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Acta Cryst. (2009). E65, m1470    [ doi:10.1107/S1600536809044092 ]

Bis(ethylenediamine-[kappa]2N,N')bis(phenytoinato-[kappa]N)cobalt(II)

X.-L. Hu, X.-Y. Xu, D.-Q. Wang and Y.-Q. Zhou

Abstract top

The title compound [systematic name: bis(2,5-dioxo-4,4-diphenylimidazolidin-1-ido-[kappa]N1)bis(ethylenediamine-[kappa]2N,N')cobalt(II)], [Co(C15H11N2O2)2(C2H8N2)2], has site symmetry \overline{1}. The CoII cation is located on an inversion center and coordinated by two phenytoin anions and two ethylenediamine ligands in a distorted octahedral geometry. In the phenytoin anion, the two phenyl rings are twisted with respect to the central hydantoin ring, making dihedral angles of 77.49 (16) and 64.55 (15)°. Intramolecular and intermolecular N-H...O hydrogen bonding is present in the crystal structure.

Comment top

5,5-Diphenylimidazoline-2,4-dione (phenytoin) compound is a widely used drug in the treatment of epilepsy and should be an excellent ligand for transition metal complex (Akitsu et al., 1997; Akitsu & Einaga, 2005). We have synthesized a series of complexes with 5,5-diphenylhydantoinate ligand (Hu et al., 2006, 2007). We report here the crystal structure of the title compound.

The compound (Fig. 1) consists of [Co(pht)2(en)2] (Hpht = 5,5-diphenylhydantoin; en = ethylendiamine) complex neutral molecule. The Co atom is coordinated by two nitrogen atoms from two Hpht ligands and four nitrogen atoms from two en ligands in a distorted octahedral CoN6 coordination environment (Table 1). The Co—N bond distances lie in the range of 2.123 (2) Å to 2.180 (2) Å. There are intra- and intermolecular N—H···O hydrogen bonds (Table 2).

Related literature top

For applications of phenytoin, see: Akitsu & Einaga (2005); Akitsu et al. (1997). For related compounds, see: Hu et al. (2006, 2007).

Experimental top

To a solution of Hpht (1 mmol) in methanol (10 ml) was added cobalt acetate tetrahydrate (0.5 mmol) and the solution of ethylenediamine (1 mmol) in methanol (10 ml). Then the mixture was sealed in a 25 ml stainless steel vessel with Teflon linear, and heated at 393 K for 50 h. After cooling to room temperature, the orange single crystals were obtained.

