The title compound, [Ni(C4H10N5)2], was prepared from an aqueous KOH solution. The coordination geometry around the Ni atom is planar, with the central metal bonded to four ligand N atoms in two bidentate ligands. The deprotonation of the ligand causes an increase of the π-conjugation in the C—N—C system, reducing the bond angle at the N atom to 118.46 (16)°.
Supporting information
CCDC reference: 189292
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (N-C) = 0.003 Å
- R factor = 0.030
- wR factor = 0.072
- Data-to-parameter ratio = 14.4
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor N(2) - H(12) ?
PLAT_420 Alert C D-H Without Acceptor N(5) - H(15B) ?
General Notes
FORMU_01 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: C8 H20 N10 Ni1
Atom count from _chemical_formula_moiety:C4 H10 N5 Ni1
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1994); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: SHELXS97 (Sheldrick, 1997); program(s) used to solve structure: SHELXS97; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: SHELXL97.
Bis(1,1-dimethylbiguande)nickel(II)
top
Crystal data top
[Ni(C4H10N5)2] | F(000) = 332 |
Mr = 315.05 | Dx = 1.620 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1564 reflections |
a = 6.412 (1) Å | θ = 2.9–27.5° |
b = 9.032 (2) Å | µ = 1.51 mm−1 |
c = 11.239 (2) Å | T = 173 K |
β = 97.05 (3)° | Block, orange |
V = 646.0 (2) Å3 | 0.40 × 0.30 × 0.20 mm |
Z = 2 | |
Data collection top
Rigaku R-AXIS RAPID IP diffractometer | 1494 independent reflections |
Radiation source: fine-focus sealed tube | 1159 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
Detector resolution: 100x100 microns pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
Oscillation scans | h = 0→8 |
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995) | k = 0→11 |
Tmin = 0.540, Tmax = 0.740 | l = −14→14 |
1564 measured reflections | |
Refinement top
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: hydrogen atoms are generated by HFIX instructions |
wR(F2) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0409P)2] where P = (Fo2 + 2Fc2)/3 |
1467 reflections | (Δ/σ)max = 0.001 |
102 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
Special details top
Experimental. ABSCOR BY T·Higashi 8 march,1995 |
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 | x | y | z | Uiso*/Ueq | |
Ni1 | 0.5000 | 0.0000 | 0.0000 | 0.01623 (12) | |
N1 | 0.4634 (2) | 0.00804 (18) | 0.16042 (15) | 0.0199 (3) | |
N2 | 0.7070 (3) | 0.14347 (19) | 0.02827 (15) | 0.0208 (4) | |
N3 | 0.9247 (3) | 0.32489 (19) | 0.12657 (14) | 0.0226 (4) | |
N4 | 0.6763 (2) | 0.21581 (18) | 0.22815 (14) | 0.0191 (4) | |
N5 | 0.4849 (3) | 0.0950 (2) | 0.35585 (16) | 0.0274 (4) | |
C1 | 0.5382 (3) | 0.1054 (2) | 0.24156 (17) | 0.0180 (4) | |
C2 | 0.7654 (3) | 0.2216 (2) | 0.12635 (17) | 0.0183 (4) | |
C3 | 1.0568 (3) | 0.3188 (3) | 0.03008 (19) | 0.0301 (5) | |
H3A | 1.1246 | 0.2216 | 0.0300 | 0.045* | |
H3B | 1.1645 | 0.3961 | 0.0423 | 0.045* | |
H3C | 0.9701 | 0.3347 | −0.0469 | 0.045* | |
C4 | 1.0354 (3) | 0.3761 (2) | 0.24075 (19) | 0.0287 (5) | |
H4A | 0.9343 | 0.3902 | 0.2985 | 0.043* | |
H4B | 1.1058 | 0.4701 | 0.2285 | 0.043* | |
H4C | 1.1400 | 0.3021 | 0.2717 | 0.043* | |
