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In the title complex, [Ni(N3)2(C3H4N2)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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016884/ob6176sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016884/ob6176Isup2.hkl
Contains datablock I

CCDC reference: 198310

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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








Comment top

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).

Experimental top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A perspective view of the locally expanded unit for (I). Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (A) −x, 1 − y, 1 − z.]
[Figure 2] Fig. 2. Cell packing diagram of (I) along the b axis. Hydrogen bonds are indicated by dashed lines.
(I) top
Crystal data top
[Ni(N3)2(C3H4N2)4]F(000) = 428
Mr = 415.10Dx = 1.475 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.787 (1) ÅCell parameters from 2860 reflections
b = 10.464 (1) Åθ = 2.0–25.0°
c = 10.866 (1) ŵ = 1.07 mm1
β = 110.67 (1)°T = 293 K
V = 934.79 (17) Å3Prism, blue
Z = 20.32 × 0.23 × 0.16 mm
Data collection top
Siemens SMART CCD
diffractometer
1630 independent reflections
Radiation source: fine-focus sealed tube1340 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ϕ and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 108
Tmin = 0.706, Tmax = 0.843k = 128
2860 measured reflectionsl = 612
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-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 reflectionsΔρmax = 0.25 e Å3
125 parametersΔρmin = 0.23 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.010 (2)
Crystal data top
[Ni(N3)2(C3H4N2)4]V = 934.79 (17) Å3
Mr = 415.10Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.787 (1) ŵ = 1.07 mm1
b = 10.464 (1) ÅT = 293 K
c = 10.866 (1) Å0.32 × 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 = 0.843Rint = 0.022
2860 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 1.06Δρmax = 0.25 e Å3
1630 reflectionsΔρmin = 0.23 e Å3
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
xyzUiso*/Ueq
Ni10.00000.50000.50000.03846 (19)
N70.0973 (2)0.31533 (18)0.51691 (19)0.0448 (5)
N60.2147 (3)0.1367 (2)0.6062 (2)0.0591 (6)
H6B0.26210.08050.66510.071*
N50.2344 (2)0.5822 (2)0.5441 (2)0.0488 (5)
N40.4970 (3)0.6155 (3)0.6224 (3)0.0731 (8)
H4B0.59880.60370.66570.088*
N30.0360 (3)0.49130 (19)0.70434 (19)0.0465 (5)
C60.1673 (3)0.2523 (3)0.6276 (3)0.0540 (6)
H6A0.18160.28480.71060.065*
C50.1021 (4)0.2337 (3)0.4205 (3)0.0572 (7)
H5A0.06120.25140.33090.069*
N20.0726 (3)0.5088 (2)0.7427 (2)0.0524 (6)
C40.3752 (3)0.5362 (3)0.6187 (3)0.0589 (7)
H4A0.38910.45880.66340.071*
C30.2697 (4)0.6958 (3)0.4980 (3)0.0689 (8)
H3A0.19330.75060.44160.083*
C20.1747 (4)0.1233 (3)0.4743 (3)0.0641 (8)
H2A0.19360.05250.43000.077*
C10.4309 (4)0.7167 (4)0.5461 (4)0.0789 (10)
H1A0.48580.78700.52990.095*
N10.1763 (4)0.5287 (3)0.7830 (3)0.0893 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0337 (3)0.0406 (3)0.0378 (3)0.00024 (17)0.00861 (18)0.00100 (17)
N70.0412 (11)0.0439 (11)0.0455 (11)0.0035 (9)0.0106 (9)0.0021 (9)
N60.0580 (14)0.0527 (13)0.0646 (15)0.0143 (11)0.0194 (11)0.0144 (11)
N50.0396 (11)0.0540 (13)0.0505 (11)0.0062 (10)0.0131 (9)0.0019 (10)
