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metal-organic compounds
Azido{2-[bis(2-hydroxyethyl)amino]ethanolato-κ4N,O,O′,O′′}cobalt(II)
aPharmacy College, Henan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China
*Correspondence e-mail: liuyanju886@163.com
In the title complex, [Co(C6H14NO3)(N3)] or [Co(teaH2)N3], the CoII atom resides in a trigonal–bipymidal O3N2 environment formed by three O atoms and one N atom from a simply deprotonated tetradentate triethanolamine ligand, and one N atom from an azide ligand. The O atoms define the equatorial plane whereas both N atoms are in axial positions. The mononuclear units are linked through O—H⋯O hydrogen-bonding interactions between the ethanol OH groups and the ethanolate O atom of a neighbouring complex into chains running parallel to [010].
Related literature
For general background to complexes including teaH3 ligands, see: Liu, Wang et al. (2008); Liu, Zhang et al. (2008
). For CoII complexes with similar ligands, see: Malaestean et al. (2010
).
Experimental
Crystal data
|
Refinement
|
|
|
Data collection: CrystalClear (Rigaku/MSC, 2006); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: SHELXTL (Sheldrick, 2008
); software used to prepare material for publication: publCIF (Westrip, 2010
).
Supporting information
https://doi.org/10.1107/S1600536810047100/wm2427sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047100/wm2427Isup2.hkl
Under stirring, 2.0 mmol teaH3, 4.0 mmol Et3N and 4.0 mmol NaN3 were added, one after another, into a 20 ml methanol solution containing 1.0 mol Co(ClO4)2.6H2O. The resulting solution was kept stirred for another hour, and then filtered. The filtrate was allowed to stand undisturbed in a sealed vessel. Crystallization took place during one week and gave crystals in a yield of 40% based on Co(ClO4)2.6H2O. The product was washed with methanol and dried in air.
H1OA and H2OA were found in difference Fourier maps and were refined freely. All other H atoms were positioned geometrically as riding atoms, with C—H = 0.97 Å and with Uiso(H) = 1.2 Ueq(C).
The design and synthesis of mononuclear compounds with strong anisotropy, potentially acting as single ion magnets, are of current interest. Podand-like or multi-dentate ligands, such as diethanolamine (deaH2) or triethanolamine (teaH3), have been employed though these ligands were also used to prepare other kinds of clusters (Liu, Wang et al., 2008; Liu, Zhang et al., 2008). In this work, we selected teaH3 as a capping ligand, and azide as another anion, generating complex (I), Co(N(CH2CH2OH)2(CH2CH2O))N3 [= Co(teaH2)N3].
In the structure of (I) each CoII atom is five-coordinate by three O atoms and one N atom from a simply deprotonated tetradentate triethanolamine ligand, and one N atom from an azide ligand in a trigonal-bipymidal coordination environment (Fig. 1). The O atoms define the equatorial plane whereas both N atoms sit in axial positions. The Co—N distances are 2.013 (3)—2.148 (3) Å, and the Co—O distances are 1.991 (2)–2.065 (2) Å. These bond length are in agreement with similar complexes with CoII in trigonal-pyramidal coordination (Malaestean et al., 2010).
The mononuclear Co(teaH2)N3 units are linked through O—H···O hydrogen bonding interactions between the ethanol OH groups and the ethanolate O atom of a neighbouring complex into chains running parallel to [010] (Fig. 2).
For general background to complexes including teaH3 ligands, see: Liu, Wang et al. (2008); Liu, Zhang et al. (2008). For CoII complexes with similar ligands, see: Malaestean et al. (2010).
Data collection: CrystalClear (Rigaku/MSC, 2006); cell
CrystalClear (Rigaku/MSC, 2006); data reduction: CrystalClear (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).[Co(C6H14NO3)(N3)] | F(000) = 516 |
Mr = 249.14 | Dx = 1.725 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2179 reflections |
a = 8.7752 (2) Å | θ = 3.4–27.5° |
b = 7.9373 (1) Å | µ = 1.78 mm−1 |
c = 14.4097 (3) Å | T = 293 K |
β = 107.084 (1)° | Pillar, red |
V = 959.37 (3) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 4 |
Rigaku Saturn CCD diffractometer | 2179 independent reflections |
Radiation source: fine-focus sealed tube | 1253 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 0.76 pixels mm-1 | θmax = 27.5°, θmin = 3.5° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −10→10 |
Tmin = 0.708, Tmax = 0.823 | l = −18→18 |
4004 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0427P)2] where P = (Fo2 + 2Fc2)/3 |
2179 reflections | (Δ/σ)max = 0.001 |
135 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
[Co(C6H14NO3)(N3)] | V = 959.37 (3) Å3 |
Mr = 249.14 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.7752 (2) Å | µ = 1.78 mm−1 |
b = 7.9373 (1) Å | T = 293 K |
c = 14.4097 (3) Å | 0.20 × 0.20 × 0.10 mm |
β = 107.084 (1)° |
Rigaku Saturn CCD diffractometer | 2179 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 1253 reflections with I > 2σ(I) |
Tmin = 0.708, Tmax = 0.823 | Rint = 0.055 |
4004 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.89 | Δρmax = 0.55 e Å−3 |
2179 reflections | Δρmin = −0.38 e Å−3 |
135 parameters |
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 | ||
Co1 | 0.49520 (5) | 0.87496 (5) | 0.81512 (3) | 0.02597 (16) | |
C1 | 0.2117 (4) | 0.6897 (4) | 0.8302 (3) | 0.0438 (10) | |
H1A | 0.1899 | 0.6223 | 0.7716 | 0.053* | |
H1B | 0.1173 | 0.6886 | 0.8522 | 0.053* | |
C2 | 0.3480 (4) | 0.6158 (5) | 0.9063 (3) | 0.0405 (9) | |
H2A | 0.3523 | 0.6638 | 0.9690 | 0.049* | |
H2B | 0.3329 | 0.4951 | 0.9096 | 0.049* | |
C3 | 0.2225 (5) | 0.9829 (4) | 0.8818 (3) | 0.0424 (10) | |
H3A | 0.2555 | 0.9297 | 0.9451 | 0.051* | |
H3B | 0.1099 | 1.0092 | 0.8665 | 0.051* | |
C4 | 0.3151 (4) | 1.1428 (4) | 0.8848 (3) | 0.0362 (9) | |
H4A | 0.2619 | 1.2139 | 0.8301 | 0.043* | |
H4B | 0.3217 | 1.2040 | 0.9441 | 0.043* | |
C5 | 0.1604 (4) | 0.9162 (5) | 0.7086 (3) | 0.0423 (10) | |
H5A | 0.1562 | 1.0382 | 0.7049 | 0.051* | |
H5B | 0.0518 | 0.8745 | 0.6925 | 0.051* | |
C6 | 0.2386 (4) | 0.8496 (5) | 0.6363 (2) | 0.0361 (9) | |
H6A | 0.2138 | 0.7309 | 0.6249 | 0.043* | |
H6B | 0.1970 | 0.9086 | 0.5751 | 0.043* | |
N1 | 0.2476 (3) | 0.8648 (3) | 0.80846 (19) | 0.0254 (6) | |
N2 | 0.7314 (3) | 0.8811 (4) | 0.8330 (2) | 0.0405 (7) | |
N3 | 0.8273 (4) | 0.8233 (4) | 0.9028 (2) | 0.0388 (8) | |
N4 | 0.9226 (5) | 0.7663 (5) | 0.9675 (3) | 0.0703 (12) | |
O1 | 0.4947 (3) | 0.6485 (3) | 0.88538 (18) | 0.0332 (6) | |
O2 | 0.4718 (3) | 1.1008 (3) | 0.88087 (18) | 0.0344 (6) | |
O3 | 0.4087 (2) | 0.8714 (3) | 0.67098 (14) | 0.0269 (5) | |
H1OA | 0.508 (6) | 1.183 (7) | 0.863 (4) | 0.11 (2)* | |
