A redetermination of bis­(5,5′-diethyl­barbiturato)bis­(imidazole)cobalt(II)

Fan, R.-Z.; Hong, P.-Z.; Song, W.-D.

doi:10.1107/S1600536807067815

metal-organic compounds

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Volume 64| Part 2| February 2008| Page m289

doi:10.1107/S1600536807067815

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A redetermination of bis(5,5′-diethylbarbiturato)bis(imidazole)cobalt(II)

Run-Zhen Fan,^a Peng-Zhi Hong ^b and Wen-Dong Song ^c ^*

^aCollege of Science, Guang Dong Ocean University, Zhanjiang 524088, People's Republic of China, ^bSchool of Food Science and Technology, Guang Dong Ocean University, Zhan Jiang 524088, People's Republic of China, and ^cCollege of Science, Guang Dong Ocean University, Zhan Jiang 524088, People's Republic of China
^*Correspondence e-mail: songwd60@126.com

(Received 16 November 2007; accepted 19 December 2007; online 4 January 2008)

The title complex, [Co(C₈H₁₂N₂O₃)₂(C₃H₄N₂)₂], whose structure was first determined by Wang & Craven [(1971). J. Chem. Soc. D, pp. 290–291], has been redetermined with improved precision. A crystallographic twofold rotation axis passes through the Co atom, which is tetrahedrally coordinated by two N atoms from two barbital ligands and two N atoms from two imidazole ligands. The molecules are self-assembled via intermolecular N—H⋯O hydrogen-bonding interactions into a supramolecular network.

Related literature

For related literature, see: Wang & Craven (1971 ).

Experimental

Crystal data

[Co(C₈H₁₂N₂O₃)₂(C₃H₄N₂)₂]
M_r = 561.47
Monoclinic, C 2/c
a = 13.3750 (3) Å
b = 10.1371 (2) Å
c = 20.5791 (4) Å
β = 100.409 (1)°
V = 2744.27 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 296 (2) K
0.32 × 0.26 × 0.25 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.813, T_max = 0.849
18228 measured reflections
3141 independent reflections
2596 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.079
S = 0.98
3141 reflections
170 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.86	2.15	2.7932 (19)	131
N4—H4⋯O3ⁱⁱ	0.86	2.12	2.9312 (18)	156
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067815/rz2187sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807067815/rz2187Isup2.hkl

checkCIF report

Comment top

In the present paper we report the redetermination of the crystal structure of the title complex using CCD data at room temperature. The structure agrees with the results reported previously by Wang & Craven (1971; CCDC refcode BARICO) with lattice parameters a = 13.362 (2) Å, b = 10.133 (2) Å, c = 20.544 (4) Å β = 100.33 (3) °), but with improved precision.

As illustrated in Figure 1, the cobalt(II) atom, possesses a crystallogarphically imposed C₂ symmetry, and displays a tetrahedral coordination geometry provided by two N atoms from two barbital ligands and two N atoms from two imidazole ligands. Intermolecular N—H···O hydrogen bonding interactions (Table 1) govern the crystal packing (Fig. 2).

Related literature top

For related literature, see: Wang & Craven (1971).

Experimental top

A mixture of cobalt nitrate (1 mmol), imidazole (1 mmol), barbital (1 mmol), NaOH (1.5 mmol) and H₂O (12 ml) was placed in a 23 ml Teflon reactor, which was heated to 433 K for three days and then cooled to room temperature at a rate of 10 K h^-1. The crystals obtained were washed with water and dryed in air.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL (Bruker, 2004).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom numbering scheme and 30% probability displacement ellipsoids. Unlabelled atoms are related to the labelled atoms by the symmetry operator (-x, y, 0.5 - z).
	Fig. 2. Packing diagram of the title compound viewed along the b axis. Intermolecluar hydrogen bonds are shown as dashed lines.

