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The crystal structure of the title compound, [Co(C3H2O4)(C7H6N2)(H2O)]n, consists of two-dimensional polymeric CoII complex layers. The octahedral coordination around a CoII atom is composed of a chelate malonate, two monodentate malonate anions from the adjacent asymmetric unit, a bez­imidazole ligand and a coordinated water molecule. Each malonate dianion links three CoII atoms related by an n-glide plane to form polymeric layers in the (010) plane. π–π stacking of the benz­imidazole ligands occurs between adjacent polymeric layers, the separation between parallel benz­imidazole rings being 3.42 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017574/lh6092sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017574/lh6092Isup2.hkl
Contains datablock I

CCDC reference: 222808

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.039
  • wR factor = 0.101
  • Data-to-parameter ratio = 12.2

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ..... 0.99
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The aromatic ππ-stacking interaction has been observed in some metal complexes with aromatic heteropolycyclic ligands, such as phenathroline, bithiazole and benzimidazole (Chen et al., 2003). A new polymeric complex, (I), with benzimidazole ligand has recently been prepared in the laboratory and its X-ray structure is presented here to show the ππ stacking occurring between the polymeric complex layers.

The crystal of (I) consists of polymeric sheets of (I). The coordination geometry around a CoII atom is illustrated in Fig. 1. The octahedral coordination geometry is formed by a chelate malonate, two monodentate malonates from adjacent asymmetric units, a benzimidazole and a coordinated water. The malonate chelates to the CoII atom with the terminal carboxyl groups in a boat coordination configuration. The Co—O(water) distance of 2.169 (2) Å is significantly longer than the average Co—O(carboxyl) distance of 2.092 (2) Å, ranging from 2.074 (2) to 2.121 (2) Å. The coordinated water molecule forms hydrogen bonds to the neighboring carboxyl groups, as shown in Fig. 1 and Table 2.

The malonate dianion plays as a bridging role in the structure. Each malonate dianion links three CoII atoms, related by an n-glide plane, to form the infinite two-dimensional polymer layers along the (010) plane (Fig. 2). The molecular packing is illustrated in Fig. 3. The parallel disposition of benzimidazole rings from the neighboring polymer layers is shown in Fig. 3. The shorter separation of 3.42 (2) Å between the neighboring benzimidazole rings suggests the existence of a ππ stacking between the adjacent polymer layers.

Experimental top

An ethanol solution (5 ml) of benzimidazole (0.236 g, 2 mmol) was mixed with an aqueous solution (10 ml) of CoCl2·6H2O (0.237 g, 1 mmol) at room temperature. An aqueous solution (8 ml) containing malonic acid (0.104 g, 1 mmol) and Na2CO3 (0.106 g, 1 mmol) was added to the above solution with stirring at room temperature. Then the mixture was refluxed for 2 h and filtered. The pink single crystals were obtained after 5 d.

Refinement top

The H atoms of water were located in a difference Fourier map and were included in structure-factor calculations with fixed positional and displacement parameters of 0.05 Å2. Other H atoms were placed in calculated positions with C—H = 0.93 Å (benzimidazole) or 0.97 Å (malonate) and N—H = 0.86 Å, and included in the final cycles of refinement in riding model, with Uiso(H) = 1.2Ueq of the carrier atom.

