metal-organic compounds
Bis({1-[(1-iminoethyl)imino]ethyl}azanido-κ2N1,N5)nickel(II) methanol monosolvate
aKey Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education of China, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, People's Republic of China
*Correspondence e-mail: weitaibao@126.com
The title compound, [Ni(C4H8N3)2]·CH3OH, contains two independent NiII atoms, each located on an inversion center and coordinated by four N atoms from two 1-[(1-iminoethyl)imino]ethyl}azanide ligands in a square-planar geometry. N—H⋯N, N—H⋯O and O—H⋯N hydrogen bonds link the complex molecules and methanol solvent molecules into a corrugated layer parallel to (001).
Related literature
For structures and applications of related compounds, see: Aromi et al. (2011); Guzei et al. (2006); Kopylovich et al. (2007); Kryatov et al. (2001); Norrestam et al. (1983).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536812046958/hy2604sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812046958/hy2604Isup2.hkl
A mixture of Ni(NO3)2.6H2O (0.029 g, 0.1 mmol) in 12 ml of acetonitrile/methanol (3:1, v/v) and 0.1 ml of 2M NaOH solution was sealed in a Teflon-lined autoclave and heated under autogenous pressure to 160°C for 3 days and then allowed to cool to room temperature at a rate of 1°C per minute. Block-shaped tan crystals of the title complex were collected in 71% yield.
H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.96, N—H = 0.86 and O—H = 0.82 Å and with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(C, O).
Acetonitrile is one of the common solvents that is widely used to study processes in solution. With most 3d-transition metal ions, acetonitrile behaves as a relatively weak monodentate ligand (Kopylovich et al., 2007; Kryatov et al., 2001), providing inorganic chemists with a perfect media for numerous reactions. As a whole, metal-promoted reactions of
have proven to be a significant tool for the synthesis of diverse compounds, and several reviews on this topic have appeared in literatures in the past decades (Aromi et al., 2011). However, a few reports showed the application of solvothermal synthetic techniques to reactions of with transition metal sources as a mean for the preparation of coordination compounds with molecular or extended structures (Guzei et al., 2006). Here we study reactions of 3d-transition metal ions with acetonitrile in order to understand the reaction system and elucidate structural features of the resultant mononuclear metal complexes.The
of the title compound contains two independent NiII atoms, each of which lies on an inversion center, and a methanol molecule, as shown in Fig. 1. Each NiII atom is in a square-planar geometry, coordinated by four N atoms from two 1-[(1-iminoethyl)imino]ethyl}azanide ligands. Two six-membered rings around the NiII atom is slightly distorted toward a boat conformation. In one six-membered ring, Ni1 and N2 atoms exist in the apex positions, while in the other ring Ni2 and N5 atoms do. The bond distances in the ligands are very similar to those observed for the simple acetamidine molecule (Norrestam et al., 1983). In the crystal, the complex molecules are linked into a one-dimensional supramolecular architecture via N4—H4···N3i, N5—H5···N3 hydrogen bonds (Table 1) [symmetry code: (i) -x+1, -y+1, -z]. The one-dimensional architectures are further linked into a two-dimensional supramolecular structure with highly corrugated architecture via O—H···N and N—H···O hydrogen bonds between the ligands and the lattice methanol molecules, as shown in Fig. 2.For structures and applications of related compounds, see: Aromi et al. (2011); Guzei et al. (2006); Kopylovich et al. (2007); Kryatov et al. (2001); Norrestam et al. (1983).
