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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021113/hg2232sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021113/hg2232Isup2.hkl
Contains datablock I

CCDC reference: 650526

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.030
  • wR factor = 0.069
  • Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT230_ALERT_2_C Hirshfeld Test Diff for N5 - N6 .. 6.63 su PLAT230_ALERT_2_C Hirshfeld Test Diff for N6 - N7 .. 5.73 su
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1 (2) 1.95
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

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.

Related literature top

For related literature, see: Albada et al. (2004); Atencio et al. (2004, 2005); Ding et al. (2005); Ghosh et al. (2006); Ghoshal et al. (2005); Sang & Xu (2006); Tadokoro & Nakasuji (2000); Xiao & Shreeve (2005).

Experimental top

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%).

Refinement top

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).

Structure description top

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.

For related literature, see: Albada et al. (2004); Atencio et al. (2004, 2005); Ding et al. (2005); Ghosh et al. (2006); Ghoshal et al. (2005); Sang & Xu (2006); Tadokoro & Nakasuji (2000); Xiao & Shreeve (2005).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of (I) with the unique atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The hydrogen-bonded network in (I). Hydrogen bonds are indicated by dashed lines.
Diazidobis(2,2'-biimidazole)nickel(II) top
Crystal data top
[Ni(N3)2(C6H6N4)2]F(000) = 840
Mr = 411.07Dx = 1.696 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 45 reflections
a = 12.6974 (18) Åθ = 4.6–23.7°
b = 8.8399 (10) ŵ = 1.24 mm1
c = 14.3537 (12) ÅT = 293 K
β = 91.803 (9)°Block, green
V = 1610.3 (3) Å30.26 × 0.20 × 0.16 mm
Z = 4
Data collection top
Bruker P4
diffractometer
1250 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.022
Graphite monochromatorθmax = 25.5°, θmin = 2.8°
ω scansh = 115
Absorption correction: psi scan
(North et al., 1968)
k = 110
Tmin = 0.743, Tmax = 0.820l = 1717
1966 measured reflections3 standard reflections every 97 reflections
1505 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H-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 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
[Ni(N3)2(C6H6N4)2]V = 1610.3 (3) Å3
Mr = 411.07Z = 4
Monoclinic, C2/cMo Kα radiation
a = 12.6974 (18) ŵ = 1.24 mm1
b = 8.8399 (10) ÅT = 293 K
c = 14.3537 (12) Å0.26 × 0.20 × 0.16 mm
β = 91.803 (9)°
Data collection top
Bruker P4
diffractometer
1250 reflections with I > 2σ(I)
Absorption correction: psi scan
(North et al., 1968)
Rint = 0.022
Tmin = 0.743, Tmax = 0.8203 standard reflections every 97 reflections
1966 measured reflections intensity decay: none
1505 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.069H-atom parameters constrained
S = 1.02Δρmax = 0.22 e Å3
1505 reflectionsΔρmin = 0.20 e Å3
124 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. 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
Ni10.25000.75000.50000.04159 (13)
N10.23120 (16)0.5740 (2)0.40210 (14)0.0440 (5)
N20.27795 (17)0.3433 (2)0.36366 (14)0.0474 (5)
H2A0.30970.25740.36550.057*
N30.34697 (15)0.5856 (2)0.56318 (13)0.0429 (5)
N40.42338 (16)0.3636 (2)0.54714 (13)0.0452 (5)
H4A0.43990.27760.52370.054*
N50.11730 (17)0.6639 (2)0.57324 (15)0.0486 (5)
N60.10387 (17)0.5322 (3)0.57872 (14)0.0477 (5)
N70.0897 (2)0.4015 (3)0.58536 (18)0.0629 (6)
C10.1773 (2)0.5320 (3)0.32153 (18)0.0504 (6)
H1A0.12870.59210.28880.061*
C20.2057 (2)0.3902 (3)0.29705 (18)0.0529 (7)
H2B0.18110.33560.24540.063*