N40.0373 (12)0.104 (2)0.0753 (17)0.0122 (14)0.0171 (11)0.0165 (16)
N30.0432 (12)0.0543 (13)0.0399 (11)0.0003 (9)0.0121 (9)0.0003 (9)
C60.0570 (16)0.0510 (15)0.0502 (15)0.0072 (13)0.0141 (12)0.0019 (12)
C50.0648 (17)0.0554 (16)0.0507 (14)0.0056 (14)0.0196 (13)0.0004 (13)
N20.0493 (13)0.0621 (14)0.0424 (11)0.0024 (11)0.0119 (10)0.0095 (10)
C40.0435 (15)0.0750 (18)0.0558 (16)0.0006 (14)0.0146 (13)0.0024 (14)
C30.0563 (18)0.0672 (19)0.081 (2)0.0123 (15)0.0209 (15)0.0103 (16)
C20.075 (2)0.0515 (16)0.0716 (19)0.0115 (15)0.0336 (16)0.0034 (14)
C10.062 (2)0.085 (2)0.093 (2)0.0260 (18)0.0323 (18)0.0063 (19)
N10.0642 (17)0.143 (3)0.0732 (18)0.0100 (17)0.0396 (15)0.0230 (17)
Geometric parameters (Å, º) top
Ni1—N7i2.095 (2)N4—C11.343 (4)
Ni1—N72.095 (2)N4—C41.344 (4)
Ni1—N5i2.124 (2)N4—H4B0.8600
Ni1—N52.124 (2)N3—N21.183 (3)
Ni1—N3i2.131 (2)C6—H6A0.9300
Ni1—N32.131 (2)C5—C21.349 (4)
N7—C61.318 (3)C5—H5A0.9300
N7—C51.364 (3)N2—N11.160 (3)
N6—C61.326 (3)C4—H4A0.9300
N6—C21.357 (3)C3—C11.343 (4)
N6—H6B0.8600C3—H3A0.9300
N5—C41.308 (3)C2—H2A0.9300
N5—C31.368 (3)C1—H1A0.9300
N7i—Ni1—N7180.0C1—N4—C4107.6 (3)
N7i—Ni1—N5i91.2 (1)C1—N4—H4B126.2
N7—Ni1—N5i88.8 (1)C4—N4—H4B126.2
N7i—Ni1—N588.8 (1)N2—N3—Ni1121.28 (17)
N7—Ni1—N591.2 (1)N7—C6—N6111.7 (2)
N5i—Ni1—N5180.0N7—C6—H6A124.1
N7i—Ni1—N3i87.9 (1)N6—C6—H6A124.1
N7—Ni1—N3i92.1 (1)C2—C5—N7110.0 (2)
N5i—Ni1—N3i90.4 (1)C2—C5—H5A125.0
N5—Ni1—N3i89.6 (1)N7—C5—H5A125.0
N7i—Ni1—N392.1 (1)N1—N2—N3177.9 (3)
N7—Ni1—N387.9 (1)N5—C4—N4111.2 (3)
N5i—Ni1—N389.6 (1)N5—C4—H4A124.4
N5—Ni1—N390.4 (1)N4—C4—H4A124.4
N3i—Ni1—N3180.0C1—C3—N5110.1 (3)
C6—N7—C5104.8 (2)C1—C3—H3A124.9
C6—N7—Ni1125.89 (17)N5—C3—H3A124.9
C5—N7—Ni1129.26 (17)C5—C2—N6106.0 (2)
C6—N6—C2107.4 (2)C5—C2—H2A127.0
C6—N6—H6B126.3N6—C2—H2A127.0
C2—N6—H6B126.3N4—C1—C3106.2 (3)
C4—N5—C3105.0 (2)N4—C1—H1A126.9
C4—N5—Ni1128.35 (19)C3—C1—H1A126.9
C3—N5—Ni1126.65 (18)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6B···N3ii0.862.062.858 (3)153
N4—H4B···N1iii0.862.092.929 (4)165
Symmetry codes: (ii) x+1/2, y1/2, z+3/2; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula[Ni(N3)2(C3H4N2)4]
Mr415.10
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)8.787 (1), 10.464 (1), 10.866 (1)
β (°) 110.67 (1)
V3)934.79 (17)
Z2
Radiation typeMo Kα
µ (mm1)1.07
Crystal size (mm)0.32 × 0.23 × 0.16
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.706, 0.843
No. of measured, independent and
observed [I > 2σ(I)] reflections
2860, 1630, 1340
Rint0.022
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.092, 1.06
No. of reflections1630
No. of parameters125
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.23

Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens, 1994), SMART and SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1994), SHELXL97.

Selected geometric parameters (Å, º) top
Ni1—N72.095 (2)N3—N21.183 (3)
Ni1—N52.124 (2)N2—N11.160 (3)
Ni1—N32.131 (2)
N7—Ni1—N5i88.8 (1)N7—Ni1—N387.9 (1)
N7—Ni1—N591.2 (1)N5—Ni1—N390.4 (1)
N7—Ni1—N3i92.1 (1)N2—N3—Ni1121.28 (17)
N5—Ni1—N3i89.6 (1)N1—N2—N3177.9 (3)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6B···N3ii0.862.062.858 (3)153
N4—H4B···N1iii0.862.092.929 (4)165
Symmetry codes: (ii) x+1/2, y1/2, z+3/2; (iii) x+1, y, z.
 

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