Acta Cryst. (2007). E63, m3082 [ doi:10.1107/S160053680705920X ]
In the title compound, [NiCl2(C10H11N3)2]·CH4O, the NiII ion lies on a crystallographic twofold axis and is coordinated in a distorted octahedral geometry by four N atoms from two bidentate naphthyridine ligands and two chlorine atoms. The unique methanol solvent molecule has half occupancy. In the crystal structure, intermolecular N-H
Cl and O-HCl hydrogen bonds connect molecules into one-dimensional chains which propagate along the c-axis direction.
All reagents and solvents were used as obtained without further purification. The CH,N elemental analyses were performed on a Perkin-Elmer model 2400 elemental analyzer.
To an methanol solution of nickel chloride hexahydrate (24 mg, 0.1 mmol), was added L (17.4 mg, 0.1 mmol) in 10 ml of methanol. The solution was stirred for a few minutes, then the solution was filtered. The solution was left standing at room temperature for several days. Light blue crystals were isolated after slow evaporation of its solution in air. Yield: 33 mg, 65%. Anal. Calcd for C21H26Cl2N6NiO: C, 49.60; H, 5.12; N, 16.53; Found: C, 49.52; H, 5.05; N, 16.47.
All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with N—H = 0.86, C—H = 0.93–0.96 and O—H = 0.82 Å. They were included in the refinement in the riding-model approximation with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(O and methyl C atoms)
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./lh2548fig1thm.gif)
| Fig. 1. The molecular structure, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry code: (A): −x + 2, y, −z + 3/2]. |
![[Figure 2]](./lh2548fig2thm.gif)
| Fig. 2. Part of the crystal structure showing hydrogen bonds as dashed lines. |
| [NiCl2(C10H11N3)2]·CH4O | F000 = 1056 |
| Mr = 508.09 | Dx = 1.278 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 1560 reflections |
| a = 13.609 (10) Å | θ = 2.5–21.3º |
| b = 15.399 (11) Å | µ = 0.96 mm−1 |
| c = 12.632 (9) Å | T = 298 (2) K |
| β = 94.337 (11)º | Block, blue |
| V = 2640 (3) Å3 | 0.18 × 0.14 × 0.12 mm |
| Z = 4 |
| Bruker SMART-APEX diffractometer | 2323 independent reflections |
| Radiation source: fine-focus sealed tube | 1552 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.053 |
| T = 298(2) K | θmax = 25.0º |
| φ and ω scans | θmin = 2.0º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→16 |
| Tmin = 0.846, Tmax = 0.894 | k = −18→14 |
| 6731 measured reflections | l = −15→14 |
| 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)] = 0.052 | H-atom parameters constrained |
| wR(F2) = 0.167 | w = 1/[σ2(Fo2) + (0.097P)2 + 0.4954P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 2323 reflections | Δρmax = 0.57 e Å−3 |
| 150 parameters | Δρmin = −0.28 e Å−3 |
| 19 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| [NiCl2(C10H11N3)2]·CH4O | V = 2640 (3) Å3 |
| Mr = 508.09 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 13.609 (10) Å | µ = 0.96 mm−1 |
| b = 15.399 (11) Å | T = 298 (2) K |
| c = 12.632 (9) Å | 0.18 × 0.14 × 0.12 mm |
| β = 94.337 (11)º |
| Bruker SMART-APEX diffractometer | 2323 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1552 reflections with I > 2σ(I) |
