


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808037902/ci2712sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808037902/ci2712Isup2.hkl |
CCDC reference: 712318
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean
(C-C) = 0.008 Å
- R factor = 0.056
- wR factor = 0.149
- Data-to-parameter ratio = 15.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for N3 -- N4 .. 21.42 su
Alert level C Value of measurement temperature given = 298.000 Value of melting point given = 0.000 PLAT220_ALERT_2_C Large Non-Solvent N Ueq(max)/Ueq(min) ... 3.45 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for N4 -- N5 .. 5.32 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N7 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT234_ALERT_4_C Large Hirshfeld Difference N6 -- N7 .. 0.12 Ang. PLAT234_ALERT_4_C Large Hirshfeld Difference C3 -- C4 .. 0.12 Ang.
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C24 H24 N16 Ni2 Atom count from _chemical_formula_moiety: PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 14
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
5,5'-Dimethyl-[2,2']bipyridine (2 mmol, 368.3 mg), sodium azide (4 mmol, 261.2 mg) and nickel acetate tetrahydrate (2 mmol, 497.8 mg) were dissolved in methanol (100 ml). The mixture was stirred for 30 min at room temperature to give a green solution. The solution was kept still in air for a week, green block-shaped crystals of the title complex were formed.
H atoms were positioned geometrically (C–H = 0.93-0.96 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(Cmethyl). The displacement ellipsoids of atoms N4 and N5 are extremely elongated and hence the Uij parameters of these atoms were restrained to an approximate isotropic behaviour. The distance between atoms N3 and N4 was restrained to 1.23 (1) Å and that between atoms N4 and N5 was restrained to 1.13 (1) Å.
Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![]() | Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. |
[Ni2(N3)4(C12H12N2)2] | F(000) = 672 |
Mr = 654.01 | Dx = 1.546 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1576 reflections |
a = 7.938 (2) Å | θ = 2.3–25.1° |
b = 15.067 (3) Å | µ = 1.39 mm−1 |
c = 11.755 (2) Å | T = 298 K |
β = 91.650 (2)° | Block, green |
V = 1405.3 (5) Å3 | 0.13 × 0.10 × 0.08 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 3060 independent reflections |
Radiation source: fine-focus sealed tube | 2165 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
ϕ and ω scan | θmax = 27.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −10→10 |
Tmin = 0.840, Tmax = 0.897 | k = −19→19 |
11588 measured reflections | l = −15→15 |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0643P)2 + 1.1062P] where P = (Fo2 + 2Fc2)/3 |