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Ni(C4H8N3)2]·CH4O | F(000) = 608 |
Mr = 287.02 | Dx = 1.387 Mg m−3 Dm = 1.37 Mg m−3 Dm measured by not measured |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9999 reflections |
a = 9.2768 (7) Å | θ = 2.4–27.7° |
b = 11.4347 (3) Å | µ = 1.41 mm−1 |
c = 12.9774 (3) Å | T = 298 K |
β = 92.961 (3)° | Block, green |
V = 1374.77 (11) Å3 | 0.23 × 0.21 × 0.19 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 2421 independent reflections |
Radiation source: fine-focus sealed tube | 1738 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
φ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −9→11 |
Tmin = 0.603, Tmax = 0.766 | k = −13→13 |
9293 measured reflections | l = −15→15 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0344P)2 + 0.7499P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2421 reflections | Δρmax = 0.33 e Å−3 |
163 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.051 (2) |
[Ni(C4H8N3)2]·CH4O | V = 1374.77 (11) Å3 |
Mr = 287.02 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.2768 (7) Å | µ = 1.41 mm−1 |
b = 11.4347 (3) Å | T = 298 K |
c = 12.9774 (3) Å | 0.23 × 0.21 × 0.19 mm |
β = 92.961 (3)° |
Bruker APEXII CCD diffractometer | 2421 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1738 reflections with I > 2σ(I) |
Tmin = 0.603, Tmax = 0.766 | Rint = 0.032 |
9293 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.33 e Å−3 |
2421 reflections | Δρmin = −0.20 e Å−3 |
163 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8993 (3) | 0.3445 (2) | 0.0859 (3) | 0.0599 (8) | |
H1A | 0.9269 | 0.3305 | 0.1572 | 0.090* | |
H1B | 0.8074 | 0.3832 | 0.0810 | 0.090* | |
H1C | 0.9704 | 0.3929 | 0.0558 | 0.090* | |
C2 | 0.8886 (3) | 0.2297 (2) | 0.02917 (19) | 0.0394 (6) | |
C3 | 0.7796 (3) | 0.1309 (2) | −0.10996 (19) | 0.0383 (6) | |
C4 | 0.6614 (3) | 0.1373 (3) | −0.1938 (2) | 0.0578 (8) | |
H4A | 0.6647 | 0.0688 | −0.2365 | 0.087* | |
H4B | 0.6747 | 0.2057 | −0.2351 | 0.087* | |
H4C | 0.5695 | 0.1413 | −0.1632 | 0.087* | |
N1 | 0.9732 (2) | 0.14471 (17) | 0.05897 (16) | 0.0391 (5) | |
H1 | 1.0248 | 0.1577 | 0.1148 | 0.047* | |
N2 | 0.8599 (2) | 0.03823 (17) | −0.10115 (15) | 0.0379 (5) | |
H2 | 0.8460 | −0.0129 | −0.1493 | 0.045* | |
N3 | 0.7895 (2) | 0.22670 (18) | −0.05010 (16) | 0.0423 (5) | |
Ni1 | 1.0000 | 0.0000 | 0.0000 | 0.03187 (16) | |
C5 | 0.4642 (3) | 0.1559 (2) | 0.1102 (3) | 0.0606 (8) | |
H5A | 0.3862 | 0.1150 | 0.0746 | 0.091* | |
H5B | 0.4685 | 0.1344 | 0.1818 | 0.091* | |
H5C | 0.5535 | 0.1357 | 0.0805 | 0.091* | |
C6 | 0.4397 (3) | 0.2853 (2) | 0.1004 (2) | 0.0407 (6) | |
C7 | 0.3098 (3) | 0.4450 (2) | 0.1593 (2) | 0.0402 (6) | |
C8 | 0.2071 (4) | 0.4860 (2) | 0.2380 (2) | 0.0561 (8) | |
H8A | 0.2570 | 0.4901 | 0.3046 | 0.084* | |
H8B | 0.1282 | 0.4319 | 0.2407 | 0.084* | |
H8C | 0.1707 | 0.5620 | 0.2190 | 0.084* | |
N4 | 0.3630 (2) | 0.52029 (17) | 0.09697 (17) | 0.0423 (6) | |
H4 | 0.3296 | 0.5902 | 0.1014 | 0.051* | |
