supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

si2051 scheme

Acta Cryst. (2007). E63, m3062    [ doi:10.1107/S1600536807058485 ]

catena-Poly[[bis(pyridine-[kappa]N)nickel(II)]-di-[mu]-azido-[kappa]4N1:N3-[bis(pyridine-[kappa]N)nickel(II)]-di-[mu]-azido-[kappa]4N1:N1]

W.-C. Song, M.-J. Zhang, Y. Tao and J.-R. Li

Abstract top

In the structure of the title compound, [Ni2(N3)4(C5H5N)4]n, neutral chains of NiII atoms are bridged alternately by double end-on and double end-to-end azide bridges. Each NiII center is located on a crystallographic general position and in a slightly distorted octahedral coordination environment with two pyridine ligands in the trans positions. Both end-on and end-to-end double azide bridges become equivalent because of the inversion centers lying between each pair of adjacent NiII atoms. In the chain, the Ni...Ni separations across the end-on and end-to-end azide bridges are 3.236 (4) and 4.975 (4) Å, respectively, and the end-on azide bridging Ni-N-Ni angle is 100.8 (2)°.

Comment top

Azido-NiII compounds with mono-N donored pyridine based co-ligands have been investigated early with respect to their metal-to-ligand π-bonding features (Nelson & Shepherd, 1965), magnetic circular dichroism and crystal field (Schreiner & Hamm, 1973). Recently, the crystal structures of two relative compounds, {[Ni(4-ethylpyridine)4(N3)]·(PF6)}n (Goher et al., 2002) and [Ni(pyridine)2(N3)2] (Liu et al., 2006) have been reported. The former has a single end-to-end azido-bridged cationic chain structure, but the latter is mono-nuclear. Different from them, the title compound, [Ni2(C5H5N)4(N3)4]n has a neutral chain structure of NiII atoms bridged alternately by double end-on and double end-to-end azido bridges.

As shown in Fig. 1, the NiII center located at the crystallographically general position is coordinated by four azido N and two pyridine N atoms in a slightly distorted octahedral environment, in which two pyridine ligands lie in the trans positions. Both end-on and end-to-end double azido bridges become equivalent because of the inversion centers lied on between each two adjacent NiII atoms, respectively. Based on the (Ni1—N3—Ni1A—N3A) plane, the out-of-plane deviation of the N3—N4—N5 group is ca 14.1 (4) °, and the dihedral angles between the mean plane and two pyridyl rings are 99.7 (4) ° for (C1—C5—N1) and 82.9 (4) ° for (C6—C10—N2), respectively. The end-to-end azido-bridged dinuclear unit has a chair configuration with the dihedral angle between the (N6—Ni1—N8B) and (N6—N8—N6B—N8B) mean plane is 143.5 (4) °. In the chain, the Ni—Ni distances across the end-on and end-to-end azido bridges are 3.236 (4) and 4.975 (4) Å, respectively, and the end-on azido bridging Ni1—N3—Ni1A angle is 100.8 (2) °. In addition, in the crystal structure such chains arrange in parallel along the a direction to finish the three-dimensional packing (Fig. 2).

Related literature top

For related literature, see: Goher et al. (2002); Liu et al. (2006); Nelson & Shepherd (1965); Schreiner & Hamm (1973).

Experimental top

A mixture of NiCl2·6H2O (24 mg, 0.1 mmol), NaN3 (26 mg, 0.4 mmol) and pyridine (20 mg, 0.25 mmol) in 10 ml of water was sealed in a Teflon-lined stainless-steel Parr bomb that was heated at 413 K for 48 h. Green crystals of the title compound were collected after the bomb was allowed to cool to room temperature spontaneously. Yield, 10% with respect to Cu(II). Caution: Azide is potentially explosive, especially in a hydrothermal manipulation. Although we have met no problems in this work, only a small amount of them should be prepared and handled with great caution.

Refinement top

H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C, N).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SHELXTL (Bruker, 1998); 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 (Bruker, 1998).

