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The crystal structure of the title compound, [Ni(C4H4O4)(C7H6N2)2(H2O)2]n, consists of a polymeric NiII complex bridged by succinate dianions. The Ni atom is located at a crystallographic inversion center. Both carboxyl groups of the succinate coordinate, in monodentate fashion, to the neighboring NiII atoms to form one-dimensional chains, and the chains link to each other via hydrogen bonds between the benz­imidazole and carboxyl group to form a two-dimensional supramolecular structure. The overlapped arrangement of parallel benz­imidazole ligands, with a separation of 3.350 (3) Å, suggests the existence of π–π-stacking interactions between adjacent chains.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803009887/ww6083sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803009887/ww6083Isup2.hkl
Contains datablock I

CCDC reference: 214778

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.028
  • wR factor = 0.074
  • Data-to-parameter ratio = 15.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

A series of transition metal complexes bridged by dicarboxylate, such as fumarate, succinate, etc., has been prepared in the laboratory. Their crystal structures show versatile coordination modes of the carboxyl groups (Chen et al., 2003). As part of this research, the structure of the title nickel(II) complex, (I), bridged by succinate has been determined by X-ray diffraction methods.

The crystal structure consists of polymeric NiII complex molecules. The coordination environment around the NiII atom is illustrated in Fig. 1. The NiII atom is located in a crystallographic inversion center. Together with two water molecules, two O atoms from different succinate ligands and two imidazole N atoms coordinate to a NiII atom with an octahedron geometry (see Table 1). The carboxyl groups of the succinate display as monodentate ligand, the uncoordinated carboxyl O atoms form hydrogen bonding with the neighboring coordinated water.

The succinate group located around another inversion center. The planar carbon skeleton inclines to the carboxyl group with a dihedral angle of 56.6 (2)°. Carboxyl groups of the succinate coordinate to the neighboring NiII atoms to form the one-dimensional polymeric chains. The adjacent chains link to each other via hydrogen bonding between the benzimidazole nitrogen and carboxyl oxygen atoms, forming the two-dimensional supramolecular structure shown in Fig. 2 and Table 2.

An overlapped disposition of parallel benzimidazole ligands is observed in the crystal structure. Neighboring benzimidazole ligands, related by the symmetry transformation (-x, 1 − y, −z), are separated by 3.350 (3) Å. These findings suggest the existence of ππ-stacking interactions between adjacent polymeric chains.

Experimental top

NiCl2·6H2O (0.48 g, 2 mmol) was added to an aqueous solution (10 ml) containing succinic acid (0.24 g, 2 mmol) and NaOH (0.16 g, 4 mmol). After the mixture was refluxed for 30 min, an ethanol solution (10 ml) of benzimidazole (0.24 g, 2 mmol) was added to the above solution with continuous stirring. The solution was refluxed for 3 h, until the color changed to pale green. The reaction mixture was cooled to room temperature and filtered. Pale green single crystals were obtained from the filtrate after one week.

Refinement top

The H atoms on C atoms were placed in calculated positions, with C—H = 0.93–0.97 Å, and included in the final cycles of refinement as riding, with Uiso(H) = 1.2Ueq of the carrier atoms. H atoms of water were placed in calculation positions (Nardelli, 1993), and were included in the final cycles of refinement with fixed coordinates and isotropic displacement parameters of 0.08 Å2.