Refinement top

H atoms were placed at calculated positions with N—H = 0.86–0.90 Å and C—H = 0.93–0.97 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex. Displacement ellipsoids are drawn at the 30% probability level. The H-atom have been omitted for clarity.
bis(2,5-dioxo-4,4-diphenylimidazolidin-1-ido- κN1)bis(ethylenediamine-κ2N,N')cobalt(II) top
Crystal data top
[Co(C15H11N2O2)2(C2H8N2)2]F(000) = 714
Mr = 681.65Dx = 1.404 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3389 reflections
a = 11.8035 (12) Åθ = 2.4–26.9°
b = 12.3439 (13) ŵ = 0.58 mm−1
c = 11.0768 (10) ÅT = 298 K
β = 92.277 (1)°Block, orange
V = 1612.6 (3) Å30.52 × 0.42 × 0.28 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		2836 independent reflections
Radiation source: fine-focus sealed tube2201 reflections with I > 2σ(I)
graphiteRint = 0.053
φ and ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→11
Tmin = 0.751, Tmax = 0.854k = −14→14
7877 measured reflectionsl = −13→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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0528P)2 + 0.9459P]
where P = (Fo2 + 2Fc2)/3
2836 reflections(Δ/σ)max = 0.001
214 parametersΔρmax = 0.45 e Å−3
0 restraintsΔρmin = −0.62 e Å−3
Crystal data top
[Co(C15H11N2O2)2(C2H8N2)2]V = 1612.6 (3) Å3
Mr = 681.65Z = 2
Monoclinic, P21/cMo Kα radiation
a = 11.8035 (12) ŵ = 0.58 mm−1
b = 12.3439 (13) ÅT = 298 K
c = 11.0768 (10) Å0.52 × 0.42 × 0.28 mm
β = 92.277 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2836 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2201 reflections with I > 2σ(I)
Tmin = 0.751, Tmax = 0.854Rint = 0.053
7877 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.120Δρmax = 0.45 e Å−3
S = 1.08Δρmin = −0.62 e Å−3
2836 reflectionsAbsolute structure: ?
214 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*/Ueq
Co10.50000.00000.00000.02790 (18)
N10.69362 (19)0.2364 (2)0.21879 (19)0.0366 (6)
H10.70280.27320.28430.044*
N20.61498 (18)0.11950 (18)0.08239 (18)0.0300 (5)
N30.63769 (19)−0.0802 (2)−0.0794 (2)0.0412 (6)
H3A0.6163−0.1046−0.15340.049*
H3B0.6959−0.0339−0.08690.049*
N40.5465 (2)−0.1072 (2)0.1492 (2)0.0437 (6)
H4A0.5499−0.07020.21930.052*
H4B0.4951−0.16060.15490.052*
O10.53186 (17)0.14774 (19)0.26695 (18)0.0513 (6)
O20.74262 (16)0.13811 (15)−0.06839 (15)0.0335 (5)
C10.6080 (2)0.1661 (2)0.1968 (2)0.0336 (6)
C20.7082 (2)0.1602 (2)0.0329 (2)0.0277 (6)
C30.7685 (2)0.2423 (2)0.1181 (2)0.0304 (6)
C40.7646 (2)0.3540 (2)0.0582 (2)0.0353 (7)