3060 reflections | (Δ/σ)max = 0.001 |
192 parameters | Δρmax = 0.67 e Å−3 |
14 restraints | Δρmin = −0.77 e Å−3 |
[Ni2(N3)4(C12H12N2)2] | V = 1405.3 (5) Å3 |
Mr = 654.01 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.938 (2) Å | µ = 1.39 mm−1 |
b = 15.067 (3) Å | T = 298 K |
c = 11.755 (2) Å | 0.13 × 0.10 × 0.08 mm |
β = 91.650 (2)° |
Bruker SMART CCD area-detector diffractometer | 3060 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2165 reflections with I > 2σ(I) |
Tmin = 0.840, Tmax = 0.897 | Rint = 0.063 |
11588 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 14 restraints |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.67 e Å−3 |
3060 reflections | Δρmin = −0.77 e Å−3 |
192 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | 0.03235 (7) | 0.44079 (4) | 0.11356 (5) | 0.0386 (2) | |
N1 | 0.2280 (5) | 0.3549 (3) | 0.1785 (4) | 0.0491 (10) | |
N2 | −0.0777 (5) | 0.3158 (3) | 0.0994 (3) | 0.0416 (9) | |
N3 | 0.0029 (5) | 0.5108 (3) | 0.2626 (4) | 0.0459 (11) | |
N4 | 0.0958 (8) | 0.5106 (4) | 0.3252 (5) | 0.0857 (18) | |
N5 | 0.1983 (12) | 0.5160 (6) | 0.4040 (7) | 0.144 (3) | |
N6 | 0.1668 (5) | 0.4913 (3) | −0.0170 (4) | 0.0583 (12) | |
N7 | 0.2901 (6) | 0.4579 (3) | −0.0571 (4) | 0.0594 (12) | |
N8 | 0.4096 (8) | 0.4282 (4) | −0.0950 (6) | 0.094 (2) | |
C1 | 0.1794 (6) | 0.2706 (3) | 0.1926 (4) | 0.0445 (11) | |
C2 | 0.2820 (7) | 0.2113 (4) | 0.2525 (5) | 0.0573 (14) | |
H2 | 0.2475 | 0.1529 | 0.2628 | 0.069* | |
C3 | 0.4356 (7) | 0.2398 (4) | 0.2967 (5) | 0.0632 (16) | |
H3 | 0.5057 | 0.2000 | 0.3357 | 0.076* | |
C4 | 0.4857 (6) | 0.3259 (4) | 0.2836 (5) | 0.0575 (14) | |
C5 | 0.3771 (6) | 0.3811 (4) | 0.2219 (5) | 0.0570 (14) | |
H5 | 0.4100 | 0.4396 | 0.2102 | 0.068* | |
C6 | 0.6485 (7) | 0.3623 (5) | 0.3348 (5) | 0.085 (2) | |
H6A | 0.6289 | 0.3847 | 0.4097 | 0.128* | |
H6B | 0.6886 | 0.4095 | 0.2878 | 0.128* | |
H6C | 0.7312 | 0.3159 | 0.3393 | 0.128* | |
C7 | 0.0139 (6) | 0.2474 (3) | 0.1428 (4) | 0.0442 (12) | |
C8 | −0.0506 (7) | 0.1625 (4) | 0.1383 (5) | 0.0626 (15) | |
H8 | 0.0127 | 0.1155 | 0.1680 | 0.075* | |
C9 | −0.2070 (8) | 0.1468 (4) | 0.0904 (5) | 0.0652 (16) | |
H9 | −0.2501 | 0.0894 | 0.0893 | 0.078* | |
C10 | −0.3023 (6) | 0.2160 (4) | 0.0433 (5) | 0.0530 (13) | |
C11 | −0.2308 (6) | 0.2993 (3) | 0.0520 (4) | 0.0477 (12) | |
H11 | −0.2925 | 0.3472 | 0.0233 | 0.057* | |
C12 | −0.4711 (7) | 0.2026 (4) | −0.0126 (5) | 0.0657 (16) | |
H12A | −0.5490 | 0.1824 | 0.0427 | 0.098* | |
H12B | −0.4629 | 0.1591 | −0.0719 | 0.098* | |
H12C | −0.5103 | 0.2577 | −0.0448 | 0.098* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0339 (3) | 0.0328 (3) | 0.0487 (4) | −0.0009 (3) | −0.0026 (2) | 0.0057 (3) |
N1 | 0.039 (2) | 0.048 (3) | 0.060 (3) | 0.0018 (19) | −0.003 (2) | 0.004 (2) |
