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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): m1349.
Published online 2010 October 2. doi:  10.1107/S1600536810038377
PMCID: PMC3009301

Diazido­(2,2′-bipyrid­yl)dimethanol­nickel(II)

Abstract

The title complex, [Ni(N3)2(C10H8N2)(CH3OH)2], lies on a twofold roation axis which runs through the NiII ion and the mid-point of the bipyridine ligand. The NiII ion is coordinated in a distorted octa­hedral environment by two azide ligands in a trans configuration. The methanol ligands are in a cis configuration and their hy­droxy groups form intra­molecular O—H(...)(N,N) hydrogen bonds with the azide ligands.

Related literature

For related structures, see: Urtiaga et al. (1995 [triangle]); Phatchimkun et al. (2009 [triangle]); Kou et al. (2008 [triangle]); Hou (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1349-scheme1.jpg

Experimental

Crystal data

  • [Ni(N3)2(C10H8N2)(CH4O)2]
  • M r = 363.04
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1349-efi1.jpg
  • a = 16.8173 (15) Å
  • b = 13.4470 (12) Å
  • c = 7.1848 (6) Å
  • β = 111.238 (1)°
  • V = 1514.4 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.31 mm−1
  • T = 293 K
  • 0.32 × 0.24 × 0.19 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008a [triangle]) T min = 0.680, T max = 0.790
  • 3647 measured reflections
  • 1333 independent reflections
  • 1247 reflections with I > 2σ(I)
  • R int = 0.012

Refinement

  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.210
  • S = 1.02
  • 1333 reflections
  • 106 parameters
  • H-atom parameters constrained
  • Δρmax = 1.08 e Å−3
  • Δρmin = −0.68 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008b [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810038377/lh5134sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038377/lh5134Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the support of the Scientific and Technical Office of WeiFang (No. 200901036).

supplementary crystallographic information

Comment

As has been known for some time, 2,2'-bipyridine is a good bidentate chelating ligand and the azido group a good bridging ligand. Here, we present a new six-coordinate nickel(II) complex based on 2,2'-bipyridine azido ligands.

The molecular structure of the title compound is shown in Fig. 1. The coordination environment of the NiII ion distorted octahedral, in which two sites are occupied by the two N atoms of the chelating 2,2'-bipyridine ligand and the trans positions are occupied by two N atoms of two azido ligands. Two O atoms of two methanol ligands complete the coordination. The Ni—Nbipyridine and Ni—Nazido bond lengths are basically consistant with the corresponding distances found in other nickel bipyridine azido copmplexes (Urtiaga, et al., 1995; Phatchimkun, et al., 2009; Kou, et al., 2008; Hou, 2008.).

Experimental

A mixture of 2,2'-bipyridine, NiCl2.6H2O (1:1, molar ratio), excessive NaN3 and methanol (20 ml) was sealed in a Teflon-lined autoclave (25 ml) and heated 353 K for 12 h. Upon cooling slowly and opening the bomb, green crystals suitable for X-ray diffraction were obtained with a yield about 55% (based on 2,2'-bipyridine).

Refinement

The H atoms bonded to C atoms were placed using the HFIX commands in SHELXL-97 (Sheldrick, 2008a), with C—H distances of 0.93 and 0.96 Å, and were allowed for as riding atoms with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(C), respectively. The hydroxy H atom could not be found in a difference map but by including it using the HFIX 43 instruction in SHELXL-97 there are likely acceptors for hydrogen bonds [see Table 1].

Figures

Fig. 1.
The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines. Unlabeled atoms are related by the symmetry operator -x+2, y, -z+1/2. ...

Crystal data

[Ni(N3)2(C10H8N2)(CH4O)2]F(000) = 752
Mr = 363.04Dx = 1.592 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1564 reflections
a = 16.8173 (15) Åθ = 2.8–27.4°
b = 13.4470 (12) ŵ = 1.31 mm1
c = 7.1848 (6) ÅT = 293 K
β = 111.238 (1)°Block, green
V = 1514.4 (2) Å30.32 × 0.24 × 0.19 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer1333 independent reflections
Radiation source: fine-focus sealed tube1247 reflections with I > 2σ(I)
graphiteRint = 0.012
[var phi] and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)h = −15→20
Tmin = 0.680, Tmax = 0.790k = −15→11
3647 measured reflectionsl = −8→8

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.210H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.1511P)2 + 7.4217P] where P = (Fo2 + 2Fc2)/3
1333 reflections(Δ/σ)max = 0.011
106 parametersΔρmax = 1.08 e Å3
0 restraintsΔρmin = −0.68 e Å3