C50.6736 (3)0.4219 (3)0.0689 (4)0.0608 (10)
H50.61480.40130.11740.073*
C60.6674 (4)0.5196 (3)0.0096 (5)0.0799 (13)
H60.60460.56420.01770.096*
C70.7544 (4)0.5513 (3)−0.0617 (3)0.0715 (12)
H70.75040.6174−0.10190.086*
C80.8464 (4)0.4856 (3)−0.0734 (3)0.0688 (12)
H80.90510.5067−0.12170.083*
C90.8516 (3)0.3875 (3)−0.0129 (3)0.0538 (9)
H90.91480.3434−0.02030.065*
C100.8891 (2)0.2084 (2)0.1586 (2)0.0329 (6)
C110.9473 (3)0.2721 (3)0.2414 (3)0.0527 (9)
H110.91470.33620.26740.063*
C121.0538 (3)0.2423 (4)0.2868 (3)0.0681 (11)
H121.09210.28640.34300.082*
C131.1027 (3)0.1489 (4)0.2494 (3)0.0681 (12)
H131.17350.12820.28120.082*
C141.0475 (3)0.0858 (3)0.1654 (3)0.0618 (10)
H141.08170.02310.13800.074*
C150.9402 (3)0.1147 (3)0.1204 (3)0.0473 (8)
H150.90250.07050.06400.057*
C160.6722 (4)−0.1698 (4)−0.0025 (4)0.0868 (14)
H16A0.6294−0.2335−0.02770.104*
H16B0.7517−0.1849−0.01430.104*
C170.6569 (4)−0.1520 (4)0.1242 (4)0.0873 (15)
H17A0.7153−0.10280.15510.105*
H17B0.6665−0.22020.16680.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0217 (3)0.0286 (3)0.0338 (3)0.0002 (2)0.00614 (19)−0.0021 (2)
N10.0347 (13)0.0453 (15)0.0303 (12)−0.0069 (11)0.0082 (10)−0.0116 (11)
N20.0266 (12)0.0330 (13)0.0308 (11)−0.0021 (10)0.0062 (9)−0.0046 (10)
N30.0299 (13)0.0402 (14)0.0542 (14)−0.0011 (11)0.0085 (11)−0.0106 (12)
N40.0394 (14)0.0436 (16)0.0480 (14)−0.0049 (12)0.0015 (11)0.0072 (12)
O10.0414 (12)0.0723 (17)0.0415 (11)−0.0166 (11)0.0190 (10)−0.0120 (11)
O20.0405 (11)0.0343 (11)0.0261 (9)−0.0047 (9)0.0082 (8)−0.0015 (8)
C10.0287 (14)0.0389 (17)0.0334 (14)−0.0016 (13)0.0036 (11)−0.0003 (12)
C20.0295 (14)0.0256 (14)0.0281 (13)−0.0009 (11)0.0035 (11)0.0019 (11)
C30.0297 (14)0.0312 (15)0.0306 (13)−0.0040 (12)0.0066 (11)−0.0051 (11)
C40.0392 (16)0.0277 (15)0.0390 (15)−0.0049 (13)0.0019 (12)−0.0058 (12)
C50.048 (2)0.047 (2)0.088 (3)0.0023 (17)0.0093 (19)0.009 (2)
C60.075 (3)0.048 (3)0.116 (4)0.015 (2)−0.003 (3)0.014 (2)
C70.114 (4)0.034 (2)0.066 (2)−0.003 (2)−0.001 (2)0.0057 (19)
C80.109 (4)0.042 (2)0.057 (2)−0.009 (2)0.029 (2)0.0037 (17)
C90.069 (2)0.0373 (19)0.0565 (19)0.0007 (17)0.0248 (17)0.0010 (16)
C100.0281 (14)0.0396 (17)0.0314 (14)−0.0046 (13)0.0058 (11)0.0019 (12)
C110.0349 (17)0.066 (2)0.0576 (19)−0.0035 (17)0.0022 (14)−0.0179 (17)
C120.0347 (19)0.107 (3)0.062 (2)−0.011 (2)−0.0046 (16)−0.019 (2)
C130.0327 (18)0.110 (4)0.062 (2)0.006 (2)−0.0013 (17)0.013 (2)
C140.047 (2)0.063 (2)0.075 (2)0.0152 (19)0.0041 (18)0.007 (2)
