Acta Cryst. (2007). E63, m1570 [ doi:10.1107/S1600536807021113 ]
Green single crystals of the title compound, [Ni(N3)2(C6H6N4)2], were obtained by reacting nickel(II) perchlorate with 2,2'-biimidazole (H2bim) and sodium azide. The azide and H2bim ligands are bonded to the Ni atom, which lies on an inversion centre, with approximately octahedral geometry. The azide anions are terminally bonded in two trans postitions. A two-dimensional supramolecular network is formed through hydrogen bonds between ligand H2bim and azide N atoms.
The ligand 2,2'-biimidazoline (H2bim) was prepared according to the method reported in the literature (Xiao & Shreeve, 2005). A solid of 2,2'-biimidazoline (0.2 mmol) was added to the methanol solution (8 ml) of Ni(ClO4)2.6H2O (0.1 mmol) and a reseda solution was obtained. To the solution, a aqueous solution (5 ml) o f NaN3 (0.6 mmol) was added carefully. The mixture was filtered and slowly evaporated to generate grass green single crystals suitable for X-ray diffraction analysis. (Yield 50%). Elemental analysis [found (calculated)] for C12H12N14Ni: C 35.40 (35.12), H 3.01 (2.95), N 47.65% (47.81%).
H atoms bound to C and N atoms were visible in difference maps and were placed using the HFIX commands in SHELXL97. All H atoms were allowed for as riding atoms (C—H 0.97 Å, N—H 0.86 Å).
Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
![[Figure 1]](./hg2232fig1thm.gif)
| Fig. 1. A view of (I) with the unique atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./hg2232fig2thm.gif)
| Fig. 2. The hydrogen-bonded network in (I). Hydrogen bonds are indicated by dashed lines. |
| [Ni(N3)2(C6H6N4)2] | F(000) = 840 |
| Mr = 411.07 | Dx = 1.696 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 45 reflections |
| a = 12.6974 (18) Å | θ = 4.6–23.7° |
| b = 8.8399 (10) Å | µ = 1.24 mm−1 |
| c = 14.3537 (12) Å | T = 293 K |
| β = 91.803 (9)° | Block, green |
| V = 1610.3 (3) Å3 | 0.26 × 0.20 × 0.16 mm |
| Z = 4 |
| Bruker P4 diffractometer | 1250 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.022 |
| graphite | θmax = 25.5°, θmin = 2.8° |
| ω scans | h = −1→15 |
| Absorption correction: psi scan (North et al., 1968) | k = −1→10 |
| Tmin = 0.743, Tmax = 0.820 | l = −17→17 |
| 1966 measured reflections | 3 standard reflections every 97 reflections |
| 1505 independent reflections | intensity decay: none |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.069 | H-atom parameters constrained |
| S = 1.02 | w = 1/[σ2(Fo2) + (0.001P)2 + 2.2P] where P = (Fo2 + 2Fc2)/3 |
| 1505 reflections | (Δ/σ)max < 0.001 |
| 124 parameters | Δρmax = 0.22 e Å−3 |
| 0 restraints | Δρmin = −0.20 e Å−3 |
| [Ni(N3)2(C6H6N4)2] | V = 1610.3 (3) Å3 |
| Mr = 411.07 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 12.6974 (18) Å | µ = 1.24 mm−1 |
| b = 8.8399 (10) Å | T = 293 K |
| c = 14.3537 (12) Å | 0.26 × 0.20 × 0.16 mm |
| β = 91.803 (9)° |
| Bruker P4 diffractometer | 1250 reflections with I > 2σ(I) |
| Absorption correction: psi scan (North et al., 1968) | Rint = 0.022 |
| Tmin = 0.743, Tmax = 0.820 | θmax = 25.5° |
| 1966 measured reflections | 3 standard reflections every 97 reflections |
| 1505 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
| wR(F2) = 0.069 | Δρmax = 0.22 e Å−3 |
| S = 1.02 | Δρmin = −0.20 e Å−3 |
| 1505 reflections | Absolute structure: ? |
| 124 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| Ni1 | 0.2500 | 0.7500 | 0.5000 | 0.04159 (13) | |
| N1 | 0.23120 (16) | 0.5740 (2) | 0.40210 (14) | 0.0440 (5) | |
| N2 | 0.27795 (17) | 0.3433 (2) | 0.36366 (14) | 0.0474 (5) | |
