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Acta Cryst. (2009). E65, m1356    [ doi:10.1107/S1600536809039592 ]

Bis[2-(benzimidazol-2-ylsulfanyl)acetato]bis(2,2'-bipyridine)cadmium(II)

L. Cheng, Y.-Y. Sun, J.-Q. Wang and Y.-W. Zhang

Abstract top

In the structure of the title compound, [Cd(C9H7N2O2S)2(C10H8N2)2], the complex molecules are located on a crystallographic twofold rotation axis and the CdII ion is octahedrally coordinated by two chelating 2,2'-bipyridine ligands and two O atoms from the carboxylate groups of two 2-(benzimidazol-2-ylsulfanyl)acetate ligands. The two carboxylate ligands adopt a cis configuration with respect to each other. Within each of these ligands, the imidazole fragments are bent back in a loop towards the acetyl groups, forming intramolecular N-H...O hydrogen bonds, which help to stablilize the mononuclear complex. Adjacent molecules are further linked by weak C-H...O hydrogen bonds, resulting in a chain along the c axis.

Comment top

Recently, the photophysical properties of coordination compounds of d10 monovalent ions of the coinage metals have attracted considerable attention. Meanwhile, benzimidazole compounds and thioether carboxylates have been widely used to construct many interesting coordination compounds. However, such compounds formed by bifunctional ligands with both benzimidazole and thioether carboxylate groups have only been rarely reported (Cheng et al. 2009, Matthews et al. 1998). Herein, we present the synthesis and structural characterization of a new coordination compound of a d10 mononuclear complex Cd(Hbia)2(2,2'-bipy)2 (H2bia = 2-(1H-benzo[d]imidazol-2-ylthio)acetic acid; 2,2'-bipy = 2,2'-bipyridine) with the bifunctional ligand H2bia.

In the structure of the title compound the complex is located on a crystallographic two fold rotation axis with one CdII cation, one Hbia and one chelating 2,2'-bipy ligand in the asymmetric unit. The CdII ion displays a distorted octahedral geometry, being surrounded by two chelating 2,2'-bipy ligands with Cd—N coordinating distances of 2.342 (2) and 2.378 (2) Å and two oxygen atoms coming from the carboxylates of two Hbia ligands, respectively, with the distance involving O atoms and Cd being 2.275 (2) Å. The angles around Cd are in the range of 69.50 (8)–158.51 (8) °. Meanwhile, the two carboxylate ligands are related by a two fold rotation axis and adopt a cis- configuration with respect to each other. Within each of these ligands the imidazole fragments are bent back in a loop towards the acetyl groups to form intramolecular N—H···O hydrogen bonds which help to stablilize the mononuclear complex (table 1). The N···O distance between N2 of the imidazole and the coordinated O atom O2 is 2.708 (3) Å. Adjacent molecules are further linked together by C—H···O hydrogen bonding between the uncoordinated oxygen atoms and the carbon atoms of 2,2'-bipyridine (C11···O1ii 3.180 (4) Å. symmetry code: ii, -x, 1-y, 1-z), resulting in a one-dimensional hydrogen bonded chain.

Related literature top

For related structures, see: Matthews et al. (1998); Cheng et al. (2009).

Experimental top

A mixture of H2bia (0.0208 g, 0.1 mmol), 2,2'-bipy (0.0156 g, 0.1 mmol), Cd(NO3)2.6H2O (0.0345 g, 0.1 mmol) and H2O (8 ml) was heated in a 15-ml Teflon-lined autoclave at 363 K for 5 days, followed by slow cooling (5 K h-1) to room temperature. The resulting mixture was washed with water, and colorless block crystals were collected and dried in air [yield 91% (76.3 mg) based on Cd(II)].

