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Acta Cryst. (2007). E63, m2356-m2357    [ doi:10.1107/S1600536807039384 ]

catena-Poly[[chloridonickel(II)]-di-[mu]-chlorido-[chloridonickel(II)]-[mu]-4,4'-methylenebis(3,5-dimethylpyrazole)-[kappa]2N2:N2']

C.-F. Huang and H.-L. Chen

Abstract top

The title compound, [NiCl2(C11H16N4)]n, is a one-dimensional polymer built up from alternating (NiCl2)2 units and bridging 4,4'-methylenebis(3,5-dimethylpyrazole) ligands. An unusual NiCl3N2 square-based pyramidal coordination arises for the metal atom. The packing is consolidated by N-H...Cl hydrogen bonds.

Comment top

Interest in one dimensional chain structures arises partly because these structures are expected to play a crucial role as precursors in the formation of two- and three-dimensional structures (Neeraj et al., 1999). In the past, the majority of one-dimensional coordination networks were found to be composed of bis-monodentate tectons (Yaghi et al., 1998; Hennigar et al., 1997), while few examples of complexes with bis-bidentate (Veltan & Rehahn, 1996; Kaes et al., 1998), and bis-tridentate tectons (Constable & Cargill Thompson, 1992; Neels et al., 1997; Loi et al., 1999) were published.

In this paper, we report the crystal structure of the title compound, (I), (Fig. 1), containing the bis-bidentate organic tecton 4,4'-methylene-bis(3,5-dimethylpyrazole) and Cl ligands. The Ni atom is coordinated by three Cl- ions and two N-bonded H2mbdpz ligands (Table 1). The four nearest atoms result in a cis-NiCl2N2 square planar geometry and a third chloride ion with a much longer Ni—Cl bond distance completes a distorted NiCl3N2 square pyramid. The alternating (NiCl2)2 groups and pairs of bridging H2mbdpz ligands form an infinite one-dimensional chain (Fig. 2). The dihedral angle between the two pyrazole rings within one ligand is 81.8 (3)°. which is slightly smaller than that in the free ligand. The Ni···Ni non-bonding distance between adjacent metal ions in the chain is 3.728 (4) Å. The structure is completed by N—H···Cl hydrogen bonds (Table 2).

Related literature top

For related literature, see: Constable & Cargill Thompson (1992); Hennigar et al. (1997); Kaes et al. (1998); Loi et al. (1999) Neels et al. (1997); Neeraj et al. (1999); Veltan & Rehahn (1996); Yaghi et al. (1998).

Experimental top

H2mbdpz (102 mg, 0.5 mmol) in ethanol (10 ml) was added to a solution of NiCl2 (12.9 mg, 0.1 mmol) in H2O (10 ml). The mixture was refuxed for 2 h with stirring, yielding a brown precipitate. The solution was then filtered to remove the precipitate, which was subsequently washed with water, methanol and acetone, and finally dried. The solid was dissolved in DMF, producing a clear solution, which was allowed to stand undisturbed at room temperature for a few weeks at which time green blocks of (I) were obtained.

Refinement top

The H atoms were refined with a riding model [C—H = 0.93–0.97Å (geometrically placed) and N—H = 0.96–0.98Å (located in a difference map); Uiso(H) = 1.2Ueq or 1.5 Ueq(carrier)]. The methyl groups were allowed to rotate but not to tip. The maximum difference peak is 1.12Å from Cl2.

