The structure determination of the title compound, [Ni(C
4H
13N
3)
2][Ni(CN)
4], reveals the presence of a complex [Ni(dien)
2]
2+ cation (dien is diethylenetriamine) and a pair of crystallographically independent half-complex [Ni(CN)
4]
2- anions in the asymmetric unit. The Ni atoms of the anions lie on crystallographic inversion centres. In the cationic unit, the ligand geometry around the nickel(II) is distorted octahedral, with the two dien ligands coordinated in
mer fashion, whereas in the anionic unit, the geometry of the nickel(II) atom is square planar. The crystal structure shows a three-dimensional hydrogen-bonding network involving alternating anionic and cationic rows placed in the (1
1) plane.
Supporting information
CCDC reference: 221621
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.012 Å
- R factor = 0.042
- wR factor = 0.078
- Data-to-parameter ratio = 15.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
GOODF_01 Alert C The least squares goodness of fit parameter lies
outside the range 0.80 <> 2.00
Goodness of fit given = 0.701
RINTA_01 Alert C The value of Rint is greater than 0.10
Rint given 0.121
PLAT_420 Alert C D-H Without Acceptor N24 - H24 ... ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check
Data collection: IPDS (Stoe & Cie, 1996); cell refinement: IPDS; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: DIRDIF99.2 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2002); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
Crystal data top
[Ni(C4H13N3)2][Ni(CN)4] | F(000) = 896 |
Mr = 427.85 | Dx = 1.403 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4000 reflections |
a = 15.138 (2) Å | θ = 2.7–30° |
b = 9.458 (1) Å | µ = 1.87 mm−1 |
c = 15.248 (2) Å | T = 293 K |
β = 111.884 (16)° | Needle, violet |
V = 2025.8 (5) Å3 | 0.51 × 0.11 × 0.09 mm |
Z = 4 | |
Data collection top
Stoe IPDS area-detector diffractometer | 3410 independent reflections |
Radiation source: fine-focus sealed tube | 1449 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.121 |
φ scans | θmax = 25°, θmin = 2.7° |
Absorption correction: analytical (X-RED; Stoe & Cie, 1996) | h = −18→18 |
Tmin = 0.744, Tmax = 0.897 | k = −11→11 |