N5 | 0.5126 (2) | 0.34436 (18) | 0.03568 (17) | 0.0406 (5) | |
H5 | 0.5765 | 0.3050 | 0.0047 | 0.049* | |
N6 | 0.3410 (2) | 0.32978 (18) | 0.16225 (16) | 0.0431 (5) | |
Ni2 | 0.5000 | 0.5000 | 0.0000 | 0.03481 (17) | |
C1A | 0.1695 (5) | 0.1778 (3) | 0.3585 (3) | 0.0868 (12) | |
H1A1 | 0.2617 | 0.1556 | 0.3894 | 0.130* | |
H1A2 | 0.0962 | 0.1268 | 0.3826 | 0.130* | |
H1A3 | 0.1484 | 0.2570 | 0.3771 | 0.130* | |
O1A | 0.1728 (2) | 0.16916 (17) | 0.25194 (14) | 0.0601 (6) | |
H1A4 | 0.2242 | 0.2210 | 0.2302 | 0.090* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0588 (19) | 0.0430 (17) | 0.076 (2) | 0.0143 (15) | −0.0105 (16) | −0.0205 (15) |
C2 | 0.0371 (15) | 0.0335 (14) | 0.0476 (15) | 0.0039 (12) | 0.0022 (12) | −0.0055 (11) |
C3 | 0.0365 (14) | 0.0359 (14) | 0.0422 (14) | 0.0038 (12) | −0.0001 (11) | 0.0030 (11) |
C4 | 0.0597 (19) | 0.0530 (18) | 0.0582 (18) | 0.0117 (15) | −0.0199 (15) | −0.0022 (14) |
N1 | 0.0408 (12) | 0.0349 (11) | 0.0408 (12) | 0.0056 (10) | −0.0048 (10) | −0.0067 (9) |
N2 | 0.0414 (13) | 0.0322 (11) | 0.0395 (12) | 0.0048 (10) | −0.0037 (9) | −0.0048 (9) |
N3 | 0.0400 (13) | 0.0359 (12) | 0.0502 (13) | 0.0094 (10) | −0.0044 (10) | −0.0036 (10) |
Ni1 | 0.0320 (3) | 0.0273 (3) | 0.0360 (3) | 0.00400 (18) | −0.00116 (18) | −0.00203 (18) |
C5 | 0.064 (2) | 0.0380 (16) | 0.081 (2) | 0.0033 (15) | 0.0155 (17) | 0.0081 (15) |
C6 | 0.0399 (15) | 0.0325 (13) | 0.0490 (16) | −0.0001 (12) | −0.0043 (12) | 0.0039 (12) |
C7 | 0.0347 (15) | 0.0402 (15) | 0.0454 (15) | −0.0010 (12) | −0.0012 (12) | −0.0033 (12) |
C8 | 0.0558 (18) | 0.0507 (19) | 0.063 (2) | −0.0025 (14) | 0.0164 (15) | −0.0092 (14) |
N4 | 0.0429 (13) | 0.0323 (12) | 0.0521 (13) | 0.0071 (10) | 0.0051 (11) | −0.0004 (10) |
N5 | 0.0389 (13) | 0.0343 (12) | 0.0484 (12) | 0.0081 (10) | 0.0023 (10) | 0.0000 (10) |
N6 | 0.0426 (13) | 0.0376 (12) | 0.0493 (13) | −0.0005 (10) | 0.0061 (11) | 0.0016 (10) |
Ni2 | 0.0339 (3) | 0.0292 (3) | 0.0413 (3) | 0.00597 (19) | 0.00096 (19) | 0.00100 (19) |
C1A | 0.124 (4) | 0.078 (3) | 0.058 (2) | −0.018 (2) | 0.006 (2) | 0.0053 (19) |
O1A | 0.0711 (15) | 0.0590 (13) | 0.0505 (12) | −0.0232 (11) | 0.0049 (10) | −0.0076 (10) |
C1—C2 | 1.506 (3) | C5—H5C | 0.9600 |
C1—H1A | 0.9600 | C6—N5 | 1.296 (3) |
C1—H1B | 0.9600 | C6—N6 | 1.348 (3) |
C1—H1C | 0.9600 | C7—N4 | 1.297 (3) |
C2—N1 | 1.295 (3) | C7—N6 | 1.349 (3) |
C2—N3 | 1.344 (3) | C7—C8 | 1.507 (4) |
C3—N2 | 1.296 (3) | C8—H8A | 0.9600 |
C3—N3 | 1.344 (3) | C8—H8B | 0.9600 |
C3—C4 | 1.506 (3) | C8—H8C | 0.9600 |
C4—H4A | 0.9600 | N4—Ni2 | 1.848 (2) |
C4—H4B | 0.9600 | N4—H4 | 0.8600 |
C4—H4C | 0.9600 | N5—Ni2 | 1.841 (2) |
N1—Ni1 | 1.8452 (19) | N5—H5 | 0.8600 |
N1—H1 | 0.8600 | Ni2—N5ii | 1.841 (2) |
N2—Ni1 | 1.851 (2) | Ni2—N4ii | 1.848 (2) |
N2—H2 | 0.8600 | C1A—O1A | 1.388 (4) |
Ni1—N1i | 1.8452 (19) | C1A—H1A1 | 0.9600 |
Ni1—N2i | 1.851 (2) | C1A—H1A2 | 0.9600 |
C5—C6 | 1.501 (3) | C1A—H1A3 | 0.9600 |
C5—H5A | 0.9600 | O1A—H1A4 | 0.8200 |
C5—H5B | 0.9600 | ||
