 |
N11—H11F···I2v | 0.90 | 2.92 | 3.735 (3) | 152 |
Symmetry codes: (ii) y, −x+2, −z; (iii) −y+3/2, −x+1, z−1/4; (iv) −x+1, y−1/2, −z+1/4; (v) y, −x+1, −z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
The crystal structures of tris(1,2-ethanediamine-N,N')zinc(II) triiodide iodide and tris(1,2-ethanediamine-N,N') nickel(II) triiodide iodide have been reported earlier (Wieczorrek, 2000). Herein, we report the synthesis and crystal structure of tris(1,2-ethanediamine-N,N')cobalt(II) triiodide iodide. This complex is isostructural with the Zn(II) and Ni(II) complexes.
As shown in Fig. 1, the title complex consists of one [Co(en)3]2+ cation, one triiodide anion, and one iodide anion. The Co atom is coordinated by three ethanediamine ligands that form a distorted octahedral environment with the Co—N bond distances ranging from 2.269 (3) to 2.290 (3) Å (Table 1). It is important to stress that compounds conating [Co(en)3]2+ cation are rare in comparison with those containing [Co(en)3]3+ (Bu et al., 2000; Jia et al., 2004; Pan et al., 2005; Stephan & Kanatzidis, 1997; Vaqueiro, 2006; Vaqueiro et al., 2004; Varand et al., 1967; Wang et al., 2003; Yu et al., 2001, 2002). The I—I bond distance of the linear triiodide anion in the present compound is 2.9322 (2) Å, which is inagreement with those found in [Zn(C2H8N2)3](I3)I and [Ni(C2H8N2)3](I3)I. The crystal structure of the title compound is shown in Figure 2. Hydrogen bonds are formed between N atoms of the ethanediamine ligands and I atoms of triiodide and iodide anions (Table 2).