11730 measured reflections | l = −18→18 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.042 | w = 1/[σ2(Fo2) + (0.013P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.078 | (Δ/σ)max = 0.001 |
S = 0.70 | Δρmax = 0.26 e Å−3 |
3410 reflections | Δρmin = −0.47 e Å−3 |
218 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00329 (18) |
Primary atom site location: structure-invariant direct methods | |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.74212 (6) | 0.06579 (8) | 0.20575 (6) | 0.0411 (2) | |
Ni2 | 0.5000 | 0.5000 | 0.0000 | 0.0434 (3) | |
Ni3 | 1.0000 | 0.5000 | 0.5000 | 0.0561 (4) | |
C1 | 0.4986 (5) | 0.3125 (8) | −0.0333 (4) | 0.0486 (19) | |
N1 | 0.4997 (4) | 0.1949 (7) | −0.0539 (4) | 0.0632 (18) | |
C2 | 0.3961 (5) | 0.4715 (7) | 0.0379 (4) | 0.052 (2) | |
N2 | 0.3341 (5) | 0.4561 (7) | 0.0606 (4) | 0.077 (2) | |
C3 | 0.8843 (6) | 0.4112 (8) | 0.4798 (5) | 0.061 (2) | |
N3 | 0.8140 (5) | 0.3553 (7) | 0.4674 (5) | 0.080 (2) | |
C4 | 1.0105 (5) | 0.3894 (10) | 0.4042 (6) | 0.089 (3) | |
N4 | 1.0171 (5) | 0.3193 (10) | 0.3467 (6) | 0.128 (4) | |
N11 | 0.6833 (3) | −0.0009 (6) | 0.0616 (3) | 0.0498 (13) | |
H11A | 0.6198 | −0.0100 | 0.0428 | 0.060* | |
H11B | 0.6959 | 0.0637 | 0.0245 | 0.060* | |
C12 | 0.7265 (5) | −0.1383 (7) | 0.0537 (5) | 0.0553 (19) | |
H12A | 0.7817 | −0.1225 | 0.0372 | 0.066* | |
H12B | 0.6809 | −0.1942 | 0.0040 | 0.066* | |
C13 | 0.7563 (5) | −0.2185 (7) | 0.1468 (5) | 0.059 (2) | |
H13A | 0.7006 | −0.2475 | 0.1592 | 0.071* | |
H13B | 0.7922 | −0.3023 | 0.1443 | 0.071* | |
N14 | 0.8148 (4) | −0.1240 (5) | 0.2209 (4) | 0.0510 (15) | |
H14 | 0.8699 | −0.1075 | 0.2117 | 0.061* | |
C15 | 0.8392 (6) | −0.1766 (7) | 0.3189 (5) | 0.067 (2) | |
H15A | 0.8837 | −0.2549 | 0.3315 | 0.080* | |
H15B | 0.7824 | −0.2086 | 0.3282 | 0.080* | |
C16 | 0.8833 (5) | −0.0548 (9) | 0.3825 (5) | 0.073 (2) | |
H16A | 0.9420 | −0.0278 | 0.3753 | 0.087* | |
H16B | 0.8984 | −0.0825 | 0.4478 | 0.087* | |
N17 | 0.8159 (4) | 0.0687 (6) | 0.3588 (3) | 0.0625 (16) | |
H17A | 0.8481 | 0.1502 | 0.3774 | 0.075* | |
H17B | 0.7741 | 0.0601 | 0.3877 | 0.075* | |
N21 | 0.6148 (3) | −0.0065 (6) | 0.2277 (3) | 0.0541 (14) | |
H21A | 0.5856 | −0.0746 | 0.1856 | 0.065* | |
H21B | 0.6310 | −0.0427 | 0.2862 | 0.065* | |