| Tmin = 0.846, Tmax = 0.894 | Rint = 0.053 |
| 6731 measured reflections |
| R[F2 > 2σ(F2)] = 0.052 | 19 restraints |
| wR(F2) = 0.167 | H-atom parameters constrained |
| S = 1.02 | Δρmax = 0.57 e Å−3 |
| 2323 reflections | Δρmin = −0.28 e Å−3 |
| 150 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 > 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 | Occ. (<1) | |
| Ni1 | 1.0000 | 0.12244 (5) | 0.7500 | 0.0366 (3) | |
| Cl1 | 1.13154 (9) | 0.01906 (8) | 0.76050 (9) | 0.0498 (4) | |
| N1 | 0.9035 (3) | 0.2275 (3) | 0.7978 (3) | 0.0450 (10) | |
| N2 | 0.9990 (3) | 0.1486 (2) | 0.9113 (3) | 0.0362 (9) | |
| N3 | 1.1018 (3) | 0.0618 (3) | 1.0176 (3) | 0.0492 (11) | |
| H3A | 1.1205 | 0.0366 | 0.9618 | 0.059* | |
| H3B | 1.1261 | 0.0460 | 1.0794 | 0.059* | |
| O1 | 0.8427 (10) | 0.3836 (8) | 0.3032 (12) | 0.142 (5) | 0.50 |
| H1 | 0.7837 | 0.3941 | 0.3035 | 0.213* | 0.50 |
| C1 | 0.9341 (3) | 0.2147 (3) | 0.9013 (3) | 0.0392 (11) | |
| C2 | 1.0359 (3) | 0.1249 (3) | 1.0084 (3) | 0.0373 (11) | |
| C3 | 1.0054 (4) | 0.1694 (4) | 1.0990 (4) | 0.0533 (14) | |
| H3 | 1.0298 | 0.1519 | 1.1664 | 0.064* | |
| C4 | 0.9421 (4) | 0.2359 (4) | 1.0888 (4) | 0.0597 (15) | |
| H4 | 0.9239 | 0.2645 | 1.1492 | 0.072* | |
| C5 | 0.9021 (4) | 0.2635 (3) | 0.9862 (4) | 0.0498 (13) | |
| C6 | 0.8347 (4) | 0.3297 (4) | 0.9603 (5) | 0.0669 (16) | |
| C7 | 0.8050 (5) | 0.3422 (4) | 0.8555 (5) | 0.0712 (17) | |
| H7 | 0.7608 | 0.3867 | 0.8370 | 0.085* | |
| C8 | 0.8387 (4) | 0.2902 (4) | 0.7755 (4) | 0.0604 (15) | |
| C9 | 0.7974 (5) | 0.3884 (4) | 1.0462 (6) | 0.096 (2) | |
| H9A | 0.8501 | 0.4251 | 1.0745 | 0.143* | |
| H9B | 0.7744 | 0.3533 | 1.1021 | 0.143* | |
| H9C | 0.7443 | 0.4237 | 1.0161 | 0.143* | |
| C10 | 0.8065 (5) | 0.3040 (5) | 0.6585 (5) | 0.096 (2) | |
| H10A | 0.8608 | 0.2923 | 0.6165 | 0.144* | |
| H10B | 0.7853 | 0.3630 | 0.6476 | 0.144* | |
| H10C | 0.7530 | 0.2654 | 0.6379 | 0.144* | |
| C11 | 0.8902 (16) | 0.4248 (14) | 0.3805 (17) | 0.155 (7) | 0.50 |
| H11A | 0.9272 | 0.4714 | 0.3524 | 0.233* | 0.50 |
| H11B | 0.9343 | 0.3855 | 0.4192 | 0.233* | 0.50 |
| H11C | 0.8442 | 0.4480 | 0.4271 | 0.233* | 0.50 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.0416 (5) | 0.0413 (6) | 0.0266 (4) | 0.000 | 0.0006 (3) | 0.000 |
| Cl1 | 0.0544 (8) | 0.0553 (9) | 0.0388 (7) | 0.0143 (6) | −0.0016 (5) | −0.0065 (5) |
| N1 | 0.045 (2) | 0.049 (3) | 0.041 (2) | 0.010 (2) | 0.0026 (17) | 0.0066 (19) |
| N2 | 0.041 (2) | 0.037 (2) | 0.0300 (18) | 0.0033 (18) | 0.0014 (16) | −0.0001 (16) |
| N3 | 0.059 (3) | 0.058 (3) | 0.029 (2) | 0.010 (2) | −0.0054 (18) | 0.0034 (19) |
| O1 | 0.130 (8) | 0.148 (8) | 0.146 (8) | 0.055 (6) | −0.005 (7) | −0.023 (7) |
| C1 | 0.041 (3) | 0.039 (3) | 0.037 (2) | 0.000 (2) | 0.005 (2) | 0.002 (2) |
| C2 | 0.038 (3) | 0.044 (3) | 0.030 (2) | −0.002 (2) | 0.0023 (19) | 0.002 (2) |
| C3 | 0.060 (3) | 0.069 (4) | 0.031 (2) | 0.000 (3) | 0.006 (2) | −0.002 (2) |
| C4 | 0.071 (4) | 0.067 (4) | 0.043 (3) | 0.001 (3) | 0.021 (3) | −0.012 (3) |
| C5 | 0.053 (3) | 0.043 (3) | 0.056 (3) | 0.001 (3) | 0.016 (2) | −0.006 (2) |