C2—C1—H1A | 109.5 | H5A—C5—H5C | 109.5 |
C2—C1—H1B | 109.5 | H5B—C5—H5C | 109.5 |
H1A—C1—H1B | 109.5 | N5—C6—N6 | 125.6 (2) |
C2—C1—H1C | 109.5 | N5—C6—C5 | 119.2 (3) |
H1A—C1—H1C | 109.5 | N6—C6—C5 | 115.2 (2) |
H1B—C1—H1C | 109.5 | N4—C7—N6 | 125.3 (3) |
N1—C2—N3 | 126.1 (2) | N4—C7—C8 | 119.4 (2) |
N1—C2—C1 | 119.0 (2) | N6—C7—C8 | 115.3 (2) |
N3—C2—C1 | 114.9 (2) | C7—C8—H8A | 109.5 |
N2—C3—N3 | 126.4 (2) | C7—C8—H8B | 109.5 |
N2—C3—C4 | 119.8 (2) | H8A—C8—H8B | 109.5 |
N3—C3—C4 | 113.8 (2) | C7—C8—H8C | 109.5 |
C3—C4—H4A | 109.5 | H8A—C8—H8C | 109.5 |
C3—C4—H4B | 109.5 | H8B—C8—H8C | 109.5 |
H4A—C4—H4B | 109.5 | C7—N4—Ni2 | 129.69 (19) |
C3—C4—H4C | 109.5 | C7—N4—H4 | 115.2 |
H4A—C4—H4C | 109.5 | Ni2—N4—H4 | 115.2 |
H4B—C4—H4C | 109.5 | C6—N5—Ni2 | 129.70 (18) |
C2—N1—Ni1 | 129.87 (18) | C6—N5—H5 | 115.1 |
C2—N1—H1 | 115.1 | Ni2—N5—H5 | 115.1 |
Ni1—N1—H1 | 115.1 | C6—N6—C7 | 120.2 (2) |
C3—N2—Ni1 | 129.38 (18) | N5ii—Ni2—N5 | 180.00 (13) |
C3—N2—H2 | 115.3 | N5ii—Ni2—N4 | 90.74 (9) |
Ni1—N2—H2 | 115.3 | N5—Ni2—N4 | 89.26 (9) |
C3—N3—C2 | 119.1 (2) | N5ii—Ni2—N4ii | 89.26 (9) |
N1—Ni1—N1i | 180.00 (13) | N5—Ni2—N4ii | 90.74 (9) |
N1—Ni1—N2 | 88.73 (9) | N4—Ni2—N4ii | 180.0 |
N1i—Ni1—N2 | 91.27 (9) | O1A—C1A—H1A1 | 109.5 |
N1—Ni1—N2i | 91.27 (9) | O1A—C1A—H1A2 | 109.5 |
N1i—Ni1—N2i | 88.73 (9) | H1A1—C1A—H1A2 | 109.5 |
N2—Ni1—N2i | 180.00 (17) | O1A—C1A—H1A3 | 109.5 |
C6—C5—H5A | 109.5 | H1A1—C1A—H1A3 | 109.5 |
C6—C5—H5B | 109.5 | H1A2—C1A—H1A3 | 109.5 |
H5A—C5—H5B | 109.5 | C1A—O1A—H1A4 | 109.5 |
C6—C5—H5C | 109.5 | ||
N3—C2—N1—Ni1 | 6.0 (4) | N6—C7—N4—Ni2 | −3.4 (4) |
C1—C2—N1—Ni1 | −173.5 (2) | C8—C7—N4—Ni2 | 174.9 (2) |
N3—C3—N2—Ni1 | 6.1 (4) | N6—C6—N5—Ni2 | −4.4 (4) |
C4—C3—N2—Ni1 | −173.7 (2) | C5—C6—N5—Ni2 | 175.8 (2) |
N2—C3—N3—C2 | −1.7 (4) | N5—C6—N6—C7 | 0.6 (4) |
C4—C3—N3—C2 | 178.2 (2) | C5—C6—N6—C7 | −179.6 (2) |
N1—C2—N3—C3 | −4.4 (4) | N4—C7—N6—C6 | 3.3 (4) |
C1—C2—N3—C3 | 175.1 (2) | C8—C7—N6—C6 | −175.1 (2) |
C2—N1—Ni1—N2 | −1.8 (2) | C6—N5—Ni2—N4 | 3.5 (2) |
C2—N1—Ni1—N2i | 178.2 (2) | C6—N5—Ni2—N4ii | −176.5 (2) |
C3—N2—Ni1—N1 | −3.9 (2) | C7—N4—Ni2—N5ii | −179.8 (2) |
C3—N2—Ni1—N1i | 176.1 (2) | C7—N4—Ni2—N5 | 0.2 (2) |
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1Aiii | 0.86 | 2.19 | 3.049 (3) | 172 |
N2—H2···O1Aiv | 0.86 | 2.23 | 3.079 (3) | 169 |
N4—H4···N3ii | 0.86 | 2.44 | 3.264 (3) | 160 |
N5—H5···N3 | 0.86 | 2.31 | 3.153 (3) | 165 |
O1A—H1A4···N6 | 0.82 | 1.90 | 2.711 (3) | 172 |
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x+1, y, z; (iv) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C4H8N3)2]·CH4O |
Mr | 287.02 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 9.2768 (7), 11.4347 (3), 12.9774 (3) |
β (°) | 92.961 (3) |
V (Å3) | 1374.77 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.41 |
Crystal size (mm) | 0.23 × 0.21 × 0.19 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.603, 0.766 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9293, 2421, 1738 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.082, 1.04 |