C22 | 0.5505 (5) | 0.1139 (8) | 0.2158 (5) | 0.069 (2) | |
H22A | 0.5151 | 0.1025 | 0.2569 | 0.083* | |
H22B | 0.5052 | 0.1171 | 0.1510 | 0.083* | |
C23 | 0.6056 (6) | 0.2499 (8) | 0.2391 (5) | 0.071 (2) | |
H23A | 0.5623 | 0.3297 | 0.2222 | 0.085* | |
H23B | 0.6429 | 0.2546 | 0.3064 | 0.085* | |
N24 | 0.6693 (4) | 0.2550 (5) | 0.1853 (4) | 0.0578 (17) | |
H24 | 0.6319 | 0.2609 | 0.1229 | 0.069* | |
C25 | 0.7366 (7) | 0.3720 (6) | 0.2070 (6) | 0.074 (2) | |
H25A | 0.7712 | 0.3795 | 0.2747 | 0.089* | |
H25B | 0.7036 | 0.4605 | 0.1841 | 0.089* | |
C26 | 0.8037 (7) | 0.3390 (9) | 0.1574 (6) | 0.086 (3) | |
H26A | 0.7694 | 0.3430 | 0.0896 | 0.103* | |
H26B | 0.8539 | 0.4093 | 0.1742 | 0.103* | |
N27 | 0.8458 (4) | 0.1971 (6) | 0.1842 (4) | 0.0606 (17) | |
H27A | 0.8981 | 0.2022 | 0.2376 | 0.073* | |
H27B | 0.8627 | 0.1613 | 0.1381 | 0.073* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0417 (5) | 0.0425 (5) | 0.0377 (4) | −0.0059 (4) | 0.0132 (4) | −0.0038 (4) |
Ni2 | 0.0446 (7) | 0.0459 (7) | 0.0375 (7) | −0.0034 (6) | 0.0129 (6) | −0.0074 (6) |
Ni3 | 0.0487 (8) | 0.0756 (9) | 0.0462 (8) | −0.0137 (7) | 0.0202 (7) | −0.0184 (7) |
C1 | 0.033 (4) | 0.059 (5) | 0.048 (4) | −0.013 (3) | 0.009 (4) | −0.011 (3) |
N1 | 0.045 (4) | 0.061 (4) | 0.076 (4) | −0.009 (3) | 0.014 (3) | −0.021 (3) |
C2 | 0.054 (4) | 0.051 (5) | 0.054 (4) | −0.015 (3) | 0.023 (4) | −0.019 (3) |
N2 | 0.071 (4) | 0.092 (6) | 0.082 (4) | −0.020 (4) | 0.043 (4) | −0.028 (4) |
C3 | 0.064 (5) | 0.080 (6) | 0.044 (4) | −0.019 (5) | 0.025 (4) | −0.021 (4) |
N3 | 0.076 (5) | 0.101 (5) | 0.077 (5) | −0.037 (4) | 0.042 (4) | −0.040 (4) |
C4 | 0.041 (4) | 0.146 (9) | 0.085 (6) | −0.038 (5) | 0.028 (5) | −0.066 (6) |
N4 | 0.066 (5) | 0.216 (9) | 0.116 (6) | −0.052 (5) | 0.052 (5) | −0.109 (7) |
N11 | 0.046 (3) | 0.057 (3) | 0.045 (3) | −0.012 (3) | 0.016 (2) | −0.012 (3) |
C12 | 0.051 (4) | 0.054 (4) | 0.060 (5) | −0.007 (3) | 0.020 (4) | −0.022 (3) |
C13 | 0.051 (5) | 0.043 (4) | 0.078 (5) | 0.001 (3) | 0.017 (4) | −0.007 (4) |
N14 | 0.049 (4) | 0.055 (4) | 0.049 (3) | −0.006 (3) | 0.018 (3) | −0.007 (3) |
C15 | 0.076 (6) | 0.058 (5) | 0.068 (5) | 0.016 (4) | 0.029 (5) | 0.010 (4) |
C16 | 0.071 (5) | 0.090 (6) | 0.046 (4) | 0.012 (5) | 0.010 (4) | 0.016 (4) |