Figures top
[Figure 1] Fig. 1. one-dimensional chain structure of the title compound with 30% displacement probability. [Herein, labelled atoms A and B correspond to symmetry oprations i and ii, respectively. (i) = 1 − x, 1 − y, 1 − z; (ii) = 2 − x, 1 − y, 1 − z]
[Figure 2] Fig. 2. three-dimensional packing of one-dimensional chains in the title compound.
catena-Poly[[bis(pyridine-κN)nickel(II)]-di-µ-azido-κ4N1:N3– [bis(pyridine-κN)nickel(II)]-di-µ-azido-κ4N1:N1] top
Crystal data top
[Ni2(N3)4(C5H5N)4]Z = 2
Mr = 300.97F000 = 308
Triclinic, P1Dx = 1.538 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.1354 (16) ÅCell parameters from 6054 reflections
b = 9.4770 (19) Åθ = 2.9–27.6º
c = 10.094 (2) ŵ = 1.49 mm−1
α = 84.66 (3)ºT = 293 (2) K
β = 67.17 (3)ºBlock, green
γ = 65.36 (3)º0.30 × 0.10 × 0.08 mm
V = 649.8 (3) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		2532 independent reflections
Radiation source: fine-focus sealed tube2127 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.037
T = 293(2) Kθmax = 26.0º
φ and ω scanθmin = 3.0º
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −10→10
Tmin = 0.913, Tmax = 1.000k = −11→11
6061 measured reflectionsl = −12→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.164  w = 1/[σ2(Fo2) + (0.0999P)2 + 0.3477P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2532 reflectionsΔρmax = 1.66 e Å−3
172 parametersΔρmin = −0.43 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni2(N3)4(C5H5N)4]γ = 65.36 (3)º
Mr = 300.97V = 649.8 (3) Å3
Triclinic, P1Z = 2
a = 8.1354 (16) ÅMo Kα
b = 9.4770 (19) ŵ = 1.49 mm−1
c = 10.094 (2) ÅT = 293 (2) K
α = 84.66 (3)º0.30 × 0.10 × 0.08 mm
β = 67.17 (3)º
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		2532 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		2127 reflections with I > 2σ(I)
Tmin = 0.913, Tmax = 1.000Rint = 0.037
6061 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.061172 parameters
wR(F2) = 0.164H-atom parameters constrained
S = 1.08Δρmax = 1.66 e Å−3
2532 reflectionsΔρmin = −0.43 e Å−3
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
Ni10.69698 (7)0.51940 (6)0.47848 (5)0.0358 (2)
N10.7466 (6)0.3698 (5)0.6423 (4)0.0435 (9)
N20.6740 (6)0.6716 (5)0.3143 (4)0.0453 (9)
N30.3937 (5)0.6239 (5)0.5965 (4)0.0423 (9)
N40.3021 (5)0.7109 (4)0.7033 (4)0.0392 (8)
N50.2148 (8)0.7941 (6)0.8059 (5)0.0725 (14)
N60.7515 (6)0.6794 (5)0.5723 (5)0.0498 (10)
N70.8790 (5)0.6417 (4)0.6133 (4)0.0423 (9)
N81.0035 (5)0.6082 (5)0.6582 (4)0.0501 (10)
C10.6961 (8)0.4251 (7)0.7757 (5)0.0545 (13)
