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Acta Cryst. (2009). E65, m468    [ doi:10.1107/S1600536809011167 ]

Aquachlorido{6,6'-dimethoxy-2,2'-[ethane-1,2-diylbis(nitrilodimethylidyne)]diphenolato-[kappa]2O1,N,N',O1'}cobalt(III) monohydrate

J. Xing

Abstract top

The title compound, [Co(C18H18N2O4)Cl(H2O)]·H2O, contains a distorted octahedral cobalt(III) complex with a 6,6'-dimethoxy-2,2'-[ethane-1,2-diylbis(nitrilodimethylidyne)]diphenolate ligand, a chloride and an aqua ligand, and also a disordered water solvent molecule (half-occupancy). The CoIII ion is coordinated in an N2O3Cl manner. Weak O-H...O hydrogen bonds may help to stabilize the crystal packing.

Comment top

The synthesis and structural investigation of Schiff base complexes have attracted much attention due to their interesting structures and wide potential applications. They play an important role in the development of coordination chemistry as well as inorganic biochemistry, catalysis, optical materials and so on (Aurangzeb et al., 1994, Hulme et al., 1997; Li et al., 2008; Fei & Fang, 2008; Zhang & Janiak, 2001). Here, we report a new Schiff base cobalt complex based on the tetradentate Schiff base ligand 6,6'-dimethoxy-2,2'-(ethane-1,2-diyldiiminodimethylene)diphenol.

The molecular structure of title compound is shown in Fig. 1. The coordination sphere for the CoIII ion in the title complex is a distorted octahedron, in which four equational positions come from two N atoms, two O atoms of the Schiff base ligand, and the other two trans ones are occupied by one chloro ion and the O atom of water molecule. The Co—O and Co—N bond lengths are basically consistent with the corresponding distances in the similar cobalt tetradentate Schiff base complex bis[[µ-bis(salicylaldehyde)ethylenediimine]-dicobalt(III) dichloride chloroform solvate(Wang, et al., 1979), while the Co—O (H2O) and the Co—Cl bond lengths are slightly longer than those found in the same complex. Additional, molecules are held together via intermolecular O—H···O and intramolecular O—H···Cl and O—H···O hydrogen bonds.

Related literature top

For related literature, see: Aurangzeb et al. (1994); Hulme et al. (1997); Li et al. (2008); Fei & Fang (2008); Wang et al. (1979); Xia et al. (2007); Zhang & Janiak (2001).

Experimental top

6,6'-dimethoxy-2,2'-(ethane-1,2-diyldiiminodimethylene)diphenol was synthesized according to a modified reported method (Xia, et al., 2007). A mixture of CoCl2.6H2O (1 mmol, 237 mg), 6,6'-dimethoxy-2,2'-(ethane-1,2-diyldiiminodimethylene)diphenol (1 mmol, 326.4 mg) and 40 ml methanol was stirred for 30 min at 323 K, before it was filtered to remove the insolvable materials. Crystals suitable for X-ray diffraction analysis were obtained by slow evaparation at room temperature for three weeks with a yield about 40%.

Refinement top

All H atoms bonded to the C atoms were placed in geometrically calculated positions with C—H = 0.96 Å for methyl H atoms, C—H = 0.97 Å for methylene H atoms, C—H = 0.93 Å for aromatic H atoms and were refined isotropic with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(C) of parent atom using a riding model. The H atoms of the disordered H2O were located from difference maps, in which the H2B and H2C were also disordered with the individual occupancy of 25%, and the O—H bond lengths were constrained to the value of 0.85 (1)Å with Uiso(H) = 1.2Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: XP (Sheldrick, 1998).