Special details

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)

xyzUiso*/Ueq
Ni11.00000.74532 (6)0.25000.0357 (4)
O10.9127 (2)0.6557 (3)0.1994 (5)0.0403 (8)
H1A0.86790.65890.07660.048*
N10.9185 (2)0.8653 (3)0.2091 (5)0.0267 (8)
N20.9797 (3)0.7545 (3)−0.0390 (6)0.0331 (10)
N30.9118 (3)0.7278 (3)−0.1552 (6)0.0393 (10)
N40.8473 (3)0.7061 (5)−0.2714 (8)0.0713 (16)
C10.8326 (2)0.8578 (3)0.1560 (6)0.0347 (10)
H10.80830.79530.15140.042*
C20.7806 (3)0.9397 (4)0.1091 (7)0.0397 (11)
H20.72200.93270.07500.048*
C30.8157 (3)1.0328 (4)0.1126 (6)0.0374 (10)
H30.78111.08890.07820.045*
C40.9035 (3)1.0414 (3)0.1684 (6)0.0323 (9)
H40.92871.10330.17230.039*
C50.9526 (2)0.9565 (3)0.2179 (5)0.0244 (8)
C60.9097 (4)0.5858 (5)0.3297 (8)0.0599 (16)
H6A0.96630.56190.40210.090*
H6B0.87450.53170.25890.090*
H6C0.88630.61380.42150.090*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ni10.0333 (6)0.0382 (6)0.0347 (6)0.0000.0114 (4)0.000
O10.0367 (17)0.0404 (19)0.0380 (17)−0.0107 (14)0.0068 (13)0.0056 (14)
N10.0201 (16)0.0322 (18)0.0275 (17)−0.0002 (13)0.0083 (13)0.0000 (13)
N20.032 (2)0.043 (2)0.024 (2)−0.0043 (14)0.0095 (18)0.0006 (13)
N30.048 (3)0.041 (2)0.031 (2)−0.0041 (19)0.016 (2)0.0055 (17)
N40.057 (3)0.100 (4)0.042 (3)−0.034 (3)0.000 (2)0.003 (3)
C10.0205 (19)0.043 (3)0.038 (2)−0.0039 (17)0.0078 (16)0.0002 (18)
C20.024 (2)0.054 (3)0.041 (2)0.0030 (19)0.0108 (18)−0.002 (2)
C30.029 (2)0.043 (3)0.037 (2)0.0113 (18)0.0087 (18)0.0006 (18)
C40.031 (2)0.033 (2)0.032 (2)0.0023 (17)0.0103 (17)−0.0023 (17)
C50.021 (2)0.033 (2)0.0198 (17)0.0004 (15)0.0069 (14)−0.0010 (15)
C60.052 (3)0.069 (4)0.049 (3)−0.024 (3)0.008 (2)0.008 (3)

Geometric parameters (Å, °)

Ni1—O11.831 (3)C1—C21.370 (7)
Ni1—O1i1.831 (3)C1—H10.9300
Ni1—N21.982 (4)C2—C31.380 (7)
Ni1—N2i1.982 (4)C2—H20.9300
Ni1—N1i2.068 (4)C3—C41.387 (6)
Ni1—N12.068 (4)C3—H30.9300
O1—C61.340 (6)C4—C51.379 (6)
O1—H1A0.9300C4—H40.9300
N1—C51.346 (5)C5—C5i1.490 (7)
N1—C11.358 (5)C6—H6A0.9600
N2—N31.199 (6)C6—H6B0.9600
N3—N41.142 (6)C6—H6C0.9600
O1—Ni1—O1i97.7 (2)N4—N3—N2176.8 (5)
O1—Ni1—N290.64 (15)N1—C1—C2121.9 (4)
O1i—Ni1—N294.04 (16)N1—C1—H1119.1
O1—Ni1—N2i94.04 (16)C2—C1—H1119.1
O1i—Ni1—N2i90.64 (15)C1—C2—C3119.6 (4)
N2—Ni1—N2i172.9 (2)C1—C2—H2120.2
O1—Ni1—N1i169.78 (14)C3—C2—H2120.2
O1i—Ni1—N1i92.41 (16)C2—C3—C4119.0 (4)
N2—Ni1—N1i87.38 (14)C2—C3—H3120.5
N2i—Ni1—N1i87.08 (15)C4—C3—H3120.5
O1—Ni1—N192.41 (16)C5—C4—C3118.8 (4)
O1i—Ni1—N1169.78 (14)C5—C4—H4120.6
N2—Ni1—N187.08 (15)C3—C4—H4120.6
N2i—Ni1—N187.38 (14)N1—C5—C4122.5 (3)
N1i—Ni1—N177.48 (19)N1—C5—C5i113.9 (2)
C6—O1—Ni1123.5 (3)C4—C5—C5i123.6 (2)
C6—O1—H1A118.2O1—C6—H6A109.5
Ni1—O1—H1A118.2O1—C6—H6B109.5
C5—N1—C1118.2 (3)H6A—C6—H6B109.5
C5—N1—Ni1117.0 (2)O1—C6—H6C109.5
C1—N1—Ni1124.4 (3)H6A—C6—H6C109.5
N3—N2—Ni1118.1 (3)H6B—C6—H6C109.5

Symmetry codes: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1a···N30.932.252.721 (4)111
O1—H1a···N40.932.483.227 (5)137

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5134).

References

  • Bruker (2001). SAINT-Plus Bruker AXS Inc., Madison,Wisconsin, USA.
  • Bruker (2004). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hou, J. (2008). Acta Cryst. E64, m1571. [PMC free article] [PubMed]
  • Kou, H. Z., Hishiya, S. & Sato, O. (2008). Inorg. Chim. Acta, 361, 2396–2406.
  • Phatchimkun, J., Kongsaeree, P., Suchaichit, N. & Chaichit, N. (2009). Acta Cryst. E65, m1020–m1021. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008a). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122. [PubMed]
  • Urtiaga, M. K., Arriortua, M. I., De Muro, I. G. & Cortes, R. (1995). Acta Cryst. C51, 62–65.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography