supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2383    [ doi:10.1107/S1600536807039487 ]

Aqua{6,6'-dimethoxy-2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato-[kappa]4O,N,N',O'}cobalt(II)

G.-B. Jiang, S.-H. Zhang and M.-H. Zeng

Abstract top

In the title compound, [Co(C18H18N2O4)(H2O)], the CoII atom is coordinated in a distorted square-pyramidal geometry defined by two O atoms and two N atoms in the basal positions, and one water molecule in the apical position. The CoII atom and water O atom lie on a symmetry plane defining Cs molecular symmetry. In the crystal structure, the ethylenediamine group is disordered over two positions with equal occupancy. Molecules are linked into chains via O-H...O hydrogen bonds.

Comment top

Using H2L [where H2L is N,N'-ethylene-bis(3-methoxysalicylaldiminato)], we have hydrothermally prepared the title compound, (I), namely Co(L)(H2O). As an example of penta coordinated Co(II) complexes there are series of complexes with 1,4-diazacycloheptane (DACH) functionalized by additional imidazole or pyridine donor pendants [CoL1Cl](ClO4)·H2O, [CoL2Cl](ClO4) and [CoL3Cl](ClO4)·CH3OH, where L1=1,4-bis(imidazole-4-ylmethyl)-DACH, L2=1,4-bis(N-1-methylimidazol-2-ylmethyl)-DACH and L3=1,4-bis(pyridyl-2-ylmethyl)-DACH that were synthesized and characterized (Guo et al., 2002). In the present structure Co(II) atom is coordinated by two phenolato oxygen atoms and two imine nitrogen atoms from L2− ligand, and one water molecule to furnish a distorted square pyramidal coordination geometry (Fig. 1, Table 1). The O atom of water molecule is at the apical position of square pyramid and the other two O atoms and two N atoms are at the base of square pyramid. The CoII and O atom of water molecule lie on a symmetry plane. The two C atoms of ethylenediamine moiety are disordered over two positions with equal occupancy. The complex generates 1-D chain through hydrogen bonds between water molecule and phenolato oxygen (Table 2 and Fig. 2).

Related literature top

For related literature, see: Guo et al. (2002).

Experimental top

2-Hydroxy-3-methoxy-benzaldehyde (0.152 g, 1 mmol), ethane-1,2-diamine (0.120 g, 2 mmol) and Co(NO3)2·6H2O (0.290 g, 1 mmol) were dissolved in a mixture solution (8 ml of methanol: acetonitrile = 1:1(v / v)). The solution was sealed in a 15 ml Teflon-lined stainless steel bomb and held at 353 K for 5 d. Then, a bomb was cooled to room temperature and red block crystals were filtered off, washed with methanol and dried at room temperature. Elemental analysis, calcd (%) for C18H20CoN2O5: C 62.78, H 5.85, N 8.13; found (%): C 62.56, H 5.92, N 8.11.