| C6 | 0.059 (4) | 0.059 (4) | 0.085 (4) | 0.014 (3) | 0.022 (3) | −0.007 (3) |
| C7 | 0.066 (4) | 0.056 (4) | 0.093 (5) | 0.027 (3) | 0.010 (4) | 0.015 (4) |
| C8 | 0.055 (3) | 0.063 (4) | 0.064 (3) | 0.017 (3) | 0.007 (3) | 0.019 (3) |
| C9 | 0.093 (5) | 0.074 (5) | 0.123 (6) | 0.026 (4) | 0.032 (5) | −0.027 (4) |
| C10 | 0.099 (5) | 0.106 (6) | 0.080 (4) | 0.035 (4) | −0.020 (4) | 0.025 (4) |
| C11 | 0.153 (11) | 0.141 (10) | 0.167 (11) | 0.034 (8) | −0.018 (8) | −0.025 (9) |
| Ni1—N2i | 2.078 (4) | C3—H3 | 0.9300 |
| Ni1—N2 | 2.078 (4) | C4—C5 | 1.432 (7) |
| Ni1—N1i | 2.197 (4) | C4—H4 | 0.9300 |
| Ni1—N1 | 2.197 (4) | C5—C6 | 1.394 (8) |
| Ni1—Cl1i | 2.3918 (18) | C6—C7 | 1.368 (9) |
| Ni1—Cl1 | 2.3918 (18) | C6—C9 | 1.529 (8) |
| N1—C8 | 1.323 (6) | C7—C8 | 1.393 (8) |
| N1—C1 | 1.356 (6) | C7—H7 | 0.9300 |
| N2—C2 | 1.340 (5) | C8—C10 | 1.524 (8) |
| N2—C1 | 1.348 (6) | C9—H9A | 0.9600 |
| N3—C2 | 1.322 (6) | C9—H9B | 0.9600 |
| N3—H3A | 0.8600 | C9—H9C | 0.9600 |
| N3—H3B | 0.8600 | C10—H10A | 0.9600 |
| O1—C11 | 1.295 (15) | C10—H10B | 0.9600 |
| O1—H1 | 0.8200 | C10—H10C | 0.9600 |
| C1—C5 | 1.405 (6) | C11—H11A | 0.9600 |
| C2—C3 | 1.422 (6) | C11—H11B | 0.9600 |
| C3—C4 | 1.338 (7) | C11—H11C | 0.9600 |
| N2i—Ni1—N2 | 157.6 (2) | C3—C4—C5 | 120.8 (5) |
| N2i—Ni1—N1i | 62.57 (14) | C3—C4—H4 | 119.6 |
| N2—Ni1—N1i | 100.08 (14) | C5—C4—H4 | 119.6 |
| N2i—Ni1—N1 | 100.08 (14) | C6—C5—C1 | 116.6 (5) |
| N2—Ni1—N1 | 62.57 (14) | C6—C5—C4 | 128.9 (5) |
| N1i—Ni1—N1 | 85.1 (2) | C1—C5—C4 | 114.4 (5) |
| N2i—Ni1—Cl1i | 97.75 (10) | C7—C6—C5 | 118.1 (5) |
| N2—Ni1—Cl1i | 97.07 (11) | C7—C6—C9 | 121.0 (6) |
| N1i—Ni1—Cl1i | 159.27 (10) | C5—C6—C9 | 120.9 (6) |
| N1—Ni1—Cl1i | 92.59 (12) | C6—C7—C8 | 122.1 (5) |
| N2i—Ni1—Cl1 | 97.07 (11) | C6—C7—H7 | 119.0 |
| N2—Ni1—Cl1 | 97.75 (10) | C8—C7—H7 | 119.0 |
| N1i—Ni1—Cl1 | 92.59 (12) | N1—C8—C7 | 121.0 (5) |
| N1—Ni1—Cl1 | 159.27 (10) | N1—C8—C10 | 116.5 (5) |
| Cl1i—Ni1—Cl1 | 96.55 (9) | C7—C8—C10 | 122.4 (5) |
| C8—N1—C1 | 117.5 (4) | C6—C9—H9A | 109.5 |
| C8—N1—Ni1 | 151.8 (4) | C6—C9—H9B | 109.5 |
| C1—N1—Ni1 | 90.7 (3) | H9A—C9—H9B | 109.5 |
| C2—N2—C1 | 119.3 (4) | C6—C9—H9C | 109.5 |
| C2—N2—Ni1 | 144.6 (3) | H9A—C9—H9C | 109.5 |
| C1—N2—Ni1 | 96.2 (3) | H9B—C9—H9C | 109.5 |
| C2—N3—H3A | 120.0 | C8—C10—H10A | 109.5 |
| C2—N3—H3B | 120.0 | C8—C10—H10B | 109.5 |
| H3A—N3—H3B | 120.0 | H10A—C10—H10B | 109.5 |
| C11—O1—H1 | 109.5 | C8—C10—H10C | 109.5 |
| N2—C1—N1 | 110.6 (4) | H10A—C10—H10C | 109.5 |
| N2—C1—C5 | 124.8 (4) | H10B—C10—H10C | 109.5 |
| N1—C1—C5 | 124.6 (4) | O1—C11—H11A | 109.5 |
| N3—C2—N2 | 119.1 (4) | O1—C11—H11B | 109.5 |
| N3—C2—C3 | 121.4 (4) | H11A—C11—H11B | 109.5 |
| N2—C2—C3 | 119.6 (4) | O1—C11—H11C | 109.5 |
| C4—C3—C2 | 121.1 (5) | H11A—C11—H11C | 109.5 |
| C4—C3—H3 | 119.4 | H11B—C11—H11C | 109.5 |
| C2—C3—H3 | 119.4 |
| Symmetry codes: (i) −x+2, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···Cl1ii | 0.82 | 2.49 | 3.250 (12) | 155 |
| N3—H3B···Cl1iii | 0.86 | 2.49 | 3.308 (4) | 159 |
| N3—H3A···Cl1 | 0.86 | 2.57 | 3.368 (4) | 154 |
| Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) x, −y, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···Cl1i | 0.82 | 2.49 | 3.250 (12) | 155 |
| N3—H3B···Cl1ii | 0.86 | 2.49 | 3.308 (4) | 159 |
| N3—H3A···Cl1 | 0.86 | 2.57 | 3.368 (4) | 154 |
| Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x, −y, z+1/2. |
The authors thank the Zhejiang Forestry University Science Foundation for financial support.
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The molecular structures and chemical properties (Kukrek et al., 2006; Che et al., 2001) of transition metal complexes of 1,8-naphthyridine (napy) and its derivatives have received much attention, as the ligands can link to metals with several coordination modes such as monodentate, chelating bidentate, and dinuclear bridging binding fashion (Gavrilova & Bosnich, 2004). 5,7-dimethyl-1,8-naphthyridin-2-amine is a potentially tridentate ligand and is capable of linking two to four metal atoms together to form metal aggregates (Oskui et al., 1999; Mintert & Sheldrick, 1995a; Oskui & Sheldrick, 1999; Mintert & Sheldrick, 1995b). The coordination chemistry of 5,7-dimethyl-1,8-naphthyridine-2-amine (L) has not been well studied although an Ni(II) complex (Ni(L)2(Cl)2)(Bayer, 1979) has been decribed in a US patent. As an extension of our study (Jin et al., 2007) on naphthyridine coordination chemistry, we have determined the crystal structure of the the title complex (Ni(L)2(Cl)2)·(CH3OH).
The title compound was obtained as blue crystals by reacting of nickel chloride hexahydrate and L in methanol. The compound is a neutral compound which is air stable and light insensitive. The complex does not dissolve in water and common organic solvent. X-ray structural analysis shows that the complex is mononuclear. The molecular structure of the compound is shown in Fig. 1.
The Ni atom lies on a crystallographic twofold axis and is coordinated to two L ligands, and two chloride ions. The Cl atoms are in a cis orientation with respect to each other (Cl1—Ni1—Cl1i = 96.55 (10)°; symmetry code: (i) −x + 2, y, −z + 3/2). Both L ligands coordinate through N atoms in a bidentate chelate fashion to form two four-membered Ni/N/C/N rings. Two chloride anions coordinate to the NiII ion to complete the distorted octahedral geometry. The amine group of the 5,7-dimethyl-1,8-naphthyridin-2-amine ligand does not form any bonding interactions with Ni atoms. All the bond lengths and bond angles in the ligand are in the normal ranges (Allen et al., 1987). The N2—C2 bond distance is 1.340 (5) Å, typical for a C—N double bond. The two naphthyridine rings are almost perpendicular to each other with the N1i—Ni1—N1—C8, N2i—Ni1—N1—C8 torsion angles of 75.41 (16), and 14.39 (14)°. N2—Ni1—N1i, and N1i—Ni1—N1 are 100.08 (14), and 85.1 (2) ° respectively. The solvent methanol molecules are bonded to the corresponding (Ni(L)2(Cl)2) moiety through hydrogen bonds and a (Ni(L)2(Cl)2) moiety is bonded to two neighbouring (Ni(L)2(Cl)2) moieties via hydrogen bonds. Hence, in the crystal structure, the compound forms 1-D chains along the c axis via intermolecular hydrogen bonds, (Fig. 2).