Figures top
[Figure 1] Fig. 1. A view of complex (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. The solvate water molecule and all the H atoms have been omitted for clarity.
Aquachlorido{6,6'-dimethoxy-2,2'-[ethane-1,2- diylbis(nitrilodimethylidyne)]diphenolato- κ2O1,N,N',O1'}cobalt(III) monohydrate top
Crystal data top
[Co(C18H18N2O4)Cl(H2O)]·H2ODx = 1.438 Mg m−3
Dm = 1.438 Mg m−3
Dm measured by not measured
Mr = 456.76Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 5356 reflections
Hall symbol: -R 3θ = 2.7–26.9°
a = 26.490 (2) ŵ = 0.98 mm−1
c = 15.6234 (17) ÅT = 293 K
V = 9494.5 (14) Å3Block, orange
Z = 180.15 × 0.13 × 0.09 mm
F(000) = 4248
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4116 independent reflections
Radiation source: fine-focus sealed tube2834 reflections with I > 2σ(I)
graphiteRint = 0.062
φ and ω scansθmax = 26.2°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −28→32
Tmin = 0.868, Tmax = 0.917k = −32→25
13737 measured reflectionsl = −19→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.074Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.259H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.1835P)2]
where P = (Fo2 + 2Fc2)/3
4116 reflections(Δ/σ)max = 0.001
274 parametersΔρmax = 1.55 e Å−3
0 restraintsΔρmin = −1.03 e Å−3
Crystal data top
[Co(C18H18N2O4)Cl(H2O)]·H2OZ = 18
Mr = 456.76Mo Kα radiation
Trigonal, R3µ = 0.98 mm−1
a = 26.490 (2) ÅT = 293 K
c = 15.6234 (17) Å0.15 × 0.13 × 0.09 mm
V = 9494.5 (14) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4116 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2834 reflections with I > 2σ(I)
Tmin = 0.868, Tmax = 0.917Rint = 0.062
13737 measured reflectionsθmax = 26.2°
Refinement top
R[F2 > 2σ(F2)] = 0.074H-atom parameters constrained
wR(F2) = 0.259Δρmax = 1.55 e Å−3
S = 1.03Δρmin = −1.03 e Å−3
4116 reflectionsAbsolute structure: ?
274 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)
Co10.73792 (3)0.12280 (3)0.59262 (4)0.0357 (3)
Cl10.62851 (7)0.08016 (8)0.61355 (10)0.0637 (5)
O10.5945 (14)0.144 (3)0.478 (3)0.057 (16)0.15 (3)
H1C0.61270.16360.43550.068*0.15 (3)
H1D0.61440.13050.50140.068*0.15 (3)
O80.5817 (6)0.1059 (11)0.4435 (11)0.058 (7)0.35 (3)
H8E0.59710.14060.42410.069*0.35 (3)
H8D0.59900.10680.48870.069*0.35 (3)
O20.7381 (4)0.2826 (4)0.3172 (5)0.055 (2)0.50
H2C0.75320.27730.27350.066*0.25
H2D0.75390.31930.32580.066*0.50
H2B0.70120.26750.31090.066*0.25
O30.74870 (15)0.07928 (14)0.6768 (2)0.0349 (8)
