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

The title complex, [Ni(N₃)₂(C₁₀H₈N₂)(CH₃OH)₂], lies on a twofold roation axis which runs through the Ni^II ion and the mid-point of the bipyridine ligand. The Ni^II 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); Phatchimkun et al. (2009); Kou et al. (2008); Hou (2008).

Experimental

Crystal data

• [Ni(N₃)₂(C₁₀H₈N₂)(CH₄O)₂]

• M_r = 363.04

• Monoclinic, C 2/c

• a = 16.8173 (15) Å

• b = 13.4470 (12) Å

• c = 7.1848 (6) Å

• β = 111.238 (1)°

• V = 1514.4 (2) ų

• 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) 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[F² > 2σ(F²)] = 0.058

• wR(F²) = 0.210

• S = 1.02

• 1333 reflections

• 106 parameters

• H-atom parameters constrained

• Δρ_max = 1.08 e Å⁻³

• Δρ_min = −0.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1a⋯N3	0.93	2.25	2.721 (4)	111
O1—H1a⋯N4	0.93	2.48	3.227 (5)	137

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

Supporting information

S1. 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 Ni^II 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—N_bipyridine and Ni—N_azido 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.).

Related literature

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

S2. 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).

S3. 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 U_iso(H) = 1.2U_eq(C) and 1.5U_eq(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].

Computing details

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

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.

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

Crystal data

[Ni(N3)2(C10H8N2)(CH4O)2]	F(000) = 752
Mr = 363.04	Dx = 1.592 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1564 reflections
a = 16.8173 (15) Å	θ = 2.8–27.4°
b = 13.4470 (12) Å	µ = 1.31 mm^−1
c = 7.1848 (6) Å	T = 293 K
β = 111.238 (1)°	Block, green
V = 1514.4 (2) Å^3	0.32 × 0.24 × 0.19 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	1333 independent reflections
Radiation source: fine-focus sealed tube	1247 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.012
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −15→20
Tmin = 0.680, Tmax = 0.790	k = −15→11
3647 measured reflections	l = −8→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.210	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.1511P)^2 + 7.4217P] where P = (Fo^2 + 2Fc^2)/3
1333 reflections	(Δ/σ)max = 0.011
106 parameters	Δρmax = 1.08 e Å^−3
0 restraints	Δρmin = −0.68 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	1.0000	0.74532 (6)	0.2500	0.0357 (4)
O1	0.9127 (2)	0.6557 (3)	0.1994 (5)	0.0403 (8)
H1A	0.8679	0.6589	0.0766	0.048*
N1	0.9185 (2)	0.8653 (3)	0.2091 (5)	0.0267 (8)
N2	0.9797 (3)	0.7545 (3)	−0.0390 (6)	0.0331 (10)
N3	0.9118 (3)	0.7278 (3)	−0.1552 (6)	0.0393 (10)
N4	0.8473 (3)	0.7061 (5)	−0.2714 (8)	0.0713 (16)
C1	0.8326 (2)	0.8578 (3)	0.1560 (6)	0.0347 (10)
H1	0.8083	0.7953	0.1514	0.042*
C2	0.7806 (3)	0.9397 (4)	0.1091 (7)	0.0397 (11)
H2	0.7220	0.9327	0.0750	0.048*
C3	0.8157 (3)	1.0328 (4)	0.1126 (6)	0.0374 (10)
H3	0.7811	1.0889	0.0782	0.045*
C4	0.9035 (3)	1.0414 (3)	0.1684 (6)	0.0323 (9)
H4	0.9287	1.1033	0.1723	0.039*
C5	0.9526 (2)	0.9565 (3)	0.2179 (5)	0.0244 (8)
C6	0.9097 (4)	0.5858 (5)	0.3297 (8)	0.0599 (16)
H6A	0.9663	0.5619	0.4021	0.090*
H6B	0.8745	0.5317	0.2589	0.090*
H6C	0.8863	0.6138	0.4215	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0333 (6)	0.0382 (6)	0.0347 (6)	0.000	0.0114 (4)	0.000
O1	0.0367 (17)	0.0404 (19)	0.0380 (17)	−0.0107 (14)	0.0068 (13)	0.0056 (14)
N1	0.0201 (16)	0.0322 (18)	0.0275 (17)	−0.0002 (13)	0.0083 (13)	0.0000 (13)
N2	0.032 (2)	0.043 (2)	0.024 (2)	−0.0043 (14)	0.0095 (18)	0.0006 (13)
N3	0.048 (3)	0.041 (2)	0.031 (2)	−0.0041 (19)	0.016 (2)	0.0055 (17)
N4	0.057 (3)	0.100 (4)	0.042 (3)	−0.034 (3)	0.000 (2)	0.003 (3)
C1	0.0205 (19)	0.043 (3)	0.038 (2)	−0.0039 (17)	0.0078 (16)	0.0002 (18)
C2	0.024 (2)	0.054 (3)	0.041 (2)	0.0030 (19)	0.0108 (18)	−0.002 (2)
C3	0.029 (2)	0.043 (3)	0.037 (2)	0.0113 (18)	0.0087 (18)	0.0006 (18)
C4	0.031 (2)	0.033 (2)	0.032 (2)	0.0023 (17)	0.0103 (17)	−0.0023 (17)
C5	0.021 (2)	0.033 (2)	0.0198 (17)	0.0004 (15)	0.0069 (14)	−0.0010 (15)
C6	0.052 (3)	0.069 (4)	0.049 (3)	−0.024 (3)	0.008 (2)	0.008 (3)