bis(5,5'-diethylbarbiturato)bis(imidazole)cobalt(II) top

Crystal data top

[Co(C₈H₁₂N₂O₃)₂(C₃H₄N₂)₂]	F(000) = 1172
M_r = 561.47	D_x = 1.359 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3600 reflections
a = 13.3750 (3) Å	θ = 1.4–28°
b = 10.1371 (2) Å	µ = 0.68 mm⁻¹
c = 20.5791 (4) Å	T = 296 K
β = 100.409 (1)°	Block, pink
V = 2744.27 (10) Å³	0.32 × 0.26 × 0.25 mm
Z = 4

Data collection top

Bruker APEXII area-detector diffractometer	3141 independent reflections
Radiation source: fine-focus sealed tube	2596 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→16
T_min = 0.813, T_max = 0.849	k = −12→13
18228 measured reflections	l = −26→26

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0343P)² + 2.0613P] where P = (F_o² + 2F_c²)/3
3141 reflections	(Δ/σ)_max < 0.001
170 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Co(C₈H₁₂N₂O₃)₂(C₃H₄N₂)₂]	V = 2744.27 (10) Å³
M_r = 561.47	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.3750 (3) Å	µ = 0.68 mm⁻¹
b = 10.1371 (2) Å	T = 296 K
c = 20.5791 (4) Å	0.32 × 0.26 × 0.25 mm
β = 100.409 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	3141 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2596 reflections with I > 2σ(I)
T_min = 0.813, T_max = 0.849	R_int = 0.029
18228 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 0.98	Δρ_max = 0.21 e Å⁻³
3141 reflections	Δρ_min = −0.29 e Å⁻³
170 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
C1	0.07766 (14)	−0.1841 (2)	0.16104 (9)	0.0574 (5)
H1	0.0212	−0.1684	0.1284	0.069*
C2	0.14986 (15)	−0.2732 (2)	0.15704 (9)	0.0579 (5)
H2	0.1533	−0.3303	0.1221	0.069*
C3	0.18454 (13)	−0.17053 (19)	0.25137 (8)	0.0524 (4)
H3	0.2178	−0.1457	0.2932	0.063*
C4	−0.01891 (13)	0.20721 (19)	0.34360 (8)	0.0502 (4)
C5	0.00221 (14)	0.3032 (2)	0.40182 (9)	0.0581 (5)
C6	0.10237 (14)	0.27581 (19)	0.44751 (8)	0.0535 (5)
C7	0.13212 (12)	0.08668 (17)	0.37956 (7)	0.0418 (4)
C8	0.0058 (2)	0.4435 (2)	0.37466 (12)	0.0845 (8)
H8A	−0.0583	0.4615	0.3456	0.101*
H8B	0.0121	0.5050	0.4113	0.101*
C9	0.0911 (3)	0.4694 (3)	0.33716 (17)	0.1117 (11)
H9A	0.1553	0.4584	0.3663	0.168*
H9B	0.0858	0.5580	0.3203	0.168*
H9C	0.0865	0.4084	0.3011	0.168*
C10	−0.08480 (17)	0.2920 (3)	0.44236 (11)	0.0849 (8)
H10A	−0.0711	0.3533	0.4791	0.102*
H10B	−0.1479	0.3190	0.4145	0.102*
C11	−0.0995 (2)	0.1564 (4)	0.46924 (16)	0.1166 (11)
H11A	−0.1180	0.0958	0.4333	0.175*
H11B	−0.1526	0.1594	0.4950	0.175*
H11C	−0.0374	0.1279	0.4966	0.175*
Co1	0.0000	0.00895 (3)	0.2500	0.03642 (10)
N1	0.09912 (10)	−0.11875 (14)	0.22073 (6)	0.0452 (3)
N2	0.21731 (12)	−0.26297 (17)	0.21478 (8)	0.0589 (4)
H2A	0.2719	−0.3087	0.2257	0.071*
N3	0.04631 (10)	0.11057 (14)	0.33481 (6)	0.0408 (3)
N4	0.15545 (11)	0.16886 (15)	0.43447 (6)	0.0497 (4)
H4	0.2089	0.1495	0.4628	0.060*
O1	0.19031 (11)	−0.00247 (13)	0.37358 (7)	0.0620 (4)
O2	−0.09826 (10)	0.21962 (16)	0.30314 (6)	0.0724 (4)
O3	0.13421 (11)	0.34732 (15)	0.49451 (7)	0.0751 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0473 (10)	0.0736 (13)	0.0437 (9)	0.0084 (10)	−0.0125 (8)	−0.0131 (9)
C2	0.0524 (11)	0.0659 (12)	0.0504 (10)	0.0040 (10)	−0.0038 (8)	−0.0171 (9)
C3	0.0449 (10)	0.0648 (12)	0.0412 (9)	0.0095 (9)	−0.0089 (7)	−0.0080 (8)
C4	0.0446 (10)	0.0619 (11)	0.0368 (8)	0.0068 (9)	−0.0122 (7)	−0.0087 (8)
C5	0.0504 (11)	0.0683 (12)	0.0452 (9)	0.0222 (9)	−0.0187 (8)	−0.0180 (9)
C6	0.0497 (10)	0.0634 (12)	0.0394 (8)	0.0134 (9)	−0.0132 (7)	−0.0120 (8)
C7	0.0401 (9)	0.0465 (9)	0.0343 (7)	−0.0006 (8)	−0.0052 (6)	−0.0031 (7)
C8	0.0978 (19)	0.0642 (14)	0.0731 (14)	0.0269 (14)	−0.0336 (14)	−0.0164 (12)
C9	0.141 (3)	0.0743 (18)	0.105 (2)	−0.0077 (18)	−0.018 (2)	0.0143 (16)
C10	0.0596 (14)	0.127 (2)	0.0608 (13)	0.0337 (15)	−0.0081 (11)	−0.0310 (14)
C11	0.096 (2)	0.168 (4)	0.090 (2)	0.012 (2)	0.0298 (17)	0.004 (2)
Co1	0.03201 (16)	0.04302 (19)	0.02885 (14)	0.000	−0.00886 (11)	0.000
N1	0.0395 (8)	0.0538 (9)	0.0371 (7)	0.0054 (6)	−0.0067 (6)	−0.0036 (6)
N2	0.0468 (9)	0.0704 (11)	0.0539 (9)	0.0185 (8)	−0.0056 (7)	−0.0098 (8)
N3	0.0375 (7)	0.0476 (8)	0.0319 (6)	0.0007 (6)	−0.0080 (5)	−0.0059 (5)
N4	0.0439 (8)	0.0590 (9)	0.0370 (7)	0.0130 (7)	−0.0174 (6)	−0.0115 (6)
O1	0.0582 (8)	0.0623 (9)	0.0564 (7)	0.0201 (7)	−0.0142 (6)	−0.0180 (6)
O2	0.0549 (8)	0.0944 (11)	0.0536 (8)	0.0226 (8)	−0.0281 (6)	−0.0210 (7)
O3	0.0684 (9)	0.0848 (10)	0.0570 (8)	0.0268 (8)	−0.0291 (7)	−0.0361 (7)