O40.76146 (16)0.18833 (15)0.6619 (2)0.0404 (8)
O50.77398 (18)0.04171 (17)0.8092 (2)0.0481 (9)
O60.78604 (19)0.25833 (17)0.7866 (3)0.0552 (10)
O70.83443 (14)0.15912 (15)0.5522 (2)0.0401 (8)
H7C0.85520.15390.58810.048*
H7D0.84990.19580.54340.048*
N10.71890 (18)0.06087 (19)0.5088 (2)0.0376 (9)
N20.73614 (19)0.1675 (2)0.4961 (3)0.0422 (10)
C10.7312 (2)−0.0054 (2)0.5961 (3)0.0417 (12)
C20.7457 (2)0.0273 (2)0.6710 (3)0.0352 (10)
C30.7579 (3)0.0050 (2)0.7421 (3)0.0429 (12)
C40.7545 (3)−0.0489 (3)0.7403 (4)0.0608 (17)
H40.7633−0.06280.78940.073*
C50.7387 (4)−0.0815 (3)0.6683 (5)0.074 (2)
H50.7354−0.11810.66850.088*
C60.7280 (3)−0.0612 (3)0.5979 (5)0.0592 (16)
H60.7182−0.08350.54820.071*
C70.7192 (2)0.0129 (2)0.5214 (3)0.0399 (11)
H70.7102−0.01180.47450.048*
C80.7796 (3)0.0185 (4)0.8876 (4)0.070 (2)
H8A0.7445−0.01770.89880.104*
H8B0.78610.04560.93290.104*
H8C0.81200.01180.88440.104*
C90.7448 (2)0.2507 (3)0.5713 (4)0.0462 (12)
C100.7583 (2)0.2354 (2)0.6479 (3)0.0406 (12)
C110.7708 (3)0.2746 (2)0.7164 (4)0.0473 (13)
C120.7685 (3)0.3254 (3)0.7061 (5)0.0666 (18)
H120.77660.35030.75250.080*
C130.7547 (4)0.3394 (3)0.6299 (6)0.079 (2)
H130.75270.37330.62430.095*
C140.7439 (3)0.3038 (3)0.5620 (5)0.0635 (17)
H140.73580.31400.50890.076*
C150.8063 (3)0.2980 (3)0.8565 (4)0.0628 (18)
H15A0.84270.33180.84150.094*
H15B0.81170.27950.90560.094*
H15C0.77810.30960.86950.094*
C160.7376 (3)0.2170 (3)0.4987 (4)0.0477 (13)
H160.73340.23170.44680.057*
C170.7351 (3)0.1387 (3)0.4155 (3)0.0537 (15)
H17A0.77450.15080.39750.064*
H17B0.71660.14960.37120.064*
C180.7020 (3)0.0749 (3)0.4289 (3)0.0537 (14)
H18A0.66060.06130.42940.064*
H18B0.70990.05550.38240.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0441 (5)0.0379 (4)0.0280 (4)0.0226 (3)−0.0021 (3)−0.0013 (2)
Cl10.0478 (9)0.0909 (12)0.0596 (10)0.0402 (9)0.0133 (7)0.0135 (8)
O10.053 (18)0.08 (3)0.05 (2)0.04 (2)0.001 (14)0.02 (2)
O80.054 (8)0.079 (15)0.050 (9)0.041 (9)0.001 (6)0.023 (9)
O20.059 (5)0.064 (5)0.038 (4)0.028 (4)−0.016 (3)−0.006 (4)
O30.048 (2)0.0316 (17)0.0316 (16)0.0247 (16)−0.0040 (14)−0.0019 (13)
O40.055 (2)0.0358 (19)0.0366 (18)0.0271 (17)−0.0075 (15)−0.0045 (14)
O50.067 (3)0.050 (2)0.0366 (19)0.036 (2)−0.0030 (17)0.0073 (16)
O60.070 (3)0.041 (2)0.052 (2)0.025 (2)−0.0006 (19)−0.0114 (17)
O70.039 (2)0.0397 (19)0.0370 (19)0.0165 (16)−0.0023 (14)0.0003 (14)
N10.035 (2)0.044 (2)0.031 (2)0.0166 (19)−0.0035 (16)−0.0091 (17)
N20.043 (2)0.052 (3)0.033 (2)0.025 (2)−0.0031 (18)0.0039 (18)