C30.29009 (19)0.4563 (3)0.42548 (16)0.0407 (5)
C40.35389 (18)0.4631 (3)0.51081 (16)0.0404 (5)
C50.4630 (2)0.4248 (3)0.62848 (17)0.0496 (6)
H5A0.51250.38120.66940.060*
C60.4157 (2)0.5619 (3)0.63756 (17)0.0495 (6)
H6A0.42800.62920.68650.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0441 (2)0.0386 (2)0.0415 (2)0.0114 (2)0.00750 (18)0.00495 (19)
N10.0469 (11)0.0422 (12)0.0424 (11)0.0072 (10)0.0066 (9)0.0045 (9)
N20.0542 (12)0.0404 (12)0.0476 (11)0.0076 (10)0.0004 (10)0.0068 (10)
N30.0432 (11)0.0445 (12)0.0406 (10)0.0109 (10)0.0050 (9)0.0037 (9)
N40.0485 (12)0.0412 (11)0.0458 (11)0.0139 (10)0.0017 (9)0.0006 (9)
N50.0504 (12)0.0400 (13)0.0550 (13)0.0096 (10)0.0016 (10)0.0034 (10)
N60.0444 (12)0.0507 (15)0.0474 (12)0.0132 (11)0.0072 (10)0.0071 (10)
N70.0670 (16)0.0400 (14)0.0808 (17)0.0074 (12)0.0097 (13)0.0061 (12)
C10.0517 (15)0.0522 (16)0.0468 (14)0.0053 (13)0.0088 (12)0.0015 (12)
C20.0585 (16)0.0552 (17)0.0444 (14)0.0006 (14)0.0080 (12)0.0089 (12)
C30.0417 (12)0.0394 (13)0.0412 (12)0.0044 (11)0.0022 (10)0.0024 (10)
C40.0387 (12)0.0402 (13)0.0423 (12)0.0074 (11)0.0015 (10)0.0012 (10)
C50.0474 (14)0.0569 (17)0.0443 (13)0.0162 (13)0.0045 (11)0.0046 (12)
C60.0481 (14)0.0573 (16)0.0426 (13)0.0131 (13)0.0065 (11)0.0039 (12)
Geometric parameters (Å, º) top
Ni1—N32.0931 (19)N4—C41.339 (3)
Ni1—N3i2.0931 (19)N4—C51.368 (3)
Ni1—N12.105 (2)N4—H4A0.8600
Ni1—N1i2.105 (2)N5—N61.180 (3)
Ni1—N52.153 (2)N6—N71.173 (3)
Ni1—N5i2.153 (2)C1—C21.354 (4)
N1—C31.319 (3)C1—H1A0.9300
N1—C11.376 (3)C2—H2B0.9300
N2—C31.342 (3)C3—C41.448 (3)
N2—C21.368 (3)C5—C61.361 (4)
N2—H2A0.8600C5—H5A0.9300
N3—C41.323 (3)C6—H6A0.9300
N3—C61.374 (3)
N3—Ni1—N3i180.00 (9)C4—N4—C5107.1 (2)
N3—Ni1—N180.13 (8)C4—N4—H4A126.5
N3i—Ni1—N199.87 (8)C5—N4—H4A126.5
N3—Ni1—N1i99.87 (8)N6—N5—Ni1119.90 (18)
N3i—Ni1—N1i80.13 (8)N7—N6—N5179.0 (3)
N1—Ni1—N1i180.0C2—C1—N1109.8 (2)
N3—Ni1—N590.09 (8)C2—C1—H1A125.1
N3i—Ni1—N589.91 (8)N1—C1—H1A125.1
N1—Ni1—N589.46 (8)C1—C2—N2106.1 (2)
N1i—Ni1—N590.54 (8)C1—C2—H2B127.0
N3—Ni1—N5i89.91 (8)N2—C2—H2B127.0
N3i—Ni1—N5i90.09 (8)N1—C3—N2111.5 (2)
N1—Ni1—N5i90.54 (8)N1—C3—C4118.7 (2)
N1i—Ni1—N5i89.46 (8)N2—C3—C4129.8 (2)
N5—Ni1—N5i180.0N3—C4—N4111.8 (2)
C3—N1—C1105.3 (2)N3—C4—C3118.0 (2)
C3—N1—Ni1111.22 (15)N4—C4—C3130.2 (2)
C1—N1—Ni1143.43 (18)C6—C5—N4106.4 (2)
C3—N2—C2107.3 (2)C6—C5—H5A126.8
C3—N2—H2A126.3N4—C5—H5A126.8
C2—N2—H2A126.3C5—C6—N3109.4 (2)
C4—N3—C6105.4 (2)C5—C6—H6A125.3
C4—N3—Ni1111.78 (15)N3—C6—H6A125.3
C6—N3—Ni1142.48 (18)
Symmetry code: (i) x+1/2, y+3/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N7ii0.862.012.822 (3)157
N4—H4A···N7ii0.862.253.020 (3)149
N4—H4A···N5iii0.862.553.044 (3)118
Symmetry codes: (ii) x+1/2, y+1/2, z+1; (iii) x+1/2, y1/2, z.

Experimental details

Crystal data
Chemical formula[Ni(N3)2(C6H6N4)2]
Mr411.07
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)12.6974 (18), 8.8399 (10), 14.3537 (12)
β (°) 91.803 (9)
V3)1610.3 (3)
Z4
Radiation typeMo Kα
µ (mm1)1.24
Crystal size (mm)0.26 × 0.20 × 0.16
Data collection
DiffractometerBruker P4
Absorption correctionPsi scan
(North et al., 1968)
Tmin, Tmax0.743, 0.820
No. of measured, independent and
observed [I > 2σ(I)] reflections
1966, 1505, 1250
Rint0.022
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.069, 1.02
No. of reflections1505
No. of parameters124
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.20

Computer programs: XSCANS (Bruker, 1997), XSCANS, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N7i0.862.012.822 (3)156.9
N4—H4A···N7i0.862.253.020 (3)148.9
N4—H4A···N5ii0.862.553.044 (3)117.71
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+1/2, y1/2, z.
 

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