Azido­{2-[bis­(2-hy­droxy­eth­yl)amino]­ethano­lato-κ4N,O,O′,O′′}cobalt(II)

Liu, Y.-J.; Yang, H.-X.; Yuan, J.; Wang, X.

doi:10.1107/S1600536810047100

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1617

https://doi.org/10.1107/S1600536810047100

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Azido{2-[bis(2-hydroxyethyl)amino]ethanolato-κ⁴N,O,O′,O′′}cobalt(II)

Yan-Ju Liu,^a ^* Huai-Xia Yang,^a Juan Yuan ^a and Xia Wang ^a

^aPharmacy College, Henan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China
^*Correspondence e-mail: liuyanju886@163.com

(Received 8 November 2010; accepted 14 November 2010; online 20 November 2010)

In the title complex, [Co(C₆H₁₄NO₃)(N₃)] or [Co(teaH₂)N₃], the Co^II 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 Co^II complexes with similar ligands, see: Malaestean et al. (2010 ).

Experimental

Crystal data

[Co(C₆H₁₄NO₃)(N₃)]
M_r = 249.14
Monoclinic, P 2₁ /c
a = 8.7752 (2) Å
b = 7.9373 (1) Å
c = 14.4097 (3) Å
β = 107.084 (1)°
V = 959.37 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.78 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.10 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.708, T_max = 0.823
4004 measured reflections
2179 independent reflections
1253 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.089
S = 0.89
2179 reflections
135 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O3	1.991 (2)
Co1—N2	2.013 (3)
Co1—O1	2.064 (2)
Co1—O2	2.065 (2)
Co1—N1	2.148 (3)

Table 2
Hydrogen-bond geometry (Å, °)

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) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2006 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810047100/wm2427sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047100/wm2427Isup2.hkl

checkCIF report

Comment top

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 Co^II 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 Co^II 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).

Related literature top

For general background to complexes including teaH₃ ligands, see: Liu, Wang et al. (2008); Liu, Zhang et al. (2008). For Co^II complexes with similar ligands, see: Malaestean et al. (2010).

Experimental top

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.

Structure description top

For general background to complexes including teaH₃ ligands, see: Liu, Wang et al. (2008); Liu, Zhang et al. (2008). For Co^II complexes with similar ligands, see: Malaestean et al. (2010).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: 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).

Figures top

	Fig. 1. View of the molecular structure of (I), showing the labelling of the atoms drawn with displacement ellipsoids at the 30% probability level. All H atoms have been omitted for clarity.
	Fig. 2. A view of the crystal packing along the c axis. Hydrogen bonds are indicated with dashed lines.

Azido{2-[bis(2-hydroxyethyl)amino]ethanolato- κ⁴N,O,O',O''}cobalt(II) top

Crystal data top

[Co(C₆H₁₄NO₃)(N₃)]	F(000) = 516
M_r = 249.14	D_x = 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

Data collection top

Rigaku Saturn CCD diffractometer	2179 independent reflections
Radiation source: fine-focus sealed tube	1253 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
Detector resolution: 0.76 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
ω scans	h = −11→11
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −10→10
T_min = 0.708, T_max = 0.823	l = −18→18
4004 measured reflections

Refinement top

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(F_o²) + (0.0427P)²] where P = (F_o² + 2F_c²)/3
2179 reflections	(Δ/σ)_max = 0.001
135 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Co(C₆H₁₄NO₃)(N₃)]	V = 959.37 (3) Å³
M_r = 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)°

Data collection top

Rigaku Saturn CCD diffractometer	2179 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	1253 reflections with I > 2σ(I)
T_min = 0.708, T_max = 0.823	R_int = 0.055
4004 measured reflections

Refinement top

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	Δρ_max = 0.55 e Å⁻³
2179 reflections	Δρ_min = −0.38 e Å⁻³
135 parameters

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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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)]
M_r	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)
T_min, T_max	0.708, 0.823
No. of measured, independent and observed [I > 2σ(I)] reflections	4004, 2179, 1253
R_int	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
Δρ_max, Δρ_min (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).

Selected bond lengths (Å) top

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)

Hydrogen-bond geometry (Å, º) top

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

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