In the title complex, [Ni(N
3)
2(C
3H
4N
2)
4], the octahedrally coordinated Ni atom, which is located at an inversion center, is coordinated by four N atoms of imidazole and two N atoms of azide ligands. The molecules are linked into a three-dimensional network through N—H
N hydrogen bonds.
Supporting information
CCDC reference: 198310
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.032
- wR factor = 0.092
- Data-to-parameter ratio = 13.0
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
To a methanol–acetone solution (1:1, 20 ml) of nickel chloride (1.00 g, 4.2 mmol) was added imidazole (1.00 g, 14.7 mmol) and sodium azide (0.60 g, 9.2 mmol). The mixture was refluxed for 30 min, then allowed to cool to room temperature. Blue prism-shaped crystals of (I) suitable for X-ray analysis were obtained after a few days.
Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: SMART and SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXL97.
Crystal data top
[Ni(N3)2(C3H4N2)4] | F(000) = 428 |
Mr = 415.10 | Dx = 1.475 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.787 (1) Å | Cell parameters from 2860 reflections |
b = 10.464 (1) Å | θ = 2.0–25.0° |
c = 10.866 (1) Å | µ = 1.07 mm−1 |
β = 110.67 (1)° | T = 293 K |
V = 934.79 (17) Å3 | Prism, blue |
Z = 2 | 0.32 × 0.23 × 0.16 mm |
Data collection top
Siemens SMART CCD diffractometer | 1630 independent reflections |
Radiation source: fine-focus sealed tube | 1340 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.6° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −10→8 |
Tmin = 0.706, Tmax = 0.843 | k = −12→8 |
2860 measured reflections | l = −6→12 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0464P)2 + 0.368P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
1630 reflections | Δρmax = 0.25 e Å−3 |
125 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.010 (2) |
Crystal data top
[Ni(N3)2(C3H4N2)4] | V = 934.79 (17) Å3 |
Mr = 415.10 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.787 (1) Å | µ = 1.07 mm−1 |
b = 10.464 (1) Å | T = 293 K |
c = 10.866 (1) Å | 0.32 × 0.23 × 0.16 mm |
β = 110.67 (1)° | |
Data collection top
Siemens SMART CCD diffractometer | 1630 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1340 reflections with I > 2σ(I) |
Tmin = 0.706, Tmax = 0.843 | Rint = 0.022 |
2860 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.25 e Å−3 |
1630 reflections | Δρmin = −0.23 e Å−3 |
125 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. All H atoms were generated geometrically and were constrained to ride on the parent atoms. The highest residual peak (0.25 e Å−3) locates at the position (0.0223, 0.4787, 0.4044), which is 1.15 Å from Ni1; the deepest hole (−0.23 e Å−3) locates at the position (0.0692, 0.4738, 0.5642), which is 0.79 Å from Ni1. 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 | x | y | z | Uiso*/Ueq | |
Ni1 | 0.0000 | 0.5000 | 0.5000 | 0.03846 (19) | |
N7 | 0.0973 (2) | 0.31533 (18) | 0.51691 (19) | 0.0448 (5) | |
N6 | 0.2147 (3) | 0.1367 (2) | 0.6062 (2) | 0.0591 (6) | |
H6B | 0.2621 | 0.0805 | 0.6651 | 0.071* | |
N5 | 0.2344 (2) | 0.5822 (2) | 0.5441 (2) | 0.0488 (5) | |
N4 | 0.4970 (3) | 0.6155 (3) | 0.6224 (3) | 0.0731 (8) | |