Refinement top

The H atom bonded to the N atom was located in a difference map and was freely refined without use of restraints. All other H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. Structure of the title compound with 30% thermal ellipsoids. Symmetry code: i: -x, y, 1/2-z. Hydrogen atoms are omitted for clarity.
[Figure 2] Fig. 2. The one-dimensional hydrogen bonding chain of the title compound.
Bis[2-(benzimidazol-2-ylsulfanyl)acetato]bis(2,2'-bipyridine)cadmium(II) top
Crystal data top
[Cd(C9H7N2O2S)2(C10H8N2)2]F(000) = 1704
Mr = 839.25Dx = 1.580 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 783 reflections
a = 26.733 (2) Åθ = 2.4–28.0°
b = 9.3043 (8) ŵ = 0.79 mm−1
c = 16.4220 (14) ÅT = 295 K
β = 120.254 (1)°Block, colorless
V = 3528.3 (5) Å30.20 × 0.18 × 0.12 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		3460 independent reflections
Radiation source: fine-focus sealed tube2946 reflections with I > 2σ(I)
graphiteRint = 0.028
φ and ω scansθmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		h = −32→30
Tmin = 0.858, Tmax = 0.911k = −11→11
9308 measured reflectionsl = −20→19
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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0305P)2 + 1.2632P]
where P = (Fo2 + 2Fc2)/3
3460 reflections(Δ/σ)max < 0.001
244 parametersΔρmax = 0.33 e Å−3
0 restraintsΔρmin = −0.47 e Å−3
Crystal data top
[Cd(C9H7N2O2S)2(C10H8N2)2]V = 3528.3 (5) Å3
Mr = 839.25Z = 4
Monoclinic, C2/cMo Kα radiation
a = 26.733 (2) ŵ = 0.79 mm−1
b = 9.3043 (8) ÅT = 295 K
c = 16.4220 (14) Å0.20 × 0.18 × 0.12 mm
β = 120.254 (1)°
Data collection top
Bruker SMART CCD
diffractometer		3460 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		2946 reflections with I > 2σ(I)
Tmin = 0.858, Tmax = 0.911Rint = 0.028
9308 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.069Δρmax = 0.33 e Å−3
S = 1.05Δρmin = −0.47 e Å−3
3460 reflectionsAbsolute structure: ?
244 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/Ueq
Cd10.00000.27478 (3)0.25000.03543 (10)
S10.15271 (3)0.05110 (8)0.52528 (4)0.04872 (19)
C10.03416 (10)0.1120 (3)0.43699 (17)0.0373 (6)
C20.08216 (10)0.0184 (3)0.51125 (16)0.0415 (6)
H2A0.0721−0.08170.49450.050*
H2B0.08430.03460.57130.050*
C30.15201 (10)−0.0542 (3)0.43638 (16)0.0388 (6)
C40.17937 (11)−0.1829 (3)0.35876 (17)0.0413 (6)
C50.20952 (13)−0.2670 (3)0.3279 (2)0.0540 (7)
H5A0.2493−0.28090.36530.065*
C60.17850 (13)−0.3294 (3)0.2399 (2)0.0567 (7)
H6A0.1979−0.38600.21790.068*
C70.11932 (13)−0.3099 (3)0.1835 (2)0.0561 (8)
H7A0.1000−0.35230.12420.067*
C80.08838 (13)−0.2290 (3)0.2134 (2)0.0524 (7)
H8A0.0486−0.21630.17590.063*
C90.11938 (10)−0.1676 (3)0.30194 (16)0.0385 (6)
C100.03449 (11)0.5176 (3)0.4126 (2)0.0494 (7)
H10A−0.00490.51040.39150.059*
C110.06748 (12)0.6067 (3)0.4870 (2)0.0539 (7)
H11A0.05110.65760.51660.065*
C120.12519 (12)0.6190 (3)0.5169 (2)0.0526 (7)
H12A0.14850.67990.56670.063*
C130.14864 (11)0.5405 (3)0.47287 (18)0.0456 (6)