H1A0.62290.53150.80030.065*
C20.7475 (9)0.3319 (7)0.8788 (6)0.0622 (14)
H2A0.70780.37490.97100.075*
C30.8581 (9)0.1744 (7)0.8438 (6)0.0687 (16)
H3A0.89900.10930.91020.082*
C40.9060 (11)0.1169 (7)0.7085 (7)0.085 (2)
H4A0.97520.01040.68240.101*
C50.8511 (10)0.2176 (7)0.6114 (6)0.0696 (17)
H5A0.88930.17670.51870.084*
C60.5810 (9)0.8266 (7)0.3467 (7)0.0645 (15)
H6A0.51880.86440.44320.077*
C70.5738 (11)0.9323 (8)0.2428 (9)0.086 (2)
H7A0.51091.03900.26850.104*
C80.6626 (11)0.8754 (9)0.0997 (9)0.085 (2)
H8A0.66030.94360.02720.102*
C90.7538 (9)0.7183 (9)0.0657 (7)0.0781 (19)
H9A0.81330.6778−0.02990.094*
C100.7559 (8)0.6207 (7)0.1759 (5)0.0556 (13)
H10A0.81800.51380.15200.067*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0275 (3)0.0467 (4)0.0376 (4)−0.0149 (3)−0.0162 (2)−0.0014 (2)
N10.036 (2)0.055 (2)0.044 (2)−0.0173 (18)−0.0219 (17)0.0041 (18)
N20.043 (2)0.048 (2)0.048 (2)−0.0200 (18)−0.0191 (18)0.0057 (18)
N30.0319 (19)0.054 (2)0.042 (2)−0.0158 (17)−0.0140 (17)−0.0113 (18)
N40.040 (2)0.041 (2)0.042 (2)−0.0144 (17)−0.0242 (18)0.0033 (18)
N50.081 (3)0.066 (3)0.053 (3)−0.017 (3)−0.018 (3)−0.018 (2)
N60.042 (2)0.053 (2)0.065 (3)−0.0164 (19)−0.032 (2)−0.005 (2)
N70.035 (2)0.046 (2)0.046 (2)−0.0158 (17)−0.0142 (17)−0.0091 (17)
N80.0293 (19)0.075 (3)0.046 (2)−0.0179 (19)−0.0166 (18)−0.008 (2)
C10.047 (3)0.068 (3)0.044 (3)−0.021 (3)−0.016 (2)0.002 (2)
C20.064 (3)0.083 (4)0.041 (3)−0.030 (3)−0.021 (3)0.007 (3)
C30.079 (4)0.075 (4)0.054 (3)−0.022 (3)−0.041 (3)0.016 (3)
C40.110 (6)0.057 (4)0.078 (4)−0.009 (4)−0.056 (4)0.005 (3)
C50.095 (5)0.057 (3)0.058 (3)−0.017 (3)−0.044 (3)−0.005 (3)
C60.077 (4)0.058 (3)0.076 (4)−0.032 (3)−0.043 (3)0.012 (3)
C70.099 (5)0.063 (4)0.120 (6)−0.038 (4)−0.066 (5)0.034 (4)
C80.093 (5)0.093 (5)0.094 (5)−0.051 (4)−0.056 (4)0.047 (4)
C90.064 (4)0.108 (5)0.056 (4)−0.035 (4)−0.022 (3)0.024 (4)
C100.052 (3)0.070 (3)0.047 (3)−0.026 (3)−0.022 (2)0.008 (3)
Geometric parameters (Å, °) top
Ni1—N12.124 (4)C1—H1A0.9300
Ni1—N22.105 (4)C2—C31.376 (8)
Ni1—N32.095 (4)C2—H2A0.9300
Ni1—N3i2.103 (4)C3—C41.365 (8)
Ni1—N62.132 (4)C3—H3A0.9300
Ni1—N8ii2.133 (4)C4—C51.371 (8)
N3—N41.195 (5)C4—H4A0.9300
N4—N51.145 (6)C5—H5A0.9300
N6—N71.172 (5)C6—C71.382 (8)
N7—N81.179 (5)C6—H6A0.9300
N1—C51.325 (7)C7—C81.382 (11)
N1—C11.334 (6)C7—H7A0.9300
N2—C101.328 (7)C8—C91.364 (10)
N2—C61.345 (7)C8—H8A0.9300
N3—Ni1i2.103 (4)C9—C101.379 (8)
N8—Ni1ii2.133 (4)C9—H9A0.9300
C1—C21.377 (7)C10—H10A0.9300
N1—Ni1—N688.38 (16)N1—C1—H1A118.5
N1—Ni1—N8ii88.52 (16)C2—C1—H1A118.5
N2—Ni1—N1173.88 (14)C3—C2—C1119.3 (5)