| H2A | 0.3097 | 0.2574 | 0.3655 | 0.057* | |
| N3 | 0.34697 (15) | 0.5856 (2) | 0.56318 (13) | 0.0429 (5) | |
| N4 | 0.42338 (16) | 0.3636 (2) | 0.54714 (13) | 0.0452 (5) | |
| H4A | 0.4399 | 0.2776 | 0.5237 | 0.054* | |
| N5 | 0.11730 (17) | 0.6639 (2) | 0.57324 (15) | 0.0486 (5) | |
| N6 | 0.10387 (17) | 0.5322 (3) | 0.57872 (14) | 0.0477 (5) | |
| N7 | 0.0897 (2) | 0.4015 (3) | 0.58536 (18) | 0.0629 (6) | |
| C1 | 0.1773 (2) | 0.5320 (3) | 0.32153 (18) | 0.0504 (6) | |
| H1A | 0.1287 | 0.5921 | 0.2888 | 0.061* | |
| C2 | 0.2057 (2) | 0.3902 (3) | 0.29705 (18) | 0.0529 (7) | |
| H2B | 0.1811 | 0.3356 | 0.2454 | 0.063* | |
| C3 | 0.29009 (19) | 0.4563 (3) | 0.42548 (16) | 0.0407 (5) | |
| C4 | 0.35389 (18) | 0.4631 (3) | 0.51081 (16) | 0.0404 (5) | |
| C5 | 0.4630 (2) | 0.4248 (3) | 0.62848 (17) | 0.0496 (6) | |
| H5A | 0.5125 | 0.3812 | 0.6694 | 0.060* | |
| C6 | 0.4157 (2) | 0.5619 (3) | 0.63756 (17) | 0.0495 (6) | |
| H6A | 0.4280 | 0.6292 | 0.6865 | 0.059* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.0441 (2) | 0.0386 (2) | 0.0415 (2) | 0.0114 (2) | −0.00750 (18) | −0.00495 (19) |
| N1 | 0.0469 (11) | 0.0422 (12) | 0.0424 (11) | 0.0072 (10) | −0.0066 (9) | −0.0045 (9) |
| N2 | 0.0542 (12) | 0.0404 (12) | 0.0476 (11) | 0.0076 (10) | −0.0004 (10) | −0.0068 (10) |
| N3 | 0.0432 (11) | 0.0445 (12) | 0.0406 (10) | 0.0109 (10) | −0.0050 (9) | −0.0037 (9) |
| N4 | 0.0485 (12) | 0.0412 (11) | 0.0458 (11) | 0.0139 (10) | 0.0017 (9) | 0.0006 (9) |
| N5 | 0.0504 (12) | 0.0400 (13) | 0.0550 (13) | 0.0096 (10) | −0.0016 (10) | −0.0034 (10) |
| N6 | 0.0444 (12) | 0.0507 (15) | 0.0474 (12) | 0.0132 (11) | −0.0072 (10) | −0.0071 (10) |
| N7 | 0.0670 (16) | 0.0400 (14) | 0.0808 (17) | 0.0074 (12) | −0.0097 (13) | −0.0061 (12) |
| C1 | 0.0517 (15) | 0.0522 (16) | 0.0468 (14) | 0.0053 (13) | −0.0088 (12) | −0.0015 (12) |
| C2 | 0.0585 (16) | 0.0552 (17) | 0.0444 (14) | −0.0006 (14) | −0.0080 (12) | −0.0089 (12) |
| C3 | 0.0417 (12) | 0.0394 (13) | 0.0412 (12) | 0.0044 (11) | 0.0022 (10) | −0.0024 (10) |
| C4 | 0.0387 (12) | 0.0402 (13) | 0.0423 (12) | 0.0074 (11) | 0.0015 (10) | 0.0012 (10) |
| C5 | 0.0474 (14) | 0.0569 (17) | 0.0443 (13) | 0.0162 (13) | −0.0045 (11) | 0.0046 (12) |
| C6 | 0.0481 (14) | 0.0573 (16) | 0.0426 (13) | 0.0131 (13) | −0.0065 (11) | −0.0039 (12) |
| Ni1—N3 | 2.0931 (19) | N4—C4 | 1.339 (3) |
| Ni1—N3i | 2.0931 (19) | N4—C5 | 1.368 (3) |
| Ni1—N1 | 2.105 (2) | N4—H4A | 0.8600 |
| Ni1—N1i | 2.105 (2) | N5—N6 | 1.180 (3) |
| Ni1—N5 | 2.153 (2) | N6—N7 | 1.173 (3) |
| Ni1—N5i | 2.153 (2) | C1—C2 | 1.354 (4) |
| N1—C3 | 1.319 (3) | C1—H1A | 0.9300 |
| N1—C1 | 1.376 (3) | C2—H2B | 0.9300 |
| N2—C3 | 1.342 (3) | C3—C4 | 1.448 (3) |
| N2—C2 | 1.368 (3) | C5—C6 | 1.361 (4) |
| N2—H2A | 0.8600 | C5—H5A | 0.9300 |
| N3—C4 | 1.323 (3) | C6—H6A | 0.9300 |
| N3—C6 | 1.374 (3) | ||
| N3—Ni1—N3i | 180.00 (9) | C4—N4—C5 | 107.1 (2) |
| N3—Ni1—N1 | 80.13 (8) | C4—N4—H4A | 126.5 |
| N3i—Ni1—N1 | 99.87 (8) | C5—N4—H4A | 126.5 |
| N3—Ni1—N1i | 99.87 (8) | N6—N5—Ni1 | 119.90 (18) |
| N3i—Ni1—N1i | 80.13 (8) | N7—N6—N5 | 179.0 (3) |
| N1—Ni1—N1i | 180.0 | C2—C1—N1 | 109.8 (2) |
| N3—Ni1—N5 | 90.09 (8) | C2—C1—H1A | 125.1 |
| N3i—Ni1—N5 | 89.91 (8) | N1—C1—H1A | 125.1 |
| N1—Ni1—N5 | 89.46 (8) | C1—C2—N2 | 106.1 (2) |
| N1i—Ni1—N5 | 90.54 (8) | C1—C2—H2B | 127.0 |
| N3—Ni1—N5i | 89.91 (8) | N2—C2—H2B | 127.0 |
| N3i—Ni1—N5i | 90.09 (8) | N1—C3—N2 | 111.5 (2) |
| N1—Ni1—N5i | 90.54 (8) | N1—C3—C4 | 118.7 (2) |
| N1i—Ni1—N5i | 89.46 (8) | N2—C3—C4 | 129.8 (2) |