No. of reflections | 2421 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.20 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1Ai | 0.86 | 2.19 | 3.049 (3) | 172 |
N2—H2···O1Aii | 0.86 | 2.23 | 3.079 (3) | 169 |
N4—H4···N3iii | 0.86 | 2.44 | 3.264 (3) | 160 |
N5—H5···N3 | 0.86 | 2.31 | 3.153 (3) | 165 |
O1A—H1A4···N6 | 0.82 | 1.90 | 2.711 (3) | 172 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z; (iii) −x+1, −y+1, −z. |
Footnotes
‡Additional correspondence author, e-mail: zhangnwnu@126.com.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (grant Nos. 21064006 and 21161018), the Natural Science Foundation of Gansu Province (1010RJZA018) and the Program for Changjiang Scholars and the Innovative Research Team in Universities of the Ministry of Education of China (IRT1177).
References
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Acetonitrile is one of the common solvents that is widely used to study processes in solution. With most 3d-transition metal ions, acetonitrile behaves as a relatively weak monodentate ligand (Kopylovich et al., 2007; Kryatov et al., 2001), providing inorganic chemists with a perfect media for numerous reactions. As a whole, metal-promoted reactions of nitriles have proven to be a significant tool for the synthesis of diverse compounds, and several reviews on this topic have appeared in literatures in the past decades (Aromi et al., 2011). However, a few reports showed the application of solvothermal synthetic techniques to reactions of nitriles with transition metal sources as a mean for the preparation of coordination compounds with molecular or extended structures (Guzei et al., 2006). Here we study reactions of 3d-transition metal ions with acetonitrile in order to understand the reaction system and elucidate structural features of the resultant mononuclear metal complexes.
The asymmetric unit of the title compound contains two independent NiII atoms, each of which lies on an inversion center, and a methanol molecule, as shown in Fig. 1. Each NiII atom is in a square-planar geometry, coordinated by four N atoms from two 1-[(1-iminoethyl)imino]ethyl}azanide ligands. Two six-membered rings around the NiII atom is slightly distorted toward a boat conformation. In one six-membered ring, Ni1 and N2 atoms exist in the apex positions, while in the other ring Ni2 and N5 atoms do. The bond distances in the ligands are very similar to those observed for the simple acetamidine molecule (Norrestam et al., 1983). In the crystal, the complex molecules are linked into a one-dimensional supramolecular architecture via N4—H4···N3i, N5—H5···N3 hydrogen bonds (Table 1) [symmetry code: (i) -x+1, -y+1, -z]. The one-dimensional architectures are further linked into a two-dimensional supramolecular structure with highly corrugated architecture via O—H···N and N—H···O hydrogen bonds between the ligands and the lattice methanol molecules, as shown in Fig. 2.