H4B | 0.5988 | 0.6037 | 0.6657 | 0.088* | |
N3 | 0.0360 (3) | 0.49130 (19) | 0.70434 (19) | 0.0465 (5) | |
C6 | 0.1673 (3) | 0.2523 (3) | 0.6276 (3) | 0.0540 (6) | |
H6A | 0.1816 | 0.2848 | 0.7106 | 0.065* | |
C5 | 0.1021 (4) | 0.2337 (3) | 0.4205 (3) | 0.0572 (7) | |
H5A | 0.0612 | 0.2514 | 0.3309 | 0.069* | |
N2 | −0.0726 (3) | 0.5088 (2) | 0.7427 (2) | 0.0524 (6) | |
C4 | 0.3752 (3) | 0.5362 (3) | 0.6187 (3) | 0.0589 (7) | |
H4A | 0.3891 | 0.4588 | 0.6634 | 0.071* | |
C3 | 0.2697 (4) | 0.6958 (3) | 0.4980 (3) | 0.0689 (8) | |
H3A | 0.1933 | 0.7506 | 0.4416 | 0.083* | |
C2 | 0.1747 (4) | 0.1233 (3) | 0.4743 (3) | 0.0641 (8) | |
H2A | 0.1936 | 0.0525 | 0.4300 | 0.077* | |
C1 | 0.4309 (4) | 0.7167 (4) | 0.5461 (4) | 0.0789 (10) | |
H1A | 0.4858 | 0.7870 | 0.5299 | 0.095* | |
N1 | −0.1763 (4) | 0.5287 (3) | 0.7830 (3) | 0.0893 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0337 (3) | 0.0406 (3) | 0.0378 (3) | −0.00024 (17) | 0.00861 (18) | 0.00100 (17) |
N7 | 0.0412 (11) | 0.0439 (11) | 0.0455 (11) | 0.0035 (9) | 0.0106 (9) | 0.0021 (9) |
N6 | 0.0580 (14) | 0.0527 (13) | 0.0646 (15) | 0.0143 (11) | 0.0194 (11) | 0.0144 (11) |
N5 | 0.0396 (11) | 0.0540 (13) | 0.0505 (11) | −0.0062 (10) | 0.0131 (9) | −0.0019 (10) |
N4 | 0.0373 (12) | 0.104 (2) | 0.0753 (17) | −0.0122 (14) | 0.0171 (11) | −0.0165 (16) |
N3 | 0.0432 (12) | 0.0543 (13) | 0.0399 (11) | −0.0003 (9) | 0.0121 (9) | −0.0003 (9) |
C6 | 0.0570 (16) | 0.0510 (15) | 0.0502 (15) | 0.0072 (13) | 0.0141 (12) | 0.0019 (12) |
C5 | 0.0648 (17) | 0.0554 (16) | 0.0507 (14) | 0.0056 (14) | 0.0196 (13) | 0.0004 (13) |
N2 | 0.0493 (13) | 0.0621 (14) | 0.0424 (11) | −0.0024 (11) | 0.0119 (10) | 0.0095 (10) |
C4 | 0.0435 (15) | 0.0750 (18) | 0.0558 (16) | −0.0006 (14) | 0.0146 (13) | −0.0024 (14) |
C3 | 0.0563 (18) | 0.0672 (19) | 0.081 (2) | −0.0123 (15) | 0.0209 (15) | 0.0103 (16) |
C2 | 0.075 (2) | 0.0515 (16) | 0.0716 (19) | 0.0115 (15) | 0.0336 (16) | −0.0034 (14) |
C1 | 0.062 (2) | 0.085 (2) | 0.093 (2) | −0.0260 (18) | 0.0323 (18) | −0.0063 (19) |
N1 | 0.0642 (17) | 0.143 (3) | 0.0732 (18) | 0.0100 (17) | 0.0396 (15) | 0.0230 (17) |
Geometric parameters (Å, º) top
Ni1—N7i | 2.095 (2) | N4—C1 | 1.343 (4) |
Ni1—N7 | 2.095 (2) | N4—C4 | 1.344 (4) |
Ni1—N5i | 2.124 (2) | N4—H4B | 0.8600 |
Ni1—N5 | 2.124 (2) | N3—N2 | 1.183 (3) |
Ni1—N3i | 2.131 (2) | C6—H6A | 0.9300 |
Ni1—N3 | 2.131 (2) | C5—C2 | 1.349 (4) |
N7—C6 | 1.318 (3) | C5—H5A | 0.9300 |
N7—C5 | 1.364 (3) | N2—N1 | 1.160 (3) |
N6—C6 | 1.326 (3) | C4—H4A | 0.9300 |
N6—C2 | 1.357 (3) | C3—C1 | 1.343 (4) |
N6—H6B | 0.8600 | C3—H3A | 0.9300 |
N5—C4 | 1.308 (3) | C2—H2A | 0.9300 |
N5—C3 | 1.368 (3) | C1—H1A | 0.9300 |
| | | |
N7i—Ni1—N7 | 180.0 | C1—N4—C4 | 107.6 (3) |
N7i—Ni1—N5i | 91.2 (1) | C1—N4—H4B | 126.2 |
N7—Ni1—N5i | 88.8 (1) | C4—N4—H4B | 126.2 |
N7i—Ni1—N5 | 88.8 (1) | N2—N3—Ni1 | 121.28 (17) |
N7—Ni1—N5 | 91.2 (1) | N7—C6—N6 | 111.7 (2) |
N5i—Ni1—N5 | 180.0 | N7—C6—H6A | 124.1 |
N7i—Ni1—N3i | 87.9 (1) | N6—C6—H6A | 124.1 |
N7—Ni1—N3i | 92.1 (1) | C2—C5—N7 | 110.0 (2) |
N5i—Ni1—N3i | 90.4 (1) | C2—C5—H5A | 125.0 |
N5—Ni1—N3i | 89.6 (1) | N7—C5—H5A | 125.0 |
N7i—Ni1—N3 | 92.1 (1) | N1—N2—N3 | 177.9 (3) |
N7—Ni1—N3 | 87.9 (1) | N5—C4—N4 | 111.2 (3) |
N5i—Ni1—N3 | 89.6 (1) | N5—C4—H4A | 124.4 |