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 molecular structure of (I), with 50% probability displacement ellipsoids. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) −x,-y, 1 − z.]
[Figure 2] Fig. 2. The molecular packing diagram, with dashed lines showing hydrogen bonding.
catena-Poly[[diaquabis(1H-benzimidazole-κN3)nickel(II)]-µ-succinato- k2O:O'] top
Crystal data top
[Ni(C4H4O4)(C7H6N2)2(H2O)2]Z = 1
Mr = 447.08F(000) = 232
Triclinic, P1Dx = 1.646 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.0244 (7) ÅCell parameters from 2206 reflections
b = 8.5982 (11) Åθ = 2.6–27.4°
c = 8.7399 (5) ŵ = 1.12 mm1
α = 100.248 (6)°T = 298 K
β = 111.981 (7)°Prism, green
γ = 104.734 (9)°0.39 × 0.19 × 0.11 mm
V = 450.91 (9) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2036 independent reflections
Radiation source: fine-focus sealed tube1913 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
Detector resolution: 10.00 pixels mm-1θmax = 27.5°, θmin = 2.6°
ω scansh = 89
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 1111
Tmin = 0.64, Tmax = 0.88l = 1111
4252 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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0375P)2 + 0.2892P]
where P = (Fo2 + 2Fc2)/3
2036 reflections(Δ/σ)max < 0.001
133 parametersΔρmax = 0.59 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
[Ni(C4H4O4)(C7H6N2)2(H2O)2]γ = 104.734 (9)°
Mr = 447.08V = 450.91 (9) Å3
Triclinic, P1Z = 1
a = 7.0244 (7) ÅMo Kα radiation
b = 8.5982 (11) ŵ = 1.12 mm1
c = 8.7399 (5) ÅT = 298 K
α = 100.248 (6)°0.39 × 0.19 × 0.11 mm
β = 111.981 (7)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2036 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
1913 reflections with I > 2σ(I)
Tmin = 0.64, Tmax = 0.88Rint = 0.015
4252 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.074H-atom parameters constrained
S = 1.11Δρmax = 0.59 e Å3
2036 reflectionsΔρmin = 0.43 e Å3
133 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
Ni0.50000.50000.50000.01674 (10)
O10.2572 (2)0.26719 (15)0.42382 (16)0.0223 (3)
O20.0967 (2)0.32317 (16)0.59500 (17)0.0267 (3)
O30.6927 (2)0.37982 (16)0.42754 (17)0.0255 (3)
N10.2349 (3)0.4384 (2)0.0384 (2)0.0274 (3)
H10.18750.37590.14280.033*
N30.3693 (2)0.51412 (19)0.24894 (19)0.0220 (3)
C20.3061 (3)0.3921 (2)0.1062 (2)0.0267 (4)
H20.31040.28470.10540.032*
C40.3732 (3)0.8149 (2)0.2864 (2)0.0266 (4)
H40.42910.84770.40650.032*
C50.3231 (4)0.9261 (3)0.1941 (3)0.0347 (5)
H50.34691.03560.25330.042*
C60.2372 (4)0.8762 (3)0.0130 (3)0.0408 (5)
H60.20510.95380.04510.049*
C70.1991 (4)0.7161 (3)0.0812 (3)0.0358 (5)
H70.14090.68340.20140.043*
C80.2519 (3)0.6049 (2)0.0121 (2)0.0240 (4)
C90.3368 (3)0.6521 (2)0.1932 (2)0.0212 (3)
C110.1251 (3)0.2230 (2)0.4862 (2)0.0203 (3)
C120.0135 (3)0.0370 (2)0.4253 (2)0.0276 (4)
H12A0.02770.02490.34620.033*
H12B0.16660.02300.36230.033*
H130.79020.33400.44740.080*
H230.68080.41120.33760.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.01906 (16)0.01398 (15)0.01748 (16)0.00472 (11)0.00874 (12)0.00552 (11)
O10.0237 (6)0.0179 (6)0.0239 (6)0.0030 (5)0.0119 (5)0.0061 (5)
O20.0324 (7)0.0223 (6)0.0295 (7)0.0079 (5)0.0185 (6)0.0088 (5)
O30.0293 (7)0.0244 (6)0.0298 (7)0.0129 (5)0.0170 (6)0.0102 (5)
N10.0330 (8)0.0291 (8)0.0174 (7)0.0122 (7)0.0092 (6)0.0037 (6)