H2OA | 0.525 (4) | 0.569 (4) | 0.870 (3) | 0.035 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0262 (2) | 0.0243 (2) | 0.0272 (2) | −0.0003 (2) | 0.00739 (18) | 0.0007 (2) |
C1 | 0.040 (2) | 0.0305 (19) | 0.064 (3) | −0.0069 (17) | 0.021 (2) | 0.0004 (18) |
C2 | 0.050 (2) | 0.0339 (19) | 0.046 (2) | 0.002 (2) | 0.0274 (19) | 0.0055 (19) |
C3 | 0.044 (2) | 0.034 (2) | 0.059 (2) | −0.0046 (18) | 0.030 (2) | −0.0111 (19) |
C4 | 0.042 (2) | 0.0266 (19) | 0.048 (2) | −0.0025 (18) | 0.0257 (18) | −0.0068 (17) |
C5 | 0.029 (2) | 0.054 (3) | 0.043 (2) | 0.0035 (18) | 0.0095 (17) | −0.0026 (18) |
C6 | 0.0263 (19) | 0.045 (2) | 0.0335 (19) | −0.0002 (17) | 0.0027 (16) | −0.0022 (17) |
N1 | 0.0282 (14) | 0.0220 (13) | 0.0280 (14) | −0.0013 (13) | 0.0114 (12) | −0.0021 (12) |
N2 | 0.0264 (16) | 0.0488 (18) | 0.0465 (19) | 0.0014 (16) | 0.0112 (15) | 0.0126 (17) |
N3 | 0.0272 (18) | 0.047 (2) | 0.045 (2) | −0.0005 (15) | 0.0145 (16) | −0.0082 (16) |
N4 | 0.046 (2) | 0.107 (3) | 0.050 (2) | 0.024 (2) | 0.001 (2) | 0.008 (2) |
O1 | 0.0377 (15) | 0.0227 (15) | 0.0420 (15) | 0.0045 (12) | 0.0163 (12) | 0.0026 (12) |
O2 | 0.0372 (15) | 0.0274 (14) | 0.0411 (14) | −0.0091 (12) | 0.0152 (11) | −0.0053 (12) |
O3 | 0.0265 (12) | 0.0302 (12) | 0.0252 (11) | 0.0039 (12) | 0.0093 (9) | 0.0022 (11) |
Co1—O3 | 1.991 (2) | C3—H3B | 0.9700 |
Co1—N2 | 2.013 (3) | C4—O2 | 1.433 (4) |
Co1—O1 | 2.064 (2) | C4—H4A | 0.9700 |
Co1—O2 | 2.065 (2) | C4—H4B | 0.9700 |
Co1—N1 | 2.148 (3) | C5—N1 | 1.475 (4) |
C1—N1 | 1.478 (4) | C5—C6 | 1.502 (5) |
C1—C2 | 1.486 (5) | C5—H5A | 0.9700 |
C1—H1A | 0.9700 | C5—H5B | 0.9700 |
C1—H1B | 0.9700 | C6—O3 | 1.439 (4) |
C2—O1 | 1.430 (4) | C6—H6A | 0.9700 |
C2—H2A | 0.9700 | C6—H6B | 0.9700 |
C2—H2B | 0.9700 | N2—N3 | 1.197 (4) |
C3—N1 | 1.476 (4) | N3—N4 | 1.147 (4) |
C3—C4 | 1.501 (5) | O1—H2OA | 0.74 (3) |
C3—H3A | 0.9700 | O2—H1OA | 0.81 (5) |
O3—Co1—N2 | 101.32 (11) | O2—C4—H4B | 110.0 |
O3—Co1—O1 | 116.37 (10) | C3—C4—H4B | 110.0 |
N2—Co1—O1 | 96.24 (12) | H4A—C4—H4B | 108.3 |
O3—Co1—O2 | 115.60 (10) | N1—C5—C6 | 111.6 (3) |
N2—Co1—O2 | 99.08 (12) | N1—C5—H5A | 109.3 |
O1—Co1—O2 | 121.07 (10) | C6—C5—H5A | 109.3 |
O3—Co1—N1 | 83.24 (9) | N1—C5—H5B | 109.3 |
N2—Co1—N1 | 175.37 (11) | C6—C5—H5B | 109.3 |
O1—Co1—N1 | 80.87 (10) | H5A—C5—H5B | 108.0 |
O2—Co1—N1 | 79.50 (10) | O3—C6—C5 | 110.8 (3) |
N1—C1—C2 | 110.6 (3) | O3—C6—H6A | 109.5 |
N1—C1—H1A | 109.5 | C5—C6—H6A | 109.5 |
C2—C1—H1A | 109.5 | O3—C6—H6B | 109.5 |
N1—C1—H1B | 109.5 | C5—C6—H6B | 109.5 |
C2—C1—H1B | 109.5 | H6A—C6—H6B | 108.1 |
H1A—C1—H1B | 108.1 | C5—N1—C3 | 112.2 (3) |
O1—C2—C1 | 110.6 (3) | C5—N1—C1 | 112.6 (3) |
O1—C2—H2A | 109.5 | C3—N1—C1 | 111.0 (3) |
C1—C2—H2A | 109.5 | C5—N1—Co1 | 105.15 (19) |
O1—C2—H2B | 109.5 | C3—N1—Co1 | 107.8 (2) |
C1—C2—H2B | 109.5 | C1—N1—Co1 | 107.6 (2) |
H2A—C2—H2B | 108.1 | N3—N2—Co1 | 122.8 (2) |
N1—C3—C4 | 111.4 (3) | N4—N3—N2 | 177.5 (4) |
N1—C3—H3A | 109.4 | C2—O1—Co1 | 113.2 (2) |
C4—C3—H3A | 109.4 | C2—O1—H2OA | 109 (3) |
N1—C3—H3B | 109.4 | Co1—O1—H2OA | 123 (3) |
C4—C3—H3B | 109.4 | C4—O2—Co1 | 116.5 (2) |
H3A—C3—H3B | 108.0 | C4—O2—H1OA | 107 (4) |