C10.040 (3)0.033 (3)0.051 (3)0.018 (2)−0.001 (2)−0.009 (2)
C20.032 (2)0.033 (2)0.043 (3)0.018 (2)0.0029 (19)0.0007 (19)
C30.052 (3)0.040 (3)0.041 (3)0.027 (3)0.004 (2)0.008 (2)
C40.083 (5)0.048 (4)0.063 (4)0.041 (4)−0.004 (3)0.008 (3)
C50.100 (6)0.042 (4)0.091 (6)0.044 (4)−0.014 (4)−0.005 (3)
C60.072 (4)0.038 (3)0.070 (4)0.029 (3)−0.002 (3)−0.013 (3)
C70.035 (3)0.037 (3)0.041 (3)0.014 (2)−0.004 (2)−0.015 (2)
C80.096 (5)0.088 (5)0.038 (3)0.056 (5)0.000 (3)0.018 (3)
C90.044 (3)0.047 (3)0.055 (3)0.028 (3)−0.001 (2)0.007 (2)
C100.040 (3)0.035 (3)0.052 (3)0.021 (2)0.004 (2)0.002 (2)
C110.047 (3)0.038 (3)0.057 (3)0.021 (3)0.002 (2)−0.005 (2)
C120.082 (5)0.046 (4)0.080 (5)0.039 (4)−0.002 (4)−0.011 (3)
C130.093 (6)0.051 (4)0.108 (6)0.047 (4)−0.005 (5)0.003 (4)
C140.068 (4)0.055 (4)0.079 (4)0.040 (3)−0.003 (3)0.008 (3)
C150.060 (4)0.053 (4)0.056 (4)0.014 (3)0.002 (3)−0.023 (3)
C160.047 (3)0.053 (3)0.046 (3)0.026 (3)−0.005 (2)0.013 (2)
C170.064 (4)0.063 (4)0.029 (3)0.028 (3)−0.005 (2)−0.001 (2)
C180.062 (4)0.066 (4)0.033 (3)0.032 (3)−0.008 (2)−0.009 (3)
Geometric parameters (Å, °) top
Co1—O31.863 (3)C2—C31.370 (7)
Co1—O41.868 (3)C3—C41.385 (8)
Co1—N21.932 (4)C4—C51.350 (9)
Co1—N11.957 (4)C4—H40.9300
Co1—O72.324 (3)C5—C61.315 (10)
Co1—Cl12.5513 (17)C5—H50.9300
O1—H1C0.8381C6—H60.9300
O1—H1D0.8514C7—H70.9300
O1—H8E0.8596C8—H8A0.9600
O1—H8D1.0649C8—H8B0.9600
O8—H1D1.1965C8—H8C0.9600
O8—H8E0.8530C9—C101.367 (8)
O8—H8D0.8360C9—C161.396 (8)
O2—H2C0.8374C9—C141.426 (8)
O2—H2D0.8561C10—C111.411 (8)
O2—H2B0.8563C11—C121.385 (9)
O3—C21.342 (6)C12—C131.350 (11)
O4—C101.309 (6)C12—H120.9300
O5—C31.347 (7)C13—C141.352 (10)
O5—C81.412 (7)C13—H130.9300
O6—C111.314 (7)C14—H140.9300
O6—C151.422 (7)C15—H15A0.9600
O7—H7C0.8439C15—H15B0.9600
O7—H7D0.8561C15—H15C0.9600
N1—C71.290 (7)C16—H160.9300
N1—C181.436 (7)C17—C181.480 (9)
N2—C161.294 (8)C17—H17A0.9700
N2—C171.465 (7)C17—H17B0.9700
C1—C71.362 (7)C18—H18A0.9700
C1—C21.391 (7)C18—H18B0.9700
C1—C61.438 (8)
O3—Co1—O494.76 (14)C6—C5—C4119.7 (6)
O3—Co1—N2171.32 (17)C6—C5—H5120.1
O4—Co1—N288.92 (18)C4—C5—H5120.1
O3—Co1—N190.48 (16)C5—C6—C1121.5 (6)
O4—Co1—N1172.92 (17)C5—C6—H6119.3
N2—Co1—N185.24 (18)C1—C6—H6119.3
O3—Co1—O788.31 (14)N1—C7—C1126.8 (5)
O4—Co1—O789.17 (15)N1—C7—H7116.6
N2—Co1—O783.87 (16)C1—C7—H7116.6
N1—Co1—O786.23 (15)O5—C8—H8A109.5
O3—Co1—Cl197.31 (12)O5—C8—H8B109.5
O4—Co1—Cl196.58 (13)H8A—C8—H8B109.5
N2—Co1—Cl190.05 (14)O5—C8—H8C109.5
N1—Co1—Cl187.44 (13)H8A—C8—H8C109.5
O7—Co1—Cl1171.56 (10)H8B—C8—H8C109.5
H1C—O1—H1D108.1C10—C9—C16119.6 (5)
H1C—O1—H8E39.0C10—C9—C14121.2 (6)
H1D—O1—H8E105.8C16—C9—C14118.9 (5)
H1C—O1—H8D113.4O4—C10—C9125.4 (5)
H1D—O1—H8D33.5O4—C10—C11118.2 (5)
H8E—O1—H8D89.9C9—C10—C11116.4 (5)
H1C—O8—H1D65.3O6—C11—C12125.9 (6)
H1C—O8—H8E16.5O6—C11—C10112.8 (5)
H1D—O8—H8E81.6C12—C11—C10121.2 (6)
H1C—O8—H8D91.9C13—C12—C11121.3 (6)
H1D—O8—H8D26.9C13—C12—H12119.4
H8E—O8—H8D108.1C11—C12—H12119.4
H2C—O2—H2D108.4C12—C13—C14119.5 (6)
H2C—O2—H2B111.0C12—C13—H13120.2
H2D—O2—H2B110.1C14—C13—H13120.2
C2—O3—Co1129.7 (3)C13—C14—C9120.3 (7)
C10—O4—Co1129.6 (3)C13—C14—H14119.8
C3—O5—C8115.2 (5)C9—C14—H14119.8
C11—O6—C15117.5 (5)O6—C15—H15A109.5
Co1—O7—H7C115.1O6—C15—H15B109.5
Co1—O7—H7D108.4H15A—C15—H15B109.5
H7C—O7—H7D108.2O6—C15—H15C109.5
C7—N1—C18122.9 (4)H15A—C15—H15C109.5
C7—N1—Co1126.7 (3)H15B—C15—H15C109.5
C18—N1—Co1110.4 (4)N2—C16—C9126.8 (5)
C16—N2—C17122.5 (5)N2—C16—H16116.6
C16—N2—Co1126.9 (4)C9—C16—H16116.6
C17—N2—Co1110.6 (4)N2—C17—C18108.7 (5)
C7—C1—C2122.6 (5)N2—C17—H17A110.0
C7—C1—C6118.7 (5)C18—C17—H17A110.0
C2—C1—C6118.7 (5)N2—C17—H17B110.0
O3—C2—C3118.8 (4)C18—C17—H17B110.0
O3—C2—C1123.6 (5)H17A—C17—H17B108.3
C3—C2—C1117.6 (5)N1—C18—C17109.6 (5)
O5—C3—C2112.2 (4)N1—C18—H18A109.7
O5—C3—C4126.4 (5)C17—C18—H18A109.7
C2—C3—C4121.4 (5)N1—C18—H18B109.7
C5—C4—C3121.0 (6)C17—C18—H18B109.7
C5—C4—H4119.5H18A—C18—H18B108.2
C3—C4—H4119.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O7—H7D···O3i0.862.442.883 (5)113
O7—H7D···O5i0.862.223.078 (5)178
O7—H7C···O6i0.842.583.033 (6)115
O7—H7C···O4i0.841.952.798 (5)178
O2—H2D···O2ii0.862.012.861 (9)178
O2—H2C···O8ii0.842.132.868 (19)147
O2—H2C···O1ii0.841.722.56 (3)175
O8—H8E···O2iii0.852.042.868 (19)163
O8—H8D···Cl10.842.343.147 (12)163
O1—H1D···Cl10.852.343.11 (3)150
Symmetry codes: (i) −x+5/3, −y+1/3, −z+4/3; (ii) x−y+1/3, x−1/3, −z+2/3; (iii) y+1/3, −x+y+2/3, −z+2/3.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O7—H7D···O3i0.862.442.883 (5)113
O7—H7D···O5i0.862.223.078 (5)178
O7—H7C···O6i0.842.583.033 (6)115
O7—H7C···O4i0.841.952.798 (5)178
O2—H2D···O2ii0.862.012.861 (9)178
O2—H2C···O8ii0.842.132.868 (19)147
O2—H2C···O1ii0.841.722.56 (3)175
O8—H8E···O2iii0.852.042.868 (19)163
O8—H8D···Cl10.842.343.147 (12)163
O1—H1D···Cl10.852.343.11 (3)150
Symmetry codes: (i) −x+5/3, −y+1/3, −z+4/3; (ii) x−y+1/3, x−1/3, −z+2/3; (iii) y+1/3, −x+y+2/3, −z+2/3.
references
References top

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