N30.0250 (7)0.0195 (7)0.0198 (7)0.0065 (6)0.0086 (6)0.0064 (6)
C20.0298 (9)0.0225 (9)0.0249 (9)0.0081 (7)0.0102 (8)0.0061 (7)
C40.0318 (10)0.0237 (9)0.0220 (9)0.0089 (7)0.0101 (8)0.0066 (7)
C50.0480 (12)0.0252 (9)0.0353 (11)0.0170 (9)0.0191 (10)0.0117 (8)
C60.0610 (15)0.0406 (12)0.0366 (12)0.0296 (11)0.0241 (11)0.0252 (10)
C70.0500 (13)0.0461 (12)0.0226 (9)0.0276 (11)0.0175 (9)0.0178 (9)
C80.0249 (8)0.0291 (9)0.0205 (8)0.0115 (7)0.0111 (7)0.0081 (7)
C90.0214 (8)0.0231 (8)0.0203 (8)0.0073 (7)0.0098 (7)0.0090 (6)
C110.0215 (8)0.0184 (8)0.0191 (8)0.0054 (7)0.0068 (7)0.0087 (6)
C120.0326 (10)0.0186 (8)0.0247 (9)0.0004 (7)0.0115 (8)0.0069 (7)
Geometric parameters (Å, º) top
Ni—O12.0733 (12)C2—H20.930
Ni—O1i2.0733 (12)C4—C51.386 (3)
Ni—N3i2.0774 (14)C4—C91.395 (3)
Ni—N32.0774 (14)C4—H40.930
Ni—O3i2.1028 (13)C5—C61.402 (3)
Ni—O32.1028 (13)C5—H50.930
O1—C111.255 (2)C6—C71.374 (3)
O2—C111.274 (2)C6—H60.930
O3—H130.852C7—C81.396 (3)
O3—H230.857C7—H70.930
N1—C21.346 (2)C8—C91.403 (2)
N1—C81.381 (2)C11—C121.519 (2)
N1—H10.860C12—C12ii1.523 (3)
N3—C21.318 (2)C12—H12A0.970
N3—C91.399 (2)C12—H12B0.970
O1—Ni—N3i89.63 (5)C5—C4—H4121.1
O1i—Ni—N3i90.37 (5)C9—C4—H4121.1
O1—Ni—N390.37 (5)C4—C5—C6121.14 (19)
O1i—Ni—N389.63 (5)C4—C5—H5119.4
O1—Ni—O3i90.09 (5)C6—C5—H5119.4
O1i—Ni—O3i89.91 (5)C7—C6—C5121.95 (19)
N3i—Ni—O3i86.82 (6)C7—C6—H6119.0
N3—Ni—O3i93.18 (6)C5—C6—H6119.0
O1—Ni—O389.91 (5)C6—C7—C8116.83 (18)
O1i—Ni—O390.09 (5)C6—C7—H7121.6
N3i—Ni—O393.18 (6)C8—C7—H7121.6
N3—Ni—O386.82 (6)N1—C8—C7132.46 (17)
C11—O1—Ni128.20 (11)N1—C8—C9105.44 (16)
Ni—O3—H13153.31C7—C8—C9122.09 (18)
Ni—O3—H2398.14C4—C9—N3130.81 (16)
H13—O3—H23106.84C4—C9—C8120.20 (17)
C2—N1—C8107.32 (15)N3—C9—C8108.99 (16)
C2—N1—H1126.3O1—C11—O2124.76 (15)
C8—N1—H1126.3O1—C11—C12117.57 (16)
C2—N3—C9105.01 (15)O2—C11—C12117.67 (16)
C2—N3—Ni126.03 (13)C11—C12—C12ii112.42 (18)
C9—N3—Ni128.92 (12)C11—C12—H12A109.1
N3—C2—N1113.25 (17)C12ii—C12—H12A109.1
N3—C2—H2123.4C11—C12—H12B109.1
N1—C2—H2123.4C12ii—C12—H12B109.1
C5—C4—C9117.79 (18)H12A—C12—H12B107.9
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2iii0.862.062.871 (2)156
O3—H13···O2iv0.852.092.878 (2)153
O3—H23···O2i0.862.242.688 (2)112
Symmetry codes: (i) x+1, y+1, z+1; (iii) x, y, z1; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formula[Ni(C4H4O4)(C7H6N2)2(H2O)2]
Mr447.08
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)7.0244 (7), 8.5982 (11), 8.7399 (5)
α, β, γ (°)100.248 (6), 111.981 (7), 104.734 (9)
V3)450.91 (9)
Z1
Radiation typeMo Kα
µ (mm1)1.12
Crystal size (mm)0.39 × 0.19 × 0.11
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.64, 0.88
No. of measured, independent and
observed [I > 2σ(I)] reflections
4252, 2036, 1913
Rint0.015
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.074, 1.11
No. of reflections2036
No. of parameters133
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.59, 0.43

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
Ni—O12.0733 (12)O2—C111.274 (2)
Ni—N32.0774 (14)C11—C121.519 (2)
Ni—O32.1028 (13)C12—C12i1.523 (3)
O1—C111.255 (2)
Symmetry code: (i) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2ii0.862.062.871 (2)156
O3—H13···O2iii0.852.092.878 (2)153
O3—H23···O2iv0.862.242.688 (2)112
Symmetry codes: (ii) x, y, z1; (iii) x+1, y, z; (iv) x+1, y+1, z+1.
 

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