N2 | 0.039 (2) | 0.040 (2) | 0.046 (2) | 0.0000 (17) | −0.0016 (18) | −0.0013 (17) |
N3 | 0.035 (2) | 0.036 (2) | 0.067 (3) | 0.0025 (18) | −0.006 (2) | −0.012 (2) |
N4 | 0.119 (5) | 0.043 (3) | 0.097 (5) | 0.001 (4) | 0.045 (4) | −0.006 (3) |
N5 | 0.165 (7) | 0.149 (6) | 0.115 (6) | −0.004 (6) | −0.029 (5) | 0.002 (5) |
N6 | 0.038 (2) | 0.066 (3) | 0.072 (3) | 0.010 (2) | 0.005 (2) | 0.021 (2) |
N7 | 0.051 (3) | 0.056 (3) | 0.070 (3) | 0.005 (2) | −0.002 (2) | 0.016 (2) |
N8 | 0.071 (4) | 0.105 (5) | 0.108 (5) | 0.037 (3) | 0.020 (3) | 0.011 (4) |
C1 | 0.048 (3) | 0.043 (3) | 0.043 (3) | 0.009 (2) | 0.004 (2) | 0.001 (2) |
C2 | 0.065 (4) | 0.048 (3) | 0.058 (3) | 0.010 (3) | 0.002 (3) | 0.002 (3) |
C3 | 0.058 (4) | 0.084 (4) | 0.047 (3) | 0.025 (3) | −0.009 (3) | 0.004 (3) |
C4 | 0.041 (3) | 0.080 (4) | 0.051 (3) | 0.008 (3) | 0.001 (2) | −0.001 (3) |
C5 | 0.044 (3) | 0.064 (4) | 0.063 (4) | −0.003 (3) | −0.001 (3) | 0.002 (3) |
C6 | 0.049 (3) | 0.131 (7) | 0.074 (4) | −0.001 (4) | −0.014 (3) | 0.003 (4) |
C7 | 0.049 (3) | 0.038 (3) | 0.046 (3) | 0.003 (2) | 0.004 (2) | 0.001 (2) |
C8 | 0.060 (4) | 0.047 (3) | 0.080 (4) | 0.003 (3) | −0.002 (3) | 0.013 (3) |
C9 | 0.067 (4) | 0.047 (3) | 0.081 (4) | −0.016 (3) | −0.001 (3) | 0.004 (3) |
C10 | 0.049 (3) | 0.056 (3) | 0.054 (3) | −0.008 (3) | 0.006 (2) | −0.004 (3) |
C11 | 0.045 (3) | 0.047 (3) | 0.050 (3) | 0.001 (2) | 0.001 (2) | 0.002 (2) |
C12 | 0.054 (3) | 0.075 (4) | 0.068 (4) | −0.020 (3) | −0.002 (3) | −0.009 (3) |
Ni1—N1 | 2.145 (4) | C3—H3 | 0.93 |
Ni1—N2 | 2.081 (4) | C4—C5 | 1.387 (7) |
Ni1—N3 | 2.064 (5) | C4—C6 | 1.512 (8) |
Ni1—N6 | 2.041 (4) | C5—H5 | 0.93 |
Ni1—N6i | 2.175 (4) | C6—H6A | 0.96 |
N1—C5 | 1.336 (6) | C6—H6B | 0.96 |
N1—C1 | 1.339 (6) | C6—H6C | 0.96 |
N2—C11 | 1.345 (6) | C7—C8 | 1.379 (7) |
N2—C7 | 1.352 (6) | C8—C9 | 1.369 (8) |
N3—N4 | 1.027 (6) | C8—H8 | 0.93 |
N4—N5 | 1.217 (7) | C9—C10 | 1.394 (8) |
N6—N7 | 1.209 (6) | C9—H9 | 0.93 |
N6—Ni1i | 2.175 (4) | C10—C11 | 1.380 (7) |
N7—N8 | 1.149 (7) | C10—C12 | 1.489 (7) |
C1—C2 | 1.387 (7) | C11—H11 | 0.93 |
C1—C7 | 1.465 (7) | C12—H12A | 0.96 |
C2—C3 | 1.380 (8) | C12—H12B | 0.96 |
C2—H2 | 0.93 | C12—H12C | 0.96 |
C3—C4 | 1.367 (8) | ||
N6—Ni1—N3 | 121.5 (2) | C3—C4—C6 | 123.2 (5) |
N6—Ni1—N2 | 120.32 (18) | C5—C4—C6 | 120.1 (6) |
N3—Ni1—N2 | 118.23 (17) | N1—C5—C4 | 123.5 (5) |
N6—Ni1—N1 | 95.97 (17) | N1—C5—H5 | 118.2 |
N3—Ni1—N1 | 96.02 (17) | C4—C5—H5 | 118.2 |
N2—Ni1—N1 | 77.30 (15) | C4—C6—H6A | 109.5 |
N6—Ni1—N6i | 79.63 (18) | C4—C6—H6B | 109.5 |
N3—Ni1—N6i | 95.99 (18) | H6A—C6—H6B | 109.5 |
N2—Ni1—N6i | 94.98 (16) | C4—C6—H6C | 109.5 |
N1—Ni1—N6i | 167.78 (18) | H6A—C6—H6C | 109.5 |
C5—N1—C1 | 119.3 (5) | H6B—C6—H6C | 109.5 |