Computing details top

Data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The coordination environment around the CoII atom in (I) with 30% probability displacement ellipsoids. Dashed lines indicate the hydrogen bonding [symmetry codes: (i) x − 1/2, 1/2 − y, 1/2 + z; (ii) x − 1/2, 1/2 − y, z − 1/2].
[Figure 2] Fig. 2. The polymeric layer structure formed by malonate linkage.
[Figure 3] Fig. 3. The molecular packing showing the π-π stacking between benzimidazole rings.
(I) top
Crystal data top
[Co(C3H2O4)(C7H6N2)(H2O)]F(000) = 604
Mr = 297.13Dx = 1.772 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6128 reflections
a = 6.7654 (10) Åθ = 2.9–25.0°
b = 21.9841 (18) ŵ = 1.56 mm1
c = 7.4945 (14) ÅT = 295 K
β = 91.944 (2)°Plate, pink
V = 1114.0 (3) Å30.25 × 0.18 × 0.10 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1995 independent reflections
Radiation source: fine-focus sealed tube1828 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
Detector resolution: 10.00 pixels mm-1θmax = 25.3°, θmin = 1.9°
ω scansh = 78
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 2626
Tmin = 0.672, Tmax = 0.851l = 98
7470 measured reflections
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0401P)2 + 2.9317P]
where P = (Fo2 + 2Fc2)/3
1995 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = 0.79 e Å3
Crystal data top
[Co(C3H2O4)(C7H6N2)(H2O)]V = 1114.0 (3) Å3
Mr = 297.13Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.7654 (10) ŵ = 1.56 mm1
b = 21.9841 (18) ÅT = 295 K
c = 7.4945 (14) Å0.25 × 0.18 × 0.10 mm
β = 91.944 (2)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1995 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
1828 reflections with I > 2σ(I)
Tmin = 0.672, Tmax = 0.851Rint = 0.019
7470 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.101H-atom parameters constrained
S = 1.12Δρmax = 0.44 e Å3
1995 reflectionsΔρmin = 0.79 e Å3
163 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*/Ueq
Co0.26052 (7)0.289972 (19)0.63585 (6)0.02086 (16)
O10.4298 (4)0.24088 (11)0.8214 (3)0.0300 (6)
O20.6051 (4)0.16303 (11)0.9275 (3)0.0269 (5)
O30.4191 (4)0.24378 (11)0.4439 (3)0.0275 (5)
O40.6116 (4)0.17026 (11)0.3451 (3)0.0311 (6)
O50.0569 (4)0.21376 (11)0.6355 (3)0.0298 (6)
N10.4732 (4)0.36040 (13)0.6495 (4)0.0274 (6)
N20.7638 (5)0.40225 (16)0.6099 (5)0.0404 (8)
H20.88600.40510.58290.048*
C10.6553 (6)0.35196 (18)0.5971 (5)0.0343 (9)
H10.70250.31500.55600.041*
C20.6855 (7)0.5098 (2)0.7054 (6)0.0484 (11)
H2A0.80750.52760.68570.058*
C30.5322 (8)0.5430 (2)0.7686 (7)0.0539 (12)
H30.55000.58430.79140.065*
C40.3503 (8)0.5164 (2)0.7995 (7)0.0534 (12)
H40.25010.54030.84450.064*
C50.3136 (6)0.45587 (18)0.7655 (6)0.0387 (9)
H50.19090.43860.78610.046*
C60.4671 (6)0.42154 (16)0.6991 (5)0.0296 (8)
C70.6530 (6)0.44825 (18)0.6716 (5)0.0363 (9)
C80.5074 (5)0.18934 (15)0.8041 (4)0.0221 (7)
C90.4775 (6)0.15551 (15)0.6285 (4)0.0266 (7)
H9A0.34480.13870.62350.032*
H9B0.56930.12160.62760.032*
C100.5052 (5)0.19316 (15)0.4609 (4)0.0223 (7)
H510.03110.21970.54550.050*
H520.02520.21310.74030.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0245 (3)0.0208 (3)0.0173 (2)0.00066 (18)0.00094 (17)0.00023 (17)
O10.0428 (15)0.0258 (13)0.0209 (12)0.0077 (11)0.0051 (11)0.0029 (10)
O20.0310 (13)0.0251 (12)0.0241 (12)0.0036 (10)0.0059 (10)0.0018 (10)
O30.0373 (14)0.0247 (12)0.0210 (12)0.0079 (11)0.0076 (10)0.0022 (10)
O40.0449 (16)0.0232 (12)0.0258 (13)0.0024 (11)0.0101 (11)0.0004 (10)
O50.0313 (14)0.0334 (14)0.0245 (13)0.0037 (11)0.0014 (10)0.0008 (10)
N10.0289 (16)0.0228 (14)0.0304 (16)0.0013 (12)0.0006 (12)0.0008 (12)
N20.0273 (17)0.0406 (19)0.053 (2)0.0059 (15)0.0007 (15)0.0050 (16)
C10.033 (2)0.0293 (19)0.041 (2)0.0011 (16)0.0017 (17)0.0050 (16)