Geometric parameters (Å, º) top

C1—C2	1.336 (3)	C8—C9	1.512 (4)
C1—N1	1.379 (2)	C8—H8A	0.9700
C1—H1	0.9300	C8—H8B	0.9700
C2—N2	1.360 (2)	C9—H9A	0.9600
C2—H2	0.9300	C9—H9B	0.9600
C3—N1	1.311 (2)	C9—H9C	0.9600
C3—N2	1.325 (2)	C10—C11	1.507 (4)
C3—H3	0.9300	C10—H10A	0.9700
C4—O2	1.231 (2)	C10—H10B	0.9700
C4—N3	1.346 (2)	C11—H11A	0.9600
C4—C5	1.529 (2)	C11—H11B	0.9600
C5—C6	1.517 (2)	C11—H11C	0.9600
C5—C8	1.532 (3)	Co1—N1ⁱ	2.0210 (14)
C5—C10	1.554 (3)	Co1—N1	2.0210 (14)
C6—O3	1.222 (2)	Co1—N3	2.0249 (12)
C6—N4	1.349 (2)	Co1—N3ⁱ	2.0249 (12)
C7—O1	1.213 (2)	N2—H2A	0.8600
C7—N3	1.3571 (19)	N4—H4	0.8600
C7—N4	1.393 (2)