Refinement top

There is positional disorder of C9 and C9'i over two equally occupied sites. It was assumed that the ethylenediamine moiety has two possible conformations, namely N1–C9(H9A/H9B)–C9'i(H9Ci/H9Di)–N1'i and N1'–C9'(H9C/H9D)–C9i(H9Ai/H9Bi)–N1i[symmetry code: (i) x, 1/2 − y, z]. H atoms of the water molecule were located in a difference Fourier map, but their distances and angles were restrained to literature values with U(H) = 1.5 times Ueq(O). All other H atoms were positioned geometrically and refined as riding atoms, with C–H distances of 0.95–0.98 Å and U(H) = 1.2–1.5 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with atom labels and the 50% probability displacement ellipsoids for non-H atoms. One of the disorder part is shown by a dashed line. The molecular symmetry Cs is generated by symmetry code: (i) x, 1/2 − y, z.
[Figure 2] Fig. 2. The packing of (I), showing two chains of molecules connected by O—H···O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted.
Aqua{6,6'-dimethoxy-2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato- κ4O,N,N',O'}cobalt(II) top
Crystal data top
[Co(C18H18N2O4)(H2O1)]F000 = 836
Mr = 403.29Dx = 1.583 Mg m−3
Orthorhombic, PnmaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 3183 reflections
a = 8.9827 (6) Åθ = 2.8–28.1º
b = 24.8632 (16) ŵ = 1.05 mm−1
c = 7.5784 (5) ÅT = 173 (2) K
V = 1692.55 (19) Å3Block, red
Z = 40.49 × 0.46 × 0.19 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer		1694 independent reflections
Radiation source: fine-focus sealed tube1389 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
T = 173(2) Kθmax = 26.0º
ω scansθmin = 2.8º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→11
Tmin = 0.628, Tmax = 0.826k = −30→20
6807 measured reflectionsl = −9→7
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.101  w = 1/[σ2(Fo2) + (0.0463P)2 + 2.1284P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
1694 reflectionsΔρmax = 0.76 e Å−3
134 parametersΔρmin = −0.39 e Å−3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Co(C18H18N2O4)(H2O1)]V = 1692.55 (19) Å3
Mr = 403.29Z = 4
Orthorhombic, PnmaMo Kα
a = 8.9827 (6) ŵ = 1.05 mm−1
b = 24.8632 (16) ÅT = 173 (2) K
c = 7.5784 (5) Å0.49 × 0.46 × 0.19 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer		1694 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1389 reflections with I > 2σ(I)
Tmin = 0.628, Tmax = 0.826Rint = 0.027
6807 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0374 restraints
wR(F2) = 0.101H atoms treated by a mixture of
independent and constrained refinement
S = 1.07Δρmax = 0.76 e Å−3
1694 reflectionsΔρmin = −0.39 e Å−3
134 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
xyzUiso*/UeqOcc. (<1)
Co10.05985 (6)0.25001.06224 (7)0.0225 (2)
C10.2009 (3)0.35745 (12)1.0129 (4)0.0270 (6)
C20.3278 (4)0.39125 (13)1.0321 (4)0.0330 (7)
C30.3227 (4)0.44530 (14)0.9907 (6)0.0467 (9)
H30.40800.46721.00910.056*
C40.1929 (5)0.46784 (15)0.9220 (6)0.0554 (11)
H40.18950.50500.89340.066*
C50.0714 (4)0.43626 (15)0.8964 (6)0.0500 (10)
H5−0.01620.45170.84780.060*
C60.0718 (3)0.38107 (13)0.9399 (4)0.0344 (7)
C70.5866 (4)0.39539 (17)1.1006 (6)0.0544 (11)
H7A0.60860.40950.98270.082*
H7B0.66790.37191.13900.082*
H7C0.57630.42541.18370.082*
C8−0.0616 (4)0.35127 (16)0.9037 (5)0.0502 (11)
H8−0.14070.37010.84800.060*
C9−0.2007 (7)0.2696 (3)0.8386 (10)0.0364 (16)0.50
H9A−0.16310.26120.72330.044*0.50
H9B−0.28890.29100.82470.044*0.50
C9'−0.2370 (6)0.2830 (3)0.9378 (10)0.0315 (14)0.50
H9C−0.30150.30630.87170.038*0.50
H9D−0.27670.27681.05370.038*0.50
N1−0.0838 (3)0.30121 (14)0.9399 (5)0.0623 (11)0.50
N1'−0.0838 (3)0.30121 (14)0.9399 (5)0.0623 (11)0.50