N17 | 0.075 (4) | 0.064 (4) | 0.049 (3) | −0.015 (4) | 0.025 (3) | −0.005 (3) |
N21 | 0.053 (3) | 0.060 (4) | 0.049 (3) | −0.011 (3) | 0.020 (3) | −0.007 (3) |
C22 | 0.054 (5) | 0.082 (6) | 0.070 (5) | 0.018 (4) | 0.023 (4) | −0.001 (4) |
C23 | 0.090 (6) | 0.057 (5) | 0.065 (5) | 0.021 (4) | 0.028 (5) | −0.007 (4) |
N24 | 0.077 (4) | 0.043 (4) | 0.048 (3) | 0.000 (3) | 0.018 (3) | −0.001 (3) |
C25 | 0.111 (7) | 0.041 (4) | 0.062 (4) | −0.004 (5) | 0.023 (5) | 0.001 (4) |
C26 | 0.103 (7) | 0.071 (6) | 0.070 (5) | −0.033 (5) | 0.016 (6) | 0.005 (4) |
N27 | 0.068 (4) | 0.059 (4) | 0.049 (3) | −0.019 (3) | 0.014 (3) | −0.001 (3) |
Geometric parameters (Å, º) top
Ni1—N24 | 2.063 (5) | N14—H14 | 0.91 |
Ni1—N14 | 2.072 (5) | C15—C16 | 1.494 (9) |
Ni1—N27 | 2.120 (5) | C15—H15A | 0.97 |
Ni1—N11 | 2.136 (4) | C15—H15B | 0.97 |
Ni1—N17 | 2.179 (5) | C16—N17 | 1.504 (8) |
Ni1—N21 | 2.185 (5) | C16—H16A | 0.97 |
Ni2—C1i | 1.843 (7) | C16—H16B | 0.97 |
Ni2—C1 | 1.843 (7) | N17—H17A | 0.90 |
Ni2—C2i | 1.887 (8) | N17—H17B | 0.90 |
Ni2—C2 | 1.887 (8) | N21—C22 | 1.466 (8) |
Ni3—C4ii | 1.851 (9) | N21—H21A | 0.90 |
Ni3—C4 | 1.851 (9) | N21—H21B | 0.90 |
Ni3—C3ii | 1.862 (8) | C22—C23 | 1.502 (9) |
Ni3—C3 | 1.862 (8) | C22—H22A | 0.97 |
C1—N1 | 1.157 (7) | C22—H22B | 0.97 |
C2—N2 | 1.124 (8) | C23—N24 | 1.481 (9) |
C3—N3 | 1.139 (8) | C23—H23A | 0.97 |
C4—N4 | 1.133 (9) | C23—H23B | 0.97 |
N11—C12 | 1.479 (7) | N24—C25 | 1.456 (9) |
N11—H11A | 0.90 | N24—H24 | 0.91 |
N11—H11B | 0.90 | C25—C26 | 1.507 (12) |
C12—C13 | 1.522 (9) | C25—H25A | 0.97 |
C12—H12A | 0.97 | C25—H25B | 0.97 |
C12—H12B | 0.97 | C26—N27 | 1.477 (9) |
C13—N14 | 1.453 (7) | C26—H26A | 0.97 |
C13—H13A | 0.97 | C26—H26B | 0.97 |
C13—H13B | 0.97 | N27—H27A | 0.90 |
N14—C15 | 1.485 (8) | N27—H27B | 0.90 |
| | | |
N24—Ni1—N14 | 177.8 (2) | N14—C15—H15B | 110.5 |
N24—Ni1—N27 | 81.6 (3) | C16—C15—H15B | 110.5 |
N14—Ni1—N27 | 97.6 (2) | H15A—C15—H15B | 108.7 |
N24—Ni1—N11 | 96.1 (2) | C15—C16—N17 | 110.1 (5) |
N14—Ni1—N11 | 81.9 (2) | C15—C16—H16A | 109.6 |
N27—Ni1—N11 | 93.6 (2) | N17—C16—H16A | 109.6 |
N24—Ni1—N17 | 100.5 (2) | C15—C16—H16B | 109.6 |
N14—Ni1—N17 | 81.5 (2) | N17—C16—H16B | 109.6 |
N27—Ni1—N17 | 92.6 (2) | H16A—C16—H16B | 108.1 |