Computing details top

Data collection: APEX2 (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level. Symmetry codes: (i) x, 1 - y, 1 + z and (ii) 1 - x, -y, 2 - z.
[Figure 2] Fig. 2. Part of a polymeric chain in (I), viewed along the a axis.
catena-Poly[[chloridonickel(II)]-di-µ-chlorido-[chloridonickel(II)]-µ-\ 4,4'-methylenebis(3,5-dimethylpyrazole)-κ2N2:N2'] top
Crystal data top
[NiCl2(C11H16N4)]Z = 2
Mr = 333.89F(000) = 344
Triclinic, P1Dx = 1.665 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.759 (3) ÅCell parameters from 3212 reflections
b = 8.879 (3) Åθ = 2.3–25.1°
c = 9.735 (3) ŵ = 1.85 mm−1
α = 79.269 (6)°T = 298 K
β = 63.584 (5)°Block, green
γ = 86.922 (5)°0.28 × 0.22 × 0.15 mm
V = 665.8 (4) Å3
Data collection top
Bruker APEX II CCD
diffractometer		2312 independent reflections
Radiation source: fine-focus sealed tube1534 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
Detector resolution: 0 pixels mm-1θmax = 25.1°, θmin = 2.3°
ω scansh = −10→9
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −7→10
Tmin = 0.626, Tmax = 0.769l = −11→11
3330 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)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.208H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.1397P)2]
where P = (Fo2 + 2Fc2)/3
2312 reflections(Δ/σ)max < 0.001
169 parametersΔρmax = 0.73 e Å−3
40 restraintsΔρmin = −1.05 e Å−3
Crystal data top
[NiCl2(C11H16N4)]γ = 86.922 (5)°
Mr = 333.89V = 665.8 (4) Å3
Triclinic, P1Z = 2
a = 8.759 (3) ÅMo Kα radiation
b = 8.879 (3) ŵ = 1.85 mm−1
c = 9.735 (3) ÅT = 298 K
α = 79.269 (6)°0.28 × 0.22 × 0.15 mm
β = 63.584 (5)°
Data collection top
Bruker APEX II CCD
diffractometer		2312 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1534 reflections with I > 2σ(I)
Tmin = 0.626, Tmax = 0.769Rint = 0.033
3330 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.065H-atom parameters constrained
wR(F2) = 0.208Δρmax = 0.73 e Å−3
S = 0.97Δρmin = −1.05 e Å−3
2312 reflectionsAbsolute structure: ?
169 parametersFlack parameter: ?
40 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
Ni20.36689 (12)0.08445 (11)0.90152 (10)0.0275 (4)
Cl10.1129 (2)0.0033 (2)1.1136 (2)0.0370 (5)
Cl20.4813 (3)−0.1538 (2)0.9274 (2)0.0384 (6)
C80.6764 (9)0.5680 (8)0.1917 (8)0.0277 (16)
N20.8976 (7)0.7132 (6)0.1257 (7)0.0324 (15)
C100.9389 (9)0.5714 (9)0.1731 (8)0.0299 (17)
C30.7286 (9)0.2395 (8)0.4362 (8)0.0295 (17)
N40.7209 (8)0.1467 (8)0.6655 (7)0.0371 (17)
N30.5559 (8)0.1395 (8)0.6870 (7)0.0373 (16)
C40.8261 (10)0.2016 (10)0.5168 (9)0.039 (2)
C60.7886 (10)0.3010 (9)0.2662 (8)0.0339 (19)
H39A0.71220.26060.23310.041*
H39B0.90050.26150.21010.041*
C70.8005 (9)0.4745 (8)0.2170 (8)0.0289 (17)
C10.4016 (10)0.1983 (10)0.5276 (9)0.042 (2)
H1C0.32090.12240.60700.063*
H1A0.42720.17660.42670.063*
H1B0.35380.29790.53640.063*
C20.5595 (10)0.1951 (8)0.5472 (9)0.0306 (17)
C51.0141 (10)0.2126 (12)0.4657 (10)0.049 (2)
H45A1.04500.31350.46910.074*
H45B1.07420.19340.36110.074*
H45C1.04380.13800.53420.074*
C90.5025 (10)0.5253 (9)0.2176 (10)0.041 (2)
H30A0.42180.53370.32190.061*
H30B0.50070.42150.20280.061*
H30C0.47280.59290.14460.061*
C111.1094 (10)0.5454 (11)0.1706 (10)0.045 (2)
H47A1.19010.62170.09190.068*
H47B1.14610.44530.14770.068*
H47C1.10200.55240.27060.068*
N10.7387 (7)0.7146 (6)0.1358 (7)0.0348 (16)
H40.75770.10150.74600.070 (6)*
H20.97690.79790.06530.069 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni20.0317 (6)0.0230 (6)0.0266 (6)0.0017 (4)−0.0143 (4)0.0015 (4)
Cl10.0349 (11)0.0368 (12)0.0387 (11)−0.0040 (9)−0.0201 (9)0.0060 (9)
Cl20.0499 (13)0.0277 (11)0.0434 (12)0.0046 (9)−0.0264 (10)−0.0058 (9)