O2—C4—C3 | 108.7 (3) | Co1—O2—H1OA | 117 (4) |
O2—C4—H4A | 110.0 | C6—O3—Co1 | 113.77 (18) |
C3—C4—H4A | 110.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1OA···O3i | 0.80 (6) | 1.80 (6) | 2.595 (3) | 176.90 |
O1—H2OA···O3ii | 0.74 (3) | 1.83 (3) | 2.573 (3) | 177.70 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C6H14NO3)(N3)] |
Mr | 249.14 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.7752 (2), 7.9373 (1), 14.4097 (3) |
β (°) | 107.084 (1) |
V (Å3) | 959.37 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.78 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Rigaku Saturn CCD |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.708, 0.823 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4004, 2179, 1253 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.089, 0.89 |
No. of reflections | 2179 |
No. of parameters | 135 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.55, −0.38 |
Computer programs: CrystalClear (Rigaku/MSC, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).
Co1—O3 | 1.991 (2) | Co1—O2 | 2.065 (2) |
Co1—N2 | 2.013 (3) | Co1—N1 | 2.148 (3) |
Co1—O1 | 2.064 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1OA···O3i | 0.80 (6) | 1.80 (6) | 2.595 (3) | 176.90 |
O1—H2OA···O3ii | 0.74 (3) | 1.83 (3) | 2.573 (3) | 177.70 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2. |
Acknowledgements
This study was supported by the Doctoral Research Fund of Henan Chinese Medicine (BSJJ2009–38).
References
Jacobson, R. (1998). REQAB. Private communication to the Rigaku Corporation, Tokyo, Japan. Google Scholar
Liu, T., Wang, B.-W., Chen, Y.-H., Wang, Z.-M. & Gao, S. (2008). Z. Anorg. Allg. Chem. 634, 778–783. Web of Science CSD CrossRef CAS Google Scholar
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The design and synthesis of mononuclear compounds with strong anisotropy, potentially acting as single ion magnets, are of current interest. Podand-like or multi-dentate ligands, such as diethanolamine (deaH2) or triethanolamine (teaH3), have been employed though these ligands were also used to prepare other kinds of clusters (Liu, Wang et al., 2008; Liu, Zhang et al., 2008). In this work, we selected teaH3 as a capping ligand, and azide as another anion, generating complex (I), Co(N(CH2CH2OH)2(CH2CH2O))N3 [= Co(teaH2)N3].
In the structure of (I) each CoII atom is five-coordinate by three O atoms and one N atom from a simply deprotonated tetradentate triethanolamine ligand, and one N atom from an azide ligand in a trigonal-bipymidal coordination environment (Fig. 1). The O atoms define the equatorial plane whereas both N atoms sit in axial positions. The Co—N distances are 2.013 (3)—2.148 (3) Å, and the Co—O distances are 1.991 (2)–2.065 (2) Å. These bond length are in agreement with similar complexes with CoII in trigonal-pyramidal coordination (Malaestean et al., 2010).
The mononuclear Co(teaH2)N3 units are linked through O—H···O hydrogen bonding interactions between the ethanol OH groups and the ethanolate O atom of a neighbouring complex into chains running parallel to [010] (Fig. 2).