N2—Ni1—N687.15 (16)C3—C2—H2A120.4
N2—Ni1—N8ii87.70 (16)C1—C2—H2A120.4
N3—Ni1—N192.67 (15)C4—C3—C2117.8 (5)
N3i—Ni1—N191.49 (15)C4—C3—H3A121.1
N3—Ni1—N291.78 (16)C2—C3—H3A121.1
N3i—Ni1—N293.47 (16)C3—C4—C5119.3 (6)
N3—Ni1—N3i79.16 (16)C3—C4—H4A120.3
N3—Ni1—N693.68 (15)C5—C4—H4A120.3
N3i—Ni1—N6172.83 (14)N1—C5—C4123.8 (5)
N3—Ni1—N8ii171.42 (14)N1—C5—H5A118.1
N3i—Ni1—N8ii92.31 (15)C4—C5—H5A118.1
N6—Ni1—N8ii94.85 (16)N2—C6—C7122.9 (6)
N7—N6—Ni1123.5 (3)N2—C6—H6A118.5
N7—N8—Ni1ii120.3 (3)C7—C6—H6A118.5
Ni1—N3—Ni1i100.84 (16)C6—C7—C8118.2 (7)
C5—N1—C1116.7 (4)C6—C7—H7A120.9
C5—N1—Ni1120.9 (3)C8—C7—H7A120.9
C1—N1—Ni1121.9 (3)C9—C8—C7119.4 (6)
C10—N2—C6117.3 (5)C9—C8—H8A120.3
C10—N2—Ni1122.3 (4)C7—C8—H8A120.3
C6—N2—Ni1120.3 (4)C8—C9—C10118.7 (6)
N4—N3—Ni1129.7 (3)C8—C9—H9A120.6
N4—N3—Ni1i126.7 (3)C10—C9—H9A120.6
N5—N4—N3179.8 (6)N2—C10—C9123.4 (6)
N6—N7—N8177.7 (5)N2—C10—H10A118.3
N1—C1—C2123.0 (5)C9—C10—H10A118.3
N3—Ni1—N1—C5128.9 (4)N1—Ni1—N3—Ni1i−91.00 (17)
N3i—Ni1—N1—C549.6 (4)N6—Ni1—N3—Ni1i−179.55 (16)
N6—Ni1—N1—C5−137.5 (4)N2—Ni1—N6—N7−132.9 (4)
N8ii—Ni1—N1—C5−42.6 (4)N1—Ni1—N6—N742.9 (4)
N3—Ni1—N1—C1−59.6 (4)N8ii—Ni1—N6—N7−45.5 (4)
N3i—Ni1—N1—C1−138.8 (4)C5—N1—C1—C2−0.1 (8)
N6—Ni1—N1—C134.0 (4)Ni1—N1—C1—C2−171.9 (4)
N8ii—Ni1—N1—C1128.9 (4)N1—C1—C2—C30.9 (9)
N3—Ni1—N2—C10−129.8 (4)C1—C2—C3—C4−2.4 (10)
N3i—Ni1—N2—C10−50.6 (4)C2—C3—C4—C53.1 (11)
N6—Ni1—N2—C10136.6 (4)C1—N1—C5—C40.8 (9)
N8ii—Ni1—N2—C1041.6 (4)Ni1—N1—C5—C4172.8 (6)
N3—Ni1—N2—C653.0 (4)C3—C4—C5—N1−2.4 (11)
N3i—Ni1—N2—C6132.3 (4)C10—N2—C6—C7−2.2 (8)
N6—Ni1—N2—C6−40.6 (4)Ni1—N2—C6—C7175.1 (5)
N8ii—Ni1—N2—C6−135.6 (4)N2—C6—C7—C81.5 (10)
N3i—Ni1—N3—N4161.8 (5)C6—C7—C8—C90.0 (11)
N2—Ni1—N3—N4−105.0 (4)C7—C8—C9—C10−0.6 (10)
N1—Ni1—N3—N470.8 (4)C6—N2—C10—C91.6 (8)
N6—Ni1—N3—N4−17.8 (4)Ni1—N2—C10—C9−175.7 (4)
N3i—Ni1—N3—Ni1i0.0C8—C9—C10—N2−0.2 (9)
N2—Ni1—N3—Ni1i93.19 (17)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1.
Acknowledgements top

The authors thank Nankai University for supporting this work.

references
References top

Bruker (1998). SMART (Version 5.051), SAINT (Version 5.01), SADABS (Version 2.03) and SHELXTL (Version 6.1). Bruker AXS Inc., Madison, Wisconsin, USA.

Goher, M. A. S., Escuer, A., Mautner, F. A. & Al-Salem, N. A. (2002). Polyhedron, 21, 1871–1876.

Liu, H.-L., Cheng, K. & Li, Z.-B. (2006). Acta Cryst. E62, m1205–m1206.

Nelson, S. M. & Shepherd, T. M. (1965). Inorg. Chem. 4, 813–817.

Schreiner, A. F. & Hamm, D. J. (1973). Inorg. Chem. 12, 2037–2048.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.