H13A0.18780.54790.49240.055*
C140.11277 (9)0.4506 (2)0.39904 (16)0.0336 (5)
C150.13512 (9)0.3589 (3)0.35035 (16)0.0339 (5)
C160.19346 (11)0.3488 (3)0.3800 (2)0.0542 (7)
H16A0.22030.40340.43070.065*
C170.21161 (12)0.2577 (3)0.3340 (2)0.0634 (9)
H17A0.25080.24960.35370.076*
C180.17124 (11)0.1788 (3)0.2589 (2)0.0525 (7)
H18A0.18240.11660.22660.063*
C190.11432 (11)0.1940 (3)0.23272 (18)0.0454 (7)
H19A0.08690.14100.18170.055*
N10.19912 (8)−0.1097 (2)0.44392 (15)0.0478 (5)
N20.10299 (9)−0.0851 (2)0.35415 (14)0.0410 (5)
N30.05612 (8)0.4404 (2)0.36884 (14)0.0390 (5)
N40.09607 (8)0.2814 (2)0.27686 (14)0.0360 (5)
O10.01181 (8)0.2029 (2)0.46217 (13)0.0559 (5)
O20.02068 (7)0.08785 (18)0.35135 (11)0.0422 (4)
H2C0.0731 (11)−0.046 (3)0.3391 (17)0.040 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02273 (14)0.04258 (17)0.03763 (15)0.0000.01272 (11)0.000
S10.0323 (3)0.0634 (5)0.0415 (4)0.0011 (3)0.0120 (3)−0.0134 (3)
C10.0281 (12)0.0453 (15)0.0395 (14)0.0012 (11)0.0178 (11)0.0034 (12)
C20.0437 (14)0.0473 (16)0.0351 (13)0.0069 (12)0.0211 (12)0.0061 (11)
C30.0293 (13)0.0463 (15)0.0354 (13)0.0004 (11)0.0123 (11)−0.0007 (11)
C40.0352 (13)0.0485 (16)0.0412 (14)0.0000 (11)0.0199 (12)0.0005 (12)
C50.0413 (16)0.067 (2)0.0592 (18)0.0054 (13)0.0293 (15)−0.0053 (15)
C60.0614 (19)0.0594 (19)0.0638 (19)0.0036 (15)0.0424 (17)−0.0084 (16)
C70.064 (2)0.0568 (19)0.0482 (17)−0.0032 (15)0.0289 (15)−0.0110 (14)
C80.0430 (16)0.0599 (18)0.0452 (16)0.0030 (13)0.0154 (13)−0.0044 (14)
C90.0357 (13)0.0404 (14)0.0376 (13)0.0031 (11)0.0170 (11)0.0038 (11)
C100.0418 (15)0.0446 (16)0.0701 (18)0.0026 (12)0.0344 (14)−0.0066 (14)
C110.0633 (19)0.0424 (16)0.0722 (19)0.0020 (14)0.0462 (17)−0.0104 (15)
C120.0540 (17)0.0482 (17)0.0573 (17)−0.0067 (13)0.0293 (15)−0.0161 (14)
C130.0363 (14)0.0483 (16)0.0512 (15)−0.0059 (12)0.0213 (12)−0.0138 (13)
C140.0288 (12)0.0340 (13)0.0379 (13)0.0002 (10)0.0167 (11)0.0002 (10)
C150.0275 (12)0.0379 (14)0.0362 (13)−0.0033 (10)0.0160 (10)−0.0032 (11)
C160.0296 (13)0.070 (2)0.0594 (17)−0.0091 (13)0.0196 (13)−0.0281 (15)
C170.0293 (14)0.088 (2)0.073 (2)−0.0054 (14)0.0259 (15)−0.0318 (18)
C180.0393 (15)0.0666 (19)0.0589 (17)−0.0006 (13)0.0302 (14)−0.0177 (15)
C190.0373 (14)0.0567 (18)0.0443 (15)−0.0087 (12)0.0220 (12)−0.0163 (13)
N10.0295 (11)0.0618 (15)0.0459 (13)0.0042 (10)0.0144 (10)−0.0054 (11)
N20.0281 (11)0.0496 (14)0.0393 (12)0.0059 (10)0.0126 (10)−0.0043 (10)
N30.0297 (11)0.0404 (12)0.0491 (12)0.0008 (9)0.0215 (10)−0.0055 (10)
N40.0267 (10)0.0443 (12)0.0366 (11)−0.0027 (9)0.0156 (9)−0.0065 (9)
O10.0470 (11)0.0704 (14)0.0491 (11)0.0212 (10)0.0234 (9)−0.0027 (10)
O20.0393 (9)0.0521 (11)0.0332 (9)0.0121 (8)0.0168 (8)0.0054 (8)
Geometric parameters (Å, °) top
Cd1—O2i2.2746 (16)C8—H8A0.9300
Cd1—O22.2746 (16)C9—N21.376 (3)
Cd1—N32.342 (2)C10—N31.336 (3)
Cd1—N3i2.3417 (19)C10—C111.369 (4)
Cd1—N4i2.3775 (19)C10—H10A0.9300
Cd1—N42.3775 (19)C11—C121.368 (4)
S1—C31.750 (2)C11—H11A0.9300
S1—C21.807 (2)C12—C131.381 (3)