C2—C1—N1	110.08 (15)	C8—C9—H9C	109.5
C2—C1—H1	125.0	H9A—C9—H9C	109.5
N1—C1—H1	125.0	H9B—C9—H9C	109.5
C1—C2—N2	105.50 (16)	C11—C10—C5	115.1 (2)
C1—C2—H2	127.3	C11—C10—H10A	108.5
N2—C2—H2	127.3	C5—C10—H10A	108.5
N1—C3—N2	111.02 (15)	C11—C10—H10B	108.5
N1—C3—H3	124.5	C5—C10—H10B	108.5
N2—C3—H3	124.5	H10A—C10—H10B	107.5
O2—C4—N3	118.95 (15)	C10—C11—H11A	109.5
O2—C4—C5	118.64 (16)	C10—C11—H11B	109.5
N3—C4—C5	122.41 (14)	H11A—C11—H11B	109.5
C6—C5—C8	108.28 (18)	C10—C11—H11C	109.5
C6—C5—C4	112.75 (15)	H11A—C11—H11C	109.5
C8—C5—C4	108.56 (16)	H11B—C11—H11C	109.5
C6—C5—C10	108.49 (16)	N1ⁱ—Co1—N1	100.33 (9)
C8—C5—C10	109.85 (19)	N1ⁱ—Co1—N3	100.60 (5)
C4—C5—C10	108.90 (17)	N1—Co1—N3	117.89 (5)
O3—C6—N4	120.88 (15)	N1ⁱ—Co1—N3ⁱ	117.89 (5)
O3—C6—C5	121.64 (16)	N1—Co1—N3ⁱ	100.60 (5)
N4—C6—C5	117.47 (14)	N3—Co1—N3ⁱ	118.85 (8)
O1—C7—N3	122.91 (14)	C3—N1—C1	105.02 (15)
O1—C7—N4	118.29 (14)	C3—N1—Co1	132.44 (12)
N3—C7—N4	118.80 (15)	C1—N1—Co1	122.06 (11)
C9—C8—C5	115.1 (2)	C3—N2—C2	108.38 (15)
C9—C8—H8A	108.5	C3—N2—H2A	125.8
C5—C8—H8A	108.5	C2—N2—H2A	125.8
C9—C8—H8B	108.5	C4—N3—C7	121.87 (13)
C5—C8—H8B	108.5	C4—N3—Co1	112.43 (10)
H8A—C8—H8B	107.5	C7—N3—Co1	125.70 (11)
C8—C9—H9A	109.5	C6—N4—C7	126.37 (14)
C8—C9—H9B	109.5	C6—N4—H4	116.8
H9A—C9—H9B	109.5	C7—N4—H4	116.8

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱⁱ	0.86	2.15	2.7932 (19)	131
N4—H4···O3ⁱⁱⁱ	0.86	2.12	2.9312 (18)	156

Symmetry codes: (ii) x+1/2, y−1/2, z; (iii) −x+1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Co(C₈H₁₂N₂O₃)₂(C₃H₄N₂)₂]
M_r	561.47
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	13.3750 (3), 10.1371 (2), 20.5791 (4)
β (°)	100.409 (1)
V (Å³)	2744.27 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.68
Crystal size (mm)	0.32 × 0.26 × 0.25

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.813, 0.849
No. of measured, independent and observed [I > 2σ(I)] reflections	18228, 3141, 2596
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.079, 0.98
No. of reflections	3141
No. of parameters	170
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.29

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Bruker, 2004), SHELXTL (Bruker, 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.86	2.15	2.7932 (19)	130.9
N4—H4···O3ⁱⁱ	0.86	2.12	2.9312 (18)	156.3

Symmetry codes: (i) x+1/2, y−1/2, z; (ii) −x+1/2, −y+1/2, −z+1.

Acknowledgements

The authors acknowledge Guang Dong Ocean University for supporting this work.

References

Bruker (2004). APEX2 (Version 1.08), SAINT (Version 7.23A) and SHELXTL (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar
Wang, B. C. & Craven, B. M. (1971). J. Chem. Soc. D, pp. 290–291. Google Scholar