| N5—Ni1—N5i | 180.0 | N3—C4—N4 | 111.8 (2) |
| C3—N1—C1 | 105.3 (2) | N3—C4—C3 | 118.0 (2) |
| C3—N1—Ni1 | 111.22 (15) | N4—C4—C3 | 130.2 (2) |
| C1—N1—Ni1 | 143.43 (18) | C6—C5—N4 | 106.4 (2) |
| C3—N2—C2 | 107.3 (2) | C6—C5—H5A | 126.8 |
| C3—N2—H2A | 126.3 | N4—C5—H5A | 126.8 |
| C2—N2—H2A | 126.3 | C5—C6—N3 | 109.4 (2) |
| C4—N3—C6 | 105.4 (2) | C5—C6—H6A | 125.3 |
| C4—N3—Ni1 | 111.78 (15) | N3—C6—H6A | 125.3 |
| C6—N3—Ni1 | 142.48 (18) |
| Symmetry codes: (i) −x+1/2, −y+3/2, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···N7ii | 0.86 | 2.01 | 2.822 (3) | 157 |
| N4—H4A···N7ii | 0.86 | 2.25 | 3.020 (3) | 149 |
| N4—H4A···N5iii | 0.86 | 2.55 | 3.044 (3) | 118 |
| Symmetry codes: (ii) −x+1/2, −y+1/2, −z+1; (iii) x+1/2, y−1/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···N7i | 0.86 | 2.01 | 2.822 (3) | 157 |
| N4—H4A···N7i | 0.86 | 2.25 | 3.020 (3) | 149 |
| N4—H4A···N5ii | 0.86 | 2.55 | 3.044 (3) | 118 |
| Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x+1/2, y−1/2, z. |
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2,2'-biimidazole and its monoanion ligand Hbim- as well as its hydrogenated derivative 2,2'-biimidazoline play an important role in the molecular self-assembly and molecular recognition in chemical, physical and biological sciences, since they not only can be coordinated to metal centers as bidentate chelate but can act as donors in hydrogen bonding interactions usually leading to higher dimensional supramolecular structures (Atencio et al., 2004; Ghosh et al., 2006; Tadokoro & Nakasuji, 2000).
To date, a variety of supramolecular architectures involving polynuclear, one-, two- and three-dimensional molecular arrangements have been obtained based on the above mentioned multifunctional ligands (Atencio et al., 2005; Ding et al., 2005; Sang & Xu, 2006; Tadokoro & Nakasuji, 2000). More recntly, two novel dicyanamido-bridged one-dimensional polymeric complexes of manganese(II) have been reported using 2,2'-biimidazole as a bidentate chelate (Ghoshal et al., 2005). It is well known that azide anion is an excellent bridging ligand and a good hydrogen bonds acceptant. Therefore, we hoped to obtain azide-bridged and hydrogen bonds-connected higher dimensional structures based on 2,2'-biimidazole and azide ligands and transitional metal ions through the control of their molar ratios. However, only a mononuclear complex Ni(H2bim)2(N3)2, (I), was obtained, and its molecular structure was reported herein.
An ORTEP drawing of the title complex is shown in Fig. 1. In the complex Ni(H2bim)2(N3)2, the central Ni atom is hexacoordinated by six N atoms from two H2bim ligands and two azide ions leading to an approximately octahedral structure. The basal plane of the octahedral coordination of the Ni(II) atom is formed by four N atoms from two bidentate chelating H2bim and the apical position is occupied by N atoms of two azide groups. The Ni—N bond distances range from from 2.0931 (19)Å to 2.153 (2) Å, which are similar to those of Ni—N bond in complex [Ni(N3)2(C6H10N4)2] (Albada et al., 2004). The Ni1—N5—N6 bond angle is 119.90 (18)°. The azide anion is nearly linear [N5—N6—N7 = 179.0 (3)°]. The N—N bond lengths of 1.180 (3)Å for N5—N6 and 1.173 (3)Å for N6—N7 are normal.
The Ni(H2bim)2(N3)2 units are connected together by the intermolecular hydrogen bonds involving uncoordinated H2bim ligand and azide nitrogen atoms as well as coordinated azide nitrogen atoms leading to two-dimensional supramolecular network.
In the IR spectrum the azide vibration is observed at 2053 cm-1.