C80.033 (4)0.022 (4)0.024 (4)0.004 (3)−0.011 (3)0.000 (3)
N20.029 (3)0.026 (4)0.039 (4)−0.001 (3)−0.016 (3)0.005 (3)
C100.029 (4)0.033 (4)0.026 (4)−0.001 (3)−0.011 (3)−0.003 (3)
C30.033 (4)0.020 (4)0.033 (4)0.001 (3)−0.014 (3)−0.001 (3)
N40.032 (4)0.044 (4)0.038 (4)−0.004 (3)−0.022 (3)0.003 (3)
N30.036 (4)0.038 (4)0.035 (4)0.009 (3)−0.017 (3)−0.001 (3)
C40.045 (5)0.039 (5)0.030 (4)0.005 (4)−0.019 (4)0.003 (4)
C60.041 (5)0.028 (4)0.031 (4)0.012 (4)−0.017 (4)−0.003 (3)
C70.035 (4)0.023 (4)0.030 (4)0.002 (3)−0.016 (3)−0.004 (3)
C10.048 (5)0.044 (5)0.037 (5)0.005 (4)−0.023 (4)−0.003 (4)
C20.036 (4)0.023 (4)0.036 (4)0.003 (3)−0.021 (4)−0.002 (3)
C50.041 (5)0.064 (7)0.046 (5)0.003 (5)−0.027 (4)0.000 (5)
C90.038 (5)0.031 (5)0.065 (6)−0.007 (4)−0.032 (4)−0.008 (4)
C110.040 (5)0.047 (6)0.046 (5)0.013 (4)−0.019 (4)−0.006 (4)
N10.032 (4)0.031 (4)0.039 (4)−0.001 (3)−0.016 (3)0.002 (3)
Geometric parameters (Å, º) top
Ni2—N31.992 (6)N3—C21.346 (9)
Ni2—N1i2.013 (6)C4—C51.497 (11)
Ni2—Cl12.294 (2)C6—C71.520 (10)
Ni2—Cl22.311 (2)C6—H39A0.9700
Ni2—Cl2ii2.713 (2)C6—H39B0.9700
Cl2—Ni2ii2.713 (2)C1—C21.476 (10)
C8—N11.355 (9)C1—H1C0.9600
C8—C71.413 (10)C1—H1A0.9600
C8—C91.488 (10)C1—H1B0.9600
N2—C101.346 (9)C5—H45A0.9600
N2—N11.351 (7)C5—H45B0.9600
N2—H20.9600C5—H45C0.9600
C10—C71.381 (10)C9—H30A0.9600
C10—C111.489 (10)C9—H30B0.9600
C3—C41.387 (11)C9—H30C0.9600
C3—C21.413 (10)C11—H47A0.9600
C3—C61.494 (10)C11—H47B0.9600
N4—C41.334 (9)C11—H47C0.9600
N4—N31.369 (8)N1—Ni2i2.013 (6)
N4—H40.9864
N3—Ni2—N1i88.6 (2)C7—C6—H39B108.1
N3—Ni2—Cl1164.9 (2)H39A—C6—H39B107.3
N1i—Ni2—Cl188.90 (16)C10—C7—C8105.6 (7)
N3—Ni2—Cl289.5 (2)C10—C7—C6127.7 (7)
N1i—Ni2—Cl2174.54 (19)C8—C7—C6126.4 (7)
Cl1—Ni2—Cl291.59 (8)C2—C1—H1C109.5
N3—Ni2—Cl2ii100.5 (2)C2—C1—H1A109.5
N1i—Ni2—Cl2ii100.84 (19)H1C—C1—H1A109.5
Cl1—Ni2—Cl2ii94.60 (8)C2—C1—H1B109.5
Cl2—Ni2—Cl2ii84.54 (8)H1C—C1—H1B109.5
Ni2—Cl2—Ni2ii95.46 (8)H1A—C1—H1B109.5
N1—C8—C7109.2 (7)N3—C2—C3109.7 (6)
N1—C8—C9121.4 (6)N3—C2—C1120.3 (7)
C7—C8—C9129.4 (7)C3—C2—C1129.9 (7)
C10—N2—N1111.6 (4)C4—C5—H45A109.5
C10—N2—H2125.4C4—C5—H45B109.5
N1—N2—H2120.8H45A—C5—H45B109.5
N2—C10—C7107.3 (6)C4—C5—H45C109.5
N2—C10—C11120.0 (7)H45A—C5—H45C109.5
C7—C10—C11132.7 (8)H45B—C5—H45C109.5
C4—C3—C2105.0 (7)C8—C9—H30A109.5
C4—C3—C6128.1 (7)C8—C9—H30B109.5
C2—C3—C6126.7 (7)H30A—C9—H30B109.5
C4—N4—N3111.0 (6)C8—C9—H30C109.5
C4—N4—H4124.8H30A—C9—H30C109.5
N3—N4—H4123.5H30B—C9—H30C109.5
C2—N3—N4106.1 (6)C10—C11—H47A109.5
C2—N3—Ni2133.1 (5)C10—C11—H47B109.5
N4—N3—Ni2120.0 (5)H47A—C11—H47B109.5
N4—C4—C3108.0 (7)C10—C11—H47C109.5
N4—C4—C5119.9 (7)H47A—C11—H47C109.5
C3—C4—C5132.0 (7)H47B—C11—H47C109.5
C3—C6—C7116.8 (6)N2—N1—C8106.2 (5)
C3—C6—H39A108.1N2—N1—Ni2i119.9 (3)
C7—C6—H39A108.1C8—N1—Ni2i133.3 (5)
C3—C6—H39B108.1
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl1iii0.962.453.227 (6)138
N2—H2···Cl1i0.962.593.123 (6)116
N4—H4···Cl1ii0.992.193.167 (7)169
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+2; (iii) x+1, y+1, z−1.
Selected bond lengths (Å) top
Ni2—N31.992 (6)Ni2—Cl22.311 (2)
Ni2—N1i2.013 (6)Ni2—Cl2ii2.713 (2)
Ni2—Cl12.294 (2)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl1iii0.962.453.227 (6)138
N2—H2···Cl1i0.962.593.123 (6)116
N4—H4···Cl1ii0.992.193.167 (7)169
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+2; (iii) x+1, y+1, z−1.
Acknowledgements top

The authors thank the Scientific and Technical Key Leading Project of Guangdong Province of China (grant No. B05119) for supporting this study.

references
References top

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