H11 | 0.399 (5) | −0.056 (4) | 0.194 (3) | 0.080* | |
H12 | 0.784 (5) | 0.156 (3) | −0.023 (3) | 0.080* | |
H15A | 0.519 (5) | 0.174 (4) | 0.396 (3) | 0.080* | |
H15B | 0.378 (6) | 0.047 (4) | 0.363 (3) | 0.080* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.01645 (17) | 0.01617 (19) | 0.01637 (19) | −0.00273 (14) | 0.00321 (12) | −0.00093 (14) |
N1 | 0.0190 (7) | 0.0204 (8) | 0.0208 (8) | −0.0047 (7) | 0.0042 (6) | −0.0008 (7) |
N2 | 0.0224 (8) | 0.0228 (9) | 0.0180 (8) | −0.0048 (7) | 0.0056 (6) | −0.0019 (7) |
N3 | 0.0223 (8) | 0.0274 (9) | 0.0188 (8) | −0.0091 (7) | 0.0061 (6) | −0.0028 (7) |
N4 | 0.0188 (8) | 0.0185 (8) | 0.0203 (9) | −0.0005 (6) | 0.0041 (6) | −0.0025 (7) |
N5 | 0.0318 (10) | 0.0295 (10) | 0.0230 (10) | −0.0092 (8) | 0.0115 (8) | −0.0061 (8) |
C1 | 0.0166 (9) | 0.0191 (9) | 0.0186 (9) | 0.0031 (7) | 0.0036 (7) | −0.0004 (8) |
C2 | 0.0161 (9) | 0.0150 (9) | 0.0238 (10) | 0.0006 (7) | 0.0023 (7) | 0.0020 (8) |
C3 | 0.0290 (11) | 0.0330 (12) | 0.0303 (12) | −0.0123 (9) | 0.0118 (9) | −0.0048 (10) |
C4 | 0.0237 (10) | 0.0364 (12) | 0.0253 (11) | −0.0131 (9) | 0.0006 (8) | −0.0033 (10) |
Geometric parameters (Å, º) top
Ni1—N1 | 1.8480 (17) | N4—C2 | 1.341 (2) |
Ni1—N1i | 1.8480 (17) | N4—C1 | 1.354 (2) |
Ni1—N2i | 1.8543 (16) | N5—C1 | 1.372 (2) |
Ni1—N2 | 1.8543 (16) | N5—H15A | 0.86 (3) |
N1—C1 | 1.314 (2) | N5—H15B | 0.83 (4) |
N1—H11 | 0.83 (3) | C3—H3A | 0.9800 |
N2—C2 | 1.324 (2) | C3—H3B | 0.9800 |
N2—H12 | 0.81 (3) | C3—H3C | 0.9800 |
N3—C2 | 1.383 (2) | C4—H4A | 0.9800 |
N3—C3 | 1.457 (2) | C4—H4B | 0.9800 |
N3—C4 | 1.463 (3) | C4—H4C | 0.9800 |
| | | |
N1i—Ni1—N1 | 180.0 | N1—C1—N4 | 127.12 (17) |
N1i—Ni1—N2 | 91.18 (7) | N1—C1—N5 | 119.47 (18) |
N1—Ni1—N2 | 88.82 (7) | N4—C1—N5 | 113.32 (17) |
N1i—Ni1—N2i | 88.82 (7) | N2—C2—N4 | 125.66 (17) |
N1—Ni1—N2i | 91.18 (7) | N2—C2—N3 | 119.64 (17) |
N2—Ni1—N2i | 180.0 | N4—C2—N3 | 114.63 (17) |
C1—N1—Ni1 | 128.60 (13) | N3—C3—H3A | 109.5 |
C1—N1—H11 | 108 (2) | N3—C3—H3B | 109.5 |
Ni1—N1—H11 | 124 (2) | H3A—C3—H3B | 109.5 |
C2—N2—Ni1 | 129.70 (14) | N3—C3—H3C | 109.5 |
C2—N2—H12 | 112 (2) | H3A—C3—H3C | 109.5 |
Ni1—N2—H12 | 118 (2) | H3B—C3—H3C | 109.5 |
C2—N3—C3 | 118.05 (17) | N3—C4—H4A | 109.5 |
C2—N3—C4 | 119.55 (16) | N3—C4—H4B | 109.5 |
C3—N3—C4 | 113.65 (17) | H4A—C4—H4B | 109.5 |
C2—N4—C1 | 118.46 (16) | N3—C4—H4C | 109.5 |
C1—N5—H15A | 111 (2) | H4A—C4—H4C | 109.5 |
C1—N5—H15B | 116 (3) | H4B—C4—H4C | 109.5 |
H15A—N5—H15B | 123 (3) | | |
| | | |
N2i—Ni1—N1—C1 | −168.71 (17) | Ni1—N2—C2—N4 | −2.8 (3) |
N2—Ni1—N1—C1 | 11.29 (17) | Ni1—N2—C2—N3 | −179.43 (14) |
N1i—Ni1—N2—C2 | 172.91 (18) | C1—N4—C2—N2 | 11.5 (3) |
N1—Ni1—N2—C2 | −7.09 (18) | C1—N4—C2—N3 | −171.65 (16) |
N1i—Ni1—N2—C2 | 172.91 (18) | C3—N3—C2—N2 | −14.8 (3) |
Ni1—N1—C1—N4 | −6.5 (3) | C4—N3—C2—N2 | −160.38 (18) |
Ni1—N1—C1—N5 | 177.29 (14) | C3—N3—C2—N4 | 168.15 (18) |
C2—N4—C1—N1 | −7.0 (3) | C4—N3—C2—N4 | 22.6 (3) |
C2—N4—C1—N5 | 169.45 (17) | | |
Symmetry code: (i) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H15A···N2ii | 0.86 (3) | 2.43 (3) | 3.269 (3) | 164 (3) |
N1—H11···N4iii | 0.83 (3) | 2.31 (4) | 3.100 (2) | 159 (3) |
Symmetry codes: (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2. |