N5—Ni1—N3 | 90.4 (1) | N4—C4—H4A | 124.4 |
N3i—Ni1—N3 | 180.0 | C1—C3—N5 | 110.1 (3) |
C6—N7—C5 | 104.8 (2) | C1—C3—H3A | 124.9 |
C6—N7—Ni1 | 125.89 (17) | N5—C3—H3A | 124.9 |
C5—N7—Ni1 | 129.26 (17) | C5—C2—N6 | 106.0 (2) |
C6—N6—C2 | 107.4 (2) | C5—C2—H2A | 127.0 |
C6—N6—H6B | 126.3 | N6—C2—H2A | 127.0 |
C2—N6—H6B | 126.3 | N4—C1—C3 | 106.2 (3) |
C4—N5—C3 | 105.0 (2) | N4—C1—H1A | 126.9 |
C4—N5—Ni1 | 128.35 (19) | C3—C1—H1A | 126.9 |
C3—N5—Ni1 | 126.65 (18) | | |
Symmetry code: (i) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6B···N3ii | 0.86 | 2.06 | 2.858 (3) | 153 |
N4—H4B···N1iii | 0.86 | 2.09 | 2.929 (4) | 165 |
Symmetry codes: (ii) −x+1/2, y−1/2, −z+3/2; (iii) x+1, y, z. |
Experimental details
Crystal data |
Chemical formula | [Ni(N3)2(C3H4N2)4] |
Mr | 415.10 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.787 (1), 10.464 (1), 10.866 (1) |
β (°) | 110.67 (1) |
V (Å3) | 934.79 (17) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.07 |
Crystal size (mm) | 0.32 × 0.23 × 0.16 |
|
Data collection |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.706, 0.843 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2860, 1630, 1340 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.092, 1.06 |
No. of reflections | 1630 |
No. of parameters | 125 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.23 |
Selected geometric parameters (Å, º) topNi1—N7 | 2.095 (2) | N3—N2 | 1.183 (3) |
Ni1—N5 | 2.124 (2) | N2—N1 | 1.160 (3) |
Ni1—N3 | 2.131 (2) | | |
| | | |
N7—Ni1—N5i | 88.8 (1) | N7—Ni1—N3 | 87.9 (1) |
N7—Ni1—N5 | 91.2 (1) | N5—Ni1—N3 | 90.4 (1) |
N7—Ni1—N3i | 92.1 (1) | N2—N3—Ni1 | 121.28 (17) |
N5—Ni1—N3i | 89.6 (1) | N1—N2—N3 | 177.9 (3) |
Symmetry code: (i) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6B···N3ii | 0.86 | 2.06 | 2.858 (3) | 153 |
N4—H4B···N1iii | 0.86 | 2.09 | 2.929 (4) | 165 |
Symmetry codes: (ii) −x+1/2, y−1/2, −z+3/2; (iii) x+1, y, z. |
Nickel(II)–azido systems have been widely studied from structural and magnetic points of view in recent years. The azide ligand can act not only as a highly effective superexchange pathway, giving antiferromagnetic coupling for end-to-end coordination between two nickel ions or ferromagnetic coupling for end-on coordination, but can also generate different nuclearity compounds (Arriortua et al., 1990; Cortes et al., 1992; Vicente et al., 1993, 1995; Ribas et al., 1993; Escuer et al., 1995, 1996). On the other hand, nickel(II)–imidazole interactions are important in biological processes. We report herein the synthesis and crystal structure of a new compound, (I), simultaneously containing imidazole and azide ligands.
As shown in Fig. 1, the Ni atom is located at the inversion center of the molecule, and is coordinated by four imidazole ligands and two azide ligands. The Ni1—N7 and Ni1—N5 bond distances are 2.095 (2) and 2.124 (2) Å, respectively (Table 1). The Ni1—N3 bond distance is 2.131 (2) Å, which is longer than that found in other nickel–azide compounds [1.991 (5) (Escuer et al., 1996), 1.872 (5) (Becalska et al., 1992) and 2.018 (8) Å (Enemark, 1971)]. The complex forms a three-dimensional network through N—H···N intermolecular hydrogen bonds (Fig. 2 and Table 2).