C1—O11.221 (3)C12—H12A0.9300
C1—O21.284 (3)C13—C141.385 (3)
C1—C21.521 (3)C13—H13A0.9300
C2—H2A0.9700C14—N31.338 (3)
C2—H2B0.9700C14—C151.485 (3)
C3—N11.308 (3)C15—N41.340 (3)
C3—N21.357 (3)C15—C161.383 (3)
C4—C51.389 (4)C16—C171.375 (4)
C4—N11.398 (3)C16—H16A0.9300
C4—C91.398 (3)C17—C181.373 (4)
C5—C61.381 (4)C17—H17A0.9300
C5—H5A0.9300C18—C191.364 (3)
C6—C71.385 (4)C18—H18A0.9300
C6—H6A0.9300C19—N41.335 (3)
C7—C81.378 (4)C19—H19A0.9300
C7—H7A0.9300N2—H2C0.80 (2)
C8—C91.383 (4)
O2i—Cd1—O280.25 (8)N2—C9—C4105.0 (2)
O2i—Cd1—N3158.50 (6)C8—C9—C4122.5 (2)
O2—Cd1—N394.35 (7)N3—C10—C11123.2 (2)
O2i—Cd1—N3i94.35 (7)N3—C10—H10A118.4
O2—Cd1—N3i158.50 (6)C11—C10—H10A118.4
N3—Cd1—N3i97.71 (10)C12—C11—C10118.3 (2)
O2i—Cd1—N4i92.44 (6)C12—C11—H11A120.9
O2—Cd1—N4i89.84 (6)C10—C11—H11A120.9
N3—Cd1—N4i108.43 (7)C11—C12—C13119.7 (3)
N3i—Cd1—N4i69.49 (6)C11—C12—H12A120.1
O2i—Cd1—N489.84 (6)C13—C12—H12A120.1
O2—Cd1—N492.44 (6)C12—C13—C14118.8 (2)
N3—Cd1—N469.49 (6)C12—C13—H13A120.6
N3i—Cd1—N4108.43 (7)C14—C13—H13A120.6
N4i—Cd1—N4177.01 (10)N3—C14—C13121.5 (2)
C3—S1—C2103.15 (12)N3—C14—C15116.5 (2)
O1—C1—O2125.2 (2)C13—C14—C15122.0 (2)
O1—C1—C2118.9 (2)N4—C15—C16120.6 (2)
O2—C1—C2115.8 (2)N4—C15—C14116.84 (19)
C1—C2—S1114.25 (17)C16—C15—C14122.5 (2)
C1—C2—H2A108.7C17—C16—C15119.7 (2)
S1—C2—H2A108.7C17—C16—H16A120.1
C1—C2—H2B108.7C15—C16—H16A120.1
S1—C2—H2B108.7C18—C17—C16119.2 (3)
H2A—C2—H2B107.6C18—C17—H17A120.4
N1—C3—N2114.3 (2)C16—C17—H17A120.4
N1—C3—S1122.47 (18)C19—C18—C17118.3 (2)
N2—C3—S1123.23 (18)C19—C18—H18A120.8
C5—C4—N1130.0 (2)C17—C18—H18A120.8
C5—C4—C9119.7 (2)N4—C19—C18123.2 (2)
N1—C4—C9110.2 (2)N4—C19—H19A118.4
C6—C5—C4117.8 (3)C18—C19—H19A118.4
C6—C5—H5A121.1C3—N1—C4103.73 (19)
C4—C5—H5A121.1C3—N2—C9106.7 (2)
C5—C6—C7121.7 (3)C3—N2—H2C121.9 (18)
C5—C6—H6A119.1C9—N2—H2C130.3 (18)
C7—C6—H6A119.1C10—N3—C14118.6 (2)
C8—C7—C6121.5 (3)C10—N3—Cd1122.20 (16)
C8—C7—H7A119.3C14—N3—Cd1119.05 (15)
C6—C7—H7A119.3C19—N4—C15119.0 (2)
C7—C8—C9116.8 (3)C19—N4—Cd1122.67 (16)
C7—C8—H8A121.6C15—N4—Cd1117.36 (14)
C9—C8—H8A121.6C1—O2—Cd1119.90 (16)
N2—C9—C8132.4 (2)
Symmetry codes: (i) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2C···O20.80 (2)1.96 (2)2.708 (3)156 (2)
C11—H11A···O1ii0.932.293.179 (3)161
Symmetry codes: (ii) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2C···O20.80 (2)1.96 (2)2.708 (3)156 (2)
C11—H11A···O1i0.932.293.179 (3)161
Symmetry codes: (i) −x, −y+1, −z+1.
Acknowledgements top

The authors thank the Program for Young Excellent Talents at Southeast University for financial support.

references
References top

Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Cheng, L., Sun, Y.-Y., Zhang, Y.-W. & Wang, J.-Q. (2009). Acta Cryst. E65, m34.

Matthews, C. J., Heath, S. L., Elsegood, M. R. J., Clegg, W., Leese, T. A. & Lockhart, J. C. (1998). J. Chem. Soc. Dalton Trans. pp. 1973–1977.

Sheldrick, G. M. (2000). SADABS. University of Göttingen, Germany

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.