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Acta Cryst. (2007). E63, m2118    [ doi:10.1107/S1600536807033582 ]

[[mu]-1,2-Disalicyloylhydrazine(2-)-[kappa]3N,O,O':[kappa]3N',O'',O''']bis[tripyridinenickel(II)] pyridine disolvate

Y.-T. Chen, J.-M. Dou, D.-C. Li, D.-Q. Wang and Y.-H. Zhu

Abstract top

The title complex, [Ni2(C14H8N2O4)(C5H5N)6]·2C5H5N, is a polymorph of a previously reported compound [Chen & Liu (2005). Chin. J. Inorg. Chem. 21, 15-20]. The 1,2-disalicyloylhydrazine ligand lies on an inversion center and coordinates to two NiII atoms. Each NiII atom is octahedrally coordinated by a phenolate O atom, a carbonyl O atom and a hydrazine N atom of the ligand and three pyridine N atoms.

Comment top

Recently, we have synthesized two metallacrowns using N-acyl-3-hydroxy-2-naphthalenecarbohydrazide (Dou et al., 2006). As an extension of our work on the structural characterization of naphthalenecarbohydrazide compounds, the title complex, (I), was synthesized and characterized by X-ray diffraction.

The complex (I) (space group I41/a) is a polymorph of the compound (space group P21/c) previously reported by Chen & Liu (2005), with the same formula [Ni2(C