N11—Ni1—N17 | 163.0 (2) | C16—N17—Ni1 | 106.2 (4) |
N24—Ni1—N21 | 81.0 (2) | C16—N17—H17A | 110.5 |
N14—Ni1—N21 | 100.0 (2) | Ni1—N17—H17A | 110.5 |
N27—Ni1—N21 | 162.3 (2) | C16—N17—H17B | 110.5 |
N11—Ni1—N21 | 90.70 (19) | Ni1—N17—H17B | 110.5 |
N17—Ni1—N21 | 88.2 (2) | H17A—N17—H17B | 108.7 |
C1i—Ni2—C1 | 180.0 | C22—N21—Ni1 | 108.7 (4) |
C1i—Ni2—C2i | 91.2 (3) | C22—N21—H21A | 109.9 |
C1—Ni2—C2i | 88.8 (3) | Ni1—N21—H21A | 109.9 |
C1i—Ni2—C2 | 88.8 (3) | C22—N21—H21B | 109.9 |
C1—Ni2—C2 | 91.2 (3) | Ni1—N21—H21B | 109.9 |
C2i—Ni2—C2 | 180.0 (3) | H21A—N21—H21B | 108.3 |
C4ii—Ni3—C4 | 180.000 (1) | N21—C22—C23 | 110.6 (6) |
C4ii—Ni3—C3ii | 88.1 (3) | N21—C22—H22A | 109.5 |
C4—Ni3—C3ii | 91.9 (3) | C23—C22—H22A | 109.5 |
C4ii—Ni3—C3 | 91.9 (3) | N21—C22—H22B | 109.5 |
C4—Ni3—C3 | 88.1 (3) | C23—C22—H22B | 109.5 |
C3ii—Ni3—C3 | 180.0 (4) | H22A—C22—H22B | 108.1 |
N1—C1—Ni2 | 178.6 (6) | N24—C23—C22 | 108.4 (6) |
N2—C2—Ni2 | 179.2 (7) | N24—C23—H23A | 110.0 |
N3—C3—Ni3 | 179.2 (8) | C22—C23—H23A | 110.0 |
N4—C4—Ni3 | 178.6 (11) | N24—C23—H23B | 110.0 |
C12—N11—Ni1 | 108.4 (4) | C22—C23—H23B | 110.0 |
C12—N11—H11A | 110.0 | H23A—C23—H23B | 108.4 |
Ni1—N11—H11A | 110.0 | C25—N24—C23 | 116.3 (6) |
C12—N11—H11B | 110.0 | C25—N24—Ni1 | 109.6 (5) |
Ni1—N11—H11B | 110.0 | C23—N24—Ni1 | 108.0 (4) |
H11A—N11—H11B | 108.4 | C25—N24—H24 | 107.5 |
N11—C12—C13 | 110.4 (6) | C23—N24—H24 | 107.5 |
N11—C12—H12A | 109.6 | Ni1—N24—H24 | 107.5 |
C13—C12—H12A | 109.6 | N24—C25—C26 | 105.9 (6) |
N11—C12—H12B | 109.6 | N24—C25—H25A | 110.6 |
C13—C12—H12B | 109.6 | C26—C25—H25A | 110.6 |
H12A—C12—H12B | 108.1 | N24—C25—H25B | 110.6 |
N14—C13—C12 | 107.5 (5) | C26—C25—H25B | 110.6 |
N14—C13—H13A | 110.2 | H25A—C25—H25B | 108.7 |
C12—C13—H13A | 110.2 | N27—C26—C25 | 110.6 (6) |
N14—C13—H13B | 110.2 | N27—C26—H26A | 109.5 |
C12—C13—H13B | 110.2 | C25—C26—H26A | 109.5 |
H13A—C13—H13B | 108.5 | N27—C26—H26B | 109.5 |
C13—N14—C15 | 115.3 (5) | C25—C26—H26B | 109.5 |
C13—N14—Ni1 | 107.6 (4) | H26A—C26—H26B | 108.1 |
C15—N14—Ni1 | 109.0 (4) | C26—N27—Ni1 | 107.9 (5) |
C13—N14—H14 | 108.3 | C26—N27—H27A | 110.1 |
C15—N14—H14 | 108.3 | Ni1—N27—H27A | 110.1 |
Ni1—N14—H14 | 108.3 | C26—N27—H27B | 110.1 |
N14—C15—C16 | 106.2 (5) | Ni1—N27—H27B | 110.1 |