C20.057 (3)0.038 (2)0.050 (3)0.020 (2)0.002 (2)0.000 (2)
C30.078 (4)0.025 (2)0.059 (3)0.007 (2)0.000 (3)0.005 (2)
C40.076 (4)0.031 (2)0.054 (3)0.014 (2)0.007 (2)0.004 (2)
C50.040 (2)0.032 (2)0.045 (2)0.0041 (17)0.0088 (18)0.0009 (17)
C60.039 (2)0.0232 (17)0.0261 (18)0.0006 (15)0.0015 (15)0.0001 (14)
C70.044 (2)0.030 (2)0.034 (2)0.0092 (17)0.0057 (17)0.0001 (16)
C80.0202 (16)0.0250 (17)0.0212 (16)0.0025 (13)0.0030 (13)0.0019 (13)
C90.037 (2)0.0208 (16)0.0225 (17)0.0005 (14)0.0016 (14)0.0009 (13)
C100.0250 (17)0.0217 (16)0.0199 (16)0.0037 (13)0.0008 (13)0.0025 (13)
Geometric parameters (Å, º) top
Co—O12.074 (2)N2—H20.86
Co—O4i2.085 (2)C1—H10.93
Co—O32.087 (2)C2—C31.366 (7)
Co—N12.114 (3)C2—C71.392 (6)
Co—O2ii2.121 (2)C2—H2A0.93
Co—O52.169 (2)C3—C41.389 (7)
O1—C81.257 (4)C3—H30.93
O2—C81.259 (4)C4—C51.375 (6)
O3—C101.260 (4)C4—H40.93
O4—C101.252 (4)C5—C61.390 (6)
O5—H510.894C5—H50.93
O5—H520.977C6—C71.409 (6)
N1—C11.319 (5)C8—C91.520 (5)
N1—C61.396 (5)C9—C101.521 (5)
N2—C11.329 (5)C9—H9A0.97
N2—C71.350 (5)C9—H9B0.97
O1—Co—O4i89.07 (10)C3—C2—C7117.7 (4)
O1—Co—O385.63 (10)C3—C2—H2A121.1
O4i—Co—O3174.47 (10)C7—C2—H2A121.1
O1—Co—N189.38 (11)C2—C3—C4121.3 (4)
O4i—Co—N190.12 (11)C2—C3—H3119.3
O3—Co—N191.41 (11)C4—C3—H3119.3
O1—Co—O2ii174.61 (10)C5—C4—C3122.1 (4)
O4i—Co—O2ii96.27 (10)C5—C4—H4118.9
O3—Co—O2ii89.04 (10)C3—C4—H4118.9
N1—Co—O2ii89.91 (10)C4—C5—C6117.3 (4)
O1—Co—O586.27 (10)C4—C5—H5121.3
O4i—Co—O590.10 (10)C6—C5—H5121.3
O3—Co—O587.98 (10)C5—C6—N1130.4 (4)
N1—Co—O5175.65 (11)C5—C6—C7120.5 (4)
O2ii—Co—O594.39 (9)N1—C6—C7109.1 (3)
C8—O1—Co128.5 (2)N2—C7—C2134.7 (4)
C8—O2—Coiii123.5 (2)N2—C7—C6104.3 (3)
C10—O3—Co127.4 (2)C2—C7—C6121.0 (4)
C10—O4—Coiv131.0 (2)O1—C8—O2123.3 (3)
Co—O5—H51107.13O1—C8—C9119.1 (3)
Co—O5—H52112.87O2—C8—C9117.6 (3)
H51—O5—H52103.1C8—C9—C10115.6 (3)
C1—N1—C6104.6 (3)C8—C9—H9A108.4
C1—N1—Co121.6 (2)C10—C9—H9A108.4
C6—N1—Co133.8 (3)C8—C9—H9B108.4
C1—N2—C7109.7 (3)C10—C9—H9B108.4
C1—N2—H2125.2H9A—C9—H9B107.4
C7—N2—H2125.2O4—C10—O3124.0 (3)
N1—C1—N2112.4 (3)O4—C10—C9116.3 (3)
N1—C1—H1123.8O3—C10—C9119.6 (3)
N2—C1—H1123.8
Symmetry codes: (i) x1/2, y+1/2, z+1/2; (ii) x1/2, y+1/2, z1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x+1/2, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H52···O3i0.981.852.689 (3)143
O5—H51···O1ii0.891.902.672 (3)143
N2—H2···O2iv0.862.433.078 (4)132
Symmetry codes: (i) x1/2, y+1/2, z+1/2; (ii) x1/2, y+1/2, z1/2; (iv) x+1/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formula[Co(C3H2O4)(C7H6N2)(H2O)]
Mr297.13
Crystal system, space groupMonoclinic, P21/n
Temperature (K)295
a, b, c (Å)6.7654 (10), 21.9841 (18), 7.4945 (14)
β (°) 91.944 (2)
V3)1114.0 (3)
Z4
Radiation typeMo Kα
µ (mm1)1.56
Crystal size (mm)0.25 × 0.18 × 0.10
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.672, 0.851
No. of measured, independent and
observed [I > 2σ(I)] reflections
7470, 1995, 1828
Rint0.019
(sin θ/λ)max1)0.601
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.101, 1.12
No. of reflections1995
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.44, 0.79

Computer programs: PROCESS-AUTO (Rigaku Corporation, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC and Rigaku, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top
Co—O12.074 (2)Co—N12.114 (3)
Co—O4i2.085 (2)Co—O2ii2.121 (2)
Co—O32.087 (2)Co—O52.169 (2)
Symmetry codes: (i) x1/2, y+1/2, z+1/2; (ii) x1/2, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H52···O3i0.981.852.689 (3)143
O5—H51···O1ii0.891.902.672 (3)143
N2—H2···O2iii0.862.433.078 (4)132
Symmetry codes: (i) x1/2, y+1/2, z+1/2; (ii) x1/2, y+1/2, z1/2; (iii) x+1/2, y+1/2, z1/2.
 

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