Geometric parameters (Å, º)

Ni1—O1	1.831 (3)	C1—C2	1.370 (7)
Ni1—O1^i	1.831 (3)	C1—H1	0.9300
Ni1—N2	1.982 (4)	C2—C3	1.380 (7)
Ni1—N2^i	1.982 (4)	C2—H2	0.9300
Ni1—N1^i	2.068 (4)	C3—C4	1.387 (6)
Ni1—N1	2.068 (4)	C3—H3	0.9300
O1—C6	1.340 (6)	C4—C5	1.379 (6)
O1—H1A	0.9300	C4—H4	0.9300
N1—C5	1.346 (5)	C5—C5^i	1.490 (7)
N1—C1	1.358 (5)	C6—H6A	0.9600
N2—N3	1.199 (6)	C6—H6B	0.9600
N3—N4	1.142 (6)	C6—H6C	0.9600
O1—Ni1—O1^i	97.7 (2)	N4—N3—N2	176.8 (5)
O1—Ni1—N2	90.64 (15)	N1—C1—C2	121.9 (4)
O1^i—Ni1—N2	94.04 (16)	N1—C1—H1	119.1
O1—Ni1—N2^i	94.04 (16)	C2—C1—H1	119.1
O1^i—Ni1—N2^i	90.64 (15)	C1—C2—C3	119.6 (4)
N2—Ni1—N2^i	172.9 (2)	C1—C2—H2	120.2
O1—Ni1—N1^i	169.78 (14)	C3—C2—H2	120.2
O1^i—Ni1—N1^i	92.41 (16)	C2—C3—C4	119.0 (4)
N2—Ni1—N1^i	87.38 (14)	C2—C3—H3	120.5
N2^i—Ni1—N1^i	87.08 (15)	C4—C3—H3	120.5
O1—Ni1—N1	92.41 (16)	C5—C4—C3	118.8 (4)
O1^i—Ni1—N1	169.78 (14)	C5—C4—H4	120.6
N2—Ni1—N1	87.08 (15)	C3—C4—H4	120.6
N2^i—Ni1—N1	87.38 (14)	N1—C5—C4	122.5 (3)
N1^i—Ni1—N1	77.48 (19)	N1—C5—C5^i	113.9 (2)
C6—O1—Ni1	123.5 (3)	C4—C5—C5^i	123.6 (2)
C6—O1—H1A	118.2	O1—C6—H6A	109.5
Ni1—O1—H1A	118.2	O1—C6—H6B	109.5
C5—N1—C1	118.2 (3)	H6A—C6—H6B	109.5
C5—N1—Ni1	117.0 (2)	O1—C6—H6C	109.5
C1—N1—Ni1	124.4 (3)	H6A—C6—H6C	109.5
N3—N2—Ni1	118.1 (3)	H6B—C6—H6C	109.5

Symmetry code: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1a···N3	0.93	2.25	2.721 (4)	111
O1—H1a···N4	0.93	2.48	3.227 (5)	137