C150.0419 (18)0.047 (2)0.0531 (18)0.0017 (16)−0.0014 (14)−0.0023 (16)
C160.079 (3)0.077 (3)0.106 (4)0.046 (3)0.026 (3)0.009 (3)
C170.072 (3)0.094 (4)0.097 (3)0.043 (3)0.011 (2)0.037 (3)
Geometric parameters (Å, °) top
Co1—N2i2.180 (2)C5—H50.9300
Co1—N22.180 (2)C6—C71.377 (6)
Co1—N32.123 (2)C6—H60.9300
Co1—N3i2.123 (2)C7—C81.365 (6)
Co1—N4i2.171 (2)C7—H70.9300
Co1—N42.171 (2)C8—C91.384 (5)
N1—C11.347 (3)C8—H80.9300
N1—C31.452 (3)C9—H90.9300
N1—H10.8600C10—C111.372 (4)
N2—C21.346 (3)C10—C151.378 (4)
N2—C11.397 (3)C11—C121.386 (5)
N3—C161.444 (5)C11—H110.9300
N3—H3A0.9000C12—C131.362 (6)
N3—H3B0.9000C12—H120.9300
N4—C171.452 (5)C13—C141.359 (5)
N4—H4A0.9000C13—H130.9300
N4—H4B0.9000C14—C151.389 (5)
O1—C11.232 (3)C14—H140.9300
O2—C21.239 (3)C15—H150.9300
C2—C31.540 (4)C16—C171.439 (6)
C3—C41.530 (4)C16—H16A0.9700
C3—C101.533 (4)C16—H16B0.9700
C4—C51.371 (4)C17—H17A0.9700
C4—C91.383 (4)C17—H17B0.9700
C5—C61.374 (5)
N3—Co1—N3i180.00 (17)C9—C4—C3120.4 (3)
N3—Co1—N4i98.26 (10)C4—C5—C6121.5 (4)
N3i—Co1—N4i81.74 (10)C4—C5—H5119.2
N3—Co1—N481.74 (10)C6—C5—H5119.2
N3i—Co1—N498.26 (10)C5—C6—C7119.8 (4)
N4i—Co1—N4180.00 (13)C5—C6—H6120.1
N3—Co1—N2i89.15 (9)C7—C6—H6120.1
N3i—Co1—N2i90.85 (9)C8—C7—C6120.0 (4)
N4i—Co1—N2i87.67 (9)C8—C7—H7120.0
N4—Co1—N2i92.33 (9)C6—C7—H7120.0
N3—Co1—N290.85 (9)C7—C8—C9119.6 (4)
N3i—Co1—N289.15 (9)C7—C8—H8120.2
N4i—Co1—N292.33 (9)C9—C8—H8120.2
N4—Co1—N287.67 (9)C4—C9—C8121.2 (4)
N2i—Co1—N2180.00 (13)C4—C9—H9119.4
C1—N1—C3111.7 (2)C8—C9—H9119.4
C1—N1—H1124.2C11—C10—C15118.2 (3)
C3—N1—H1124.2C11—C10—C3118.2 (3)
C2—N2—C1107.1 (2)C15—C10—C3123.5 (3)
C2—N2—Co1125.97 (16)C10—C11—C12120.9 (4)
C1—N2—Co1126.87 (17)C10—C11—H11119.5
C16—N3—Co1108.4 (2)C12—C11—H11119.5
C16—N3—H3A110.0C13—C12—C11120.2 (4)
Co1—N3—H3A110.0C13—C12—H12119.9
C16—N3—H3B110.0C11—C12—H12119.9
Co1—N3—H3B110.0C14—C13—C12119.8 (3)
H3A—N3—H3B108.4C14—C13—H13120.1
C17—N4—Co1106.7 (2)C12—C13—H13120.1
C17—N4—H4A110.4C13—C14—C15120.2 (4)
Co1—N4—H4A110.4C13—C14—H14119.9
C17—N4—H4B110.4C15—C14—H14119.9
Co1—N4—H4B110.4C10—C15—C14120.6 (3)
H4A—N4—H4B108.6C10—C15—H15119.7
O1—C1—N1124.4 (3)C14—C15—H15119.7
O1—C1—N2124.6 (3)C17—C16—N3114.5 (3)
N1—C1—N2111.0 (2)C17—C16—H16A108.6
O2—C2—N2126.1 (2)N3—C16—H16A108.6
O2—C2—C3122.7 (2)C17—C16—H16B108.6
N2—C2—C3111.2 (2)N3—C16—H16B108.6
N1—C3—C4111.7 (2)H16A—C16—H16B107.6
N1—C3—C10110.4 (2)C16—C17—N4113.1 (3)
C4—C3—C10112.6 (2)C16—C17—H17A109.0
N1—C3—C299.0 (2)N4—C17—H17A109.0
C4—C3—C2108.7 (2)C16—C17—H17B109.0