N14—C15—H15A | 110.5 | H27A—N27—H27B | 108.4 |
C16—C15—H15A | 110.5 | | |
| | | |
N24—Ni1—N11—C12 | 178.4 (4) | N24—Ni1—N21—C22 | 0.3 (4) |
N14—Ni1—N11—C12 | −0.6 (4) | N14—Ni1—N21—C22 | −177.7 (4) |
N27—Ni1—N11—C12 | 96.5 (4) | N27—Ni1—N21—C22 | 8.3 (8) |
N17—Ni1—N11—C12 | −14.4 (10) | N11—Ni1—N21—C22 | −95.8 (4) |
N21—Ni1—N11—C12 | −100.6 (4) | N17—Ni1—N21—C22 | 101.2 (4) |
Ni1—N11—C12—C13 | 27.7 (6) | Ni1—N21—C22—C23 | −27.2 (7) |
N11—C12—C13—N14 | −52.1 (7) | N21—C22—C23—N24 | 51.2 (8) |
C12—C13—N14—C15 | 171.6 (6) | C22—C23—N24—C25 | −173.2 (6) |
C12—C13—N14—Ni1 | 49.8 (6) | C22—C23—N24—Ni1 | −49.5 (6) |
N27—Ni1—N14—C13 | −119.9 (4) | N27—Ni1—N24—C25 | −23.3 (5) |
N11—Ni1—N14—C13 | −27.4 (4) | N11—Ni1—N24—C25 | −116.0 (5) |
N17—Ni1—N14—C13 | 148.6 (5) | N17—Ni1—N24—C25 | 67.8 (5) |
N21—Ni1—N14—C13 | 61.9 (5) | N21—Ni1—N24—C25 | 154.3 (5) |
N27—Ni1—N14—C15 | 114.5 (5) | N27—Ni1—N24—C23 | −150.9 (5) |
N11—Ni1—N14—C15 | −153.0 (5) | N11—Ni1—N24—C23 | 116.4 (4) |
N17—Ni1—N14—C15 | 23.0 (5) | N17—Ni1—N24—C23 | −59.9 (5) |
N21—Ni1—N14—C15 | −63.7 (5) | N21—Ni1—N24—C23 | 26.6 (4) |
C13—N14—C15—C16 | −170.0 (6) | C23—N24—C25—C26 | 169.9 (6) |
Ni1—N14—C15—C16 | −49.0 (7) | Ni1—N24—C25—C26 | 47.0 (7) |
N14—C15—C16—N17 | 57.0 (8) | N24—C25—C26—N27 | −53.9 (8) |
C15—C16—N17—Ni1 | −36.2 (7) | C25—C26—N27—Ni1 | 33.9 (7) |
N24—Ni1—N17—C16 | −172.2 (4) | N24—Ni1—N27—C26 | −6.1 (4) |
N14—Ni1—N17—C16 | 7.0 (5) | N14—Ni1—N27—C26 | 171.9 (4) |
N27—Ni1—N17—C16 | −90.3 (5) | N11—Ni1—N27—C26 | 89.6 (5) |
N11—Ni1—N17—C16 | 20.7 (11) | N17—Ni1—N27—C26 | −106.3 (5) |
N21—Ni1—N17—C16 | 107.4 (5) | N21—Ni1—N27—C26 | −14.1 (9) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···N1iii | 0.90 | 2.57 | 3.288 (8) | 138 |
N11—H11A···N1 | 0.90 | 2.69 | 3.258 (8) | 122 |
N11—H11B···N3iv | 0.90 | 2.39 | 3.161 (9) | 144 |
N14—H14···N4v | 0.91 | 2.31 | 3.128 (10) | 150 |
N17—H17A···N3 | 0.90 | 2.54 | 3.183 (9) | 129 |
N17—H17B···N2vi | 0.90 | 2.29 | 3.143 (9) | 159 |
N21—H21A···N1iii | 0.90 | 2.25 | 3.127 (7) | 165 |
N21—H21B···N2vi | 0.90 | 2.19 | 3.046 (8) | 158 |
N27—H27A···N4 | 0.90 | 2.24 | 3.067 (8) | 153 |
Symmetry codes: (iii) −x+1, −y, −z; (iv) x, −y+1/2, z−1/2; (v) −x+2, y−1/2, −z+1/2; (vi) −x+1, y−1/2, −z+1/2. |