O10.2129 (2)0.30725 (8)1.0632 (3)0.0276 (5)
O20.4510 (2)0.36547 (10)1.0954 (3)0.0431 (6)
O1W−0.0369 (3)0.25001.3095 (4)0.0244 (6)
H1W−0.082 (3)0.2221 (2)1.346 (4)0.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0178 (3)0.0214 (3)0.0284 (3)0.000−0.0003 (2)0.000
C10.0252 (15)0.0241 (15)0.0317 (15)−0.0012 (12)0.0006 (12)0.0019 (12)
C20.0308 (17)0.0279 (16)0.0402 (18)−0.0021 (14)−0.0052 (14)0.0066 (14)
C30.044 (2)0.0273 (18)0.069 (2)−0.0093 (16)−0.0113 (19)0.0082 (17)
C40.054 (2)0.0252 (18)0.087 (3)−0.0007 (17)−0.008 (2)0.020 (2)
C50.039 (2)0.0367 (19)0.074 (3)0.0063 (16)−0.0083 (19)0.0234 (19)
C60.0291 (16)0.0326 (17)0.0416 (18)0.0003 (14)−0.0011 (15)0.0117 (14)
C70.036 (2)0.058 (2)0.070 (3)−0.0231 (18)−0.0205 (18)0.030 (2)
C80.0273 (17)0.052 (2)0.072 (3)−0.0039 (16)−0.0160 (17)0.037 (2)
C90.024 (3)0.040 (4)0.045 (4)0.006 (3)−0.008 (3)0.010 (3)
C9'0.016 (3)0.038 (4)0.040 (4)0.006 (3)0.003 (3)0.006 (3)
N10.0272 (16)0.060 (2)0.100 (3)−0.0151 (15)−0.0277 (17)0.051 (2)
N1'0.0272 (16)0.060 (2)0.100 (3)−0.0151 (15)−0.0277 (17)0.051 (2)
O10.0208 (10)0.0209 (10)0.0412 (12)−0.0009 (8)−0.0020 (9)0.0054 (9)
O20.0276 (12)0.0335 (12)0.0682 (17)−0.0103 (10)−0.0141 (11)0.0174 (12)
O1W0.0225 (14)0.0217 (14)0.0291 (15)0.0000.0029 (12)0.000
Geometric parameters (Å, °) top
Co1—O1i1.979 (2)C5—H50.9500
Co1—O11.979 (2)C6—C81.435 (5)
Co1—N1i2.036 (3)C7—O21.427 (4)
Co1—N12.036 (3)C7—H7A0.9800
Co1—O1W2.066 (3)C7—H7B0.9800
C1—O11.309 (3)C7—H7C0.9800
C1—C61.413 (4)C8—N11.290 (5)
C1—C21.424 (4)C8—H80.9500
C2—O21.366 (4)C9—N11.519 (6)
C2—C31.381 (4)C9—H9A0.9601
C3—C41.394 (5)C9—H9B0.9600
C3—H30.9500C9'—H9C0.9599
C4—C51.359 (6)C9'—H9D0.9600
C4—H40.9500O1W—H1W0.848 (10)
C5—C61.411 (5)
O1i—Co1—O191.99 (12)C3—C4—H4120.2
O1i—Co1—N1i89.55 (10)C4—C5—C6121.8 (3)
O1—Co1—N1i153.09 (15)C4—C5—H5119.1
O1i—Co1—N1153.09 (15)C6—C5—H5119.1
O1—Co1—N189.55 (10)C5—C6—C1119.9 (3)
N1i—Co1—N177.4 (2)C5—C6—C8117.1 (3)
O1i—Co1—O1W106.80 (8)C1—C6—C8123.1 (3)
O1—Co1—O1W106.80 (8)N1—C8—C6125.9 (3)
N1i—Co1—O1W98.41 (13)N1—C8—H8117.0
N1—Co1—O1W98.41 (13)C6—C8—H8117.0
O1—C1—C6125.3 (3)N1—C9—H9A109.3
O1—C1—C2117.8 (3)N1—C9—H9B109.8
C6—C1—C2116.9 (3)H9A—C9—H9B108.1
O2—C2—C3124.3 (3)H9C—C9'—H9D110.5
O2—C2—C1114.1 (3)C8—N1—C9119.9 (4)
C3—C2—C1121.7 (3)C8—N1—Co1127.0 (2)
C2—C3—C4120.2 (3)C9—N1—Co1110.2 (3)
C2—C3—H3119.9C1—O1—Co1128.85 (18)
C4—C3—H3119.9C2—O2—C7117.2 (3)
C5—C4—C3119.5 (3)Co1—O1W—H1W119.5 (17)
C5—C4—H4120.2
Symmetry codes: (i) x, −y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1ii0.848 (10)2.100 (18)2.830 (3)144.0 (17)
O1W—H1W···O2ii0.848 (10)2.242 (10)2.962 (2)142.7 (19)
Symmetry codes: (ii) x−1/2, −y+1/2, −z+5/2.
Table 1
Selected geometric parameters (Å, °) top
Co1—O11.979 (2)Co1—O1W2.066 (3)
Co1—N12.036 (3)
O1i—Co1—O191.99 (12)O1—Co1—O1W106.80 (8)
O1—Co1—N189.55 (10)N1—Co1—O1W98.41 (13)
N1i—Co1—N177.4 (2)
Symmetry codes: (i) x, −y+1/2, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1ii0.848 (10)2.100 (18)2.830 (3)144.0 (17)
O1W—H1W···O2ii0.848 (10)2.242 (10)2.962 (2)142.7 (19)
Symmetry codes: (ii) x−1/2, −y+1/2, −z+5/2.
Acknowledgements top

We acknowledge financial support by the NSFC (Nos. 30460153 and 20561001) and the Natural Science Foundation of Guangxi Province (No. 0447019).

references
References top

Bruker (2001). SMART. Version 5.054. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2003). SAINT-Plus. Version 6.45. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2005). SHELXTL. Version 6.14. Bruker AXS Inc., Madison, Wisconsin, USA.

Guo, Y.-M., Du, M. & Bu, X.-H. (2002). J. Mol. Struct. 610, 27–31.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.