C10—C3—C2113.6 (2)N4—C17—H17B109.0
C5—C4—C9117.9 (3)H17A—C17—H17B107.8
C5—C4—C3121.6 (3)
N3—Co1—N2—C236.0 (2)O2—C2—C3—C463.0 (3)
N3i—Co1—N2—C2−144.0 (2)N2—C2—C3—C4−115.9 (2)
N4i—Co1—N2—C2−62.3 (2)O2—C2—C3—C10−63.3 (3)
N4—Co1—N2—C2117.7 (2)N2—C2—C3—C10117.7 (2)
N2i—Co1—N2—C2−164 (100)N1—C3—C4—C5−22.4 (4)
N3—Co1—N2—C1−142.2 (2)C10—C3—C4—C5−147.3 (3)
N3i—Co1—N2—C137.8 (2)C2—C3—C4—C585.8 (3)
N4i—Co1—N2—C1119.5 (2)N1—C3—C4—C9160.3 (3)
N4—Co1—N2—C1−60.5 (2)C10—C3—C4—C935.4 (4)
N2i—Co1—N2—C118 (100)C2—C3—C4—C9−91.5 (3)
N3i—Co1—N3—C1663 (100)C9—C4—C5—C61.0 (5)
N4i—Co1—N3—C16−170.8 (3)C3—C4—C5—C6−176.4 (3)
N4—Co1—N3—C169.2 (3)C4—C5—C6—C7−0.5 (7)
N2i—Co1—N3—C16−83.3 (3)C5—C6—C7—C80.0 (7)
N2—Co1—N3—C1696.7 (3)C6—C7—C8—C9−0.2 (6)
N3—Co1—N4—C1713.2 (3)C5—C4—C9—C8−1.2 (5)
N3i—Co1—N4—C17−166.8 (3)C3—C4—C9—C8176.2 (3)
N4i—Co1—N4—C17−140 (100)C7—C8—C9—C40.8 (6)
N2i—Co1—N4—C17102.0 (3)N1—C3—C10—C11−65.3 (3)
N2—Co1—N4—C17−78.0 (3)C4—C3—C10—C1160.3 (3)
C3—N1—C1—O1−178.6 (3)C2—C3—C10—C11−175.5 (3)
C3—N1—C1—N2−0.7 (3)N1—C3—C10—C15111.6 (3)
C2—N2—C1—O1179.1 (3)C4—C3—C10—C15−122.8 (3)
Co1—N2—C1—O1−2.4 (4)C2—C3—C10—C151.5 (4)
C2—N2—C1—N11.1 (3)C15—C10—C11—C12−1.0 (5)
Co1—N2—C1—N1179.62 (18)C3—C10—C11—C12176.2 (3)
C1—N2—C2—O2180.0 (3)C10—C11—C12—C130.2 (6)
Co1—N2—C2—O21.5 (4)C11—C12—C13—C141.3 (6)
C1—N2—C2—C3−1.1 (3)C12—C13—C14—C15−1.9 (6)
Co1—N2—C2—C3−179.66 (16)C11—C10—C15—C140.3 (5)
C1—N1—C3—C4114.4 (3)C3—C10—C15—C14−176.6 (3)
C1—N1—C3—C10−119.5 (3)C13—C14—C15—C101.1 (5)
C1—N1—C3—C20.0 (3)Co1—N3—C16—C17−31.8 (5)
O2—C2—C3—N1179.7 (2)N3—C16—C17—N446.5 (6)
N2—C2—C3—N10.7 (3)Co1—N4—C17—C16−34.6 (5)
Symmetry codes: (i) −x+1, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2ii0.862.002.861 (3)173
N3—H3A···O1i0.902.182.947 (3)143
N3—H3B···O20.902.202.966 (3)143
Symmetry codes: (ii) x, −y+1/2, z+1/2; (i) −x+1, −y, −z.
Table 1
Selected geometric parameters (Å) top
Co1—N22.180 (2)Co1—N42.171 (2)
Co1—N32.123 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.862.002.861 (3)173
N3—H3A···O1ii0.902.182.947 (3)143
N3—H3B···O20.902.202.966 (3)143
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z.
Acknowledgements top

We are grateful for financial support from the Key Project for Fundamental Research of the Education Committee of Jiangsu Province (07KJA15011) and the Natural Science Foundation of Huaihai Institute of Technology, China (KX07042).

references
References top

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