C5—N1—Ni1 | 125.6 (4) | N2—C7—C8 | 119.8 (5) |
C1—N1—Ni1 | 114.1 (3) | N2—C7—C1 | 115.8 (4) |
C11—N2—C7 | 119.0 (4) | C8—C7—C1 | 124.3 (5) |
C11—N2—Ni1 | 124.9 (3) | C9—C8—C7 | 120.5 (5) |
C7—N2—Ni1 | 116.1 (3) | C9—C8—H8 | 119.8 |
N4—N3—Ni1 | 120.7 (5) | C7—C8—H8 | 119.8 |
N3—N4—N5 | 174.4 (8) | C8—C9—C10 | 120.6 (5) |
N7—N6—Ni1 | 125.8 (4) | C8—C9—H9 | 119.7 |
N7—N6—Ni1i | 125.2 (4) | C10—C9—H9 | 119.7 |
Ni1—N6—Ni1i | 100.37 (18) | C11—C10—C9 | 115.7 (5) |
N8—N7—N6 | 178.1 (6) | C11—C10—C12 | 121.3 (5) |
N1—C1—C2 | 120.5 (5) | C9—C10—C12 | 123.0 (5) |
N1—C1—C7 | 115.8 (4) | N2—C11—C10 | 124.3 (5) |
C2—C1—C7 | 123.8 (5) | N2—C11—H11 | 117.8 |
C3—C2—C1 | 119.3 (5) | C10—C11—H11 | 117.8 |
C3—C2—H2 | 120.3 | C10—C12—H12A | 109.5 |
C1—C2—H2 | 120.3 | C10—C12—H12B | 109.5 |
C4—C3—C2 | 120.7 (5) | H12A—C12—H12B | 109.5 |
C4—C3—H3 | 119.7 | C10—C12—H12C | 109.5 |
C2—C3—H3 | 119.7 | H12A—C12—H12C | 109.5 |
C3—C4—C5 | 116.7 (5) | H12B—C12—H12C | 109.5 |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ni2(N3)4(C12H12N2)2] |
Mr | 654.01 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 7.938 (2), 15.067 (3), 11.755 (2) |
β (°) | 91.650 (2) |
V (Å3) | 1405.3 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.39 |
Crystal size (mm) | 0.13 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.840, 0.897 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11588, 3060, 2165 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.149, 1.03 |
No. of reflections | 3060 |
No. of parameters | 192 |
No. of restraints | 14 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.77 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).
Ni1—N1 | 2.145 (4) | Ni1—N6 | 2.041 (4) |
Ni1—N2 | 2.081 (4) | Ni1—N6i | 2.175 (4) |
Ni1—N3 | 2.064 (5) |
Symmetry code: (i) −x, −y+1, −z. |
Polynuclear complexes play an important role in many fields, such as catalysis and magnetism (Dey et al., 2007; Jiang et al., 2005; Abramo et al., 2002). The main strategy for the design of the polynuclear complexes is to use suitable bridging ligands. In this paper, we report the synthesis and molecular structure of the title azide-bridged dinuclear nickel(II) complex derived from 5,5'-dimethyl-[2,2']bipyridine.
The molecule of the title complex is located on a crystallographic centre of inversion (Fig. 1). The complex contains two NiL (L is 5,5'-dimethyl-[2,2']bipyridine) units connected to each other by two bridging azide ligands. The NiII atom in the complex is five-coordinated by two N atoms of 5,5'-dimethyl-[2,2']bipyridine ligand and by three N atoms from three azide ligands in a trigonal-bipyramidal geometry. The bond lengths subtended at the metal center are within normal ranges (Song et al., 2007; Fu et al., 2005). The Ni···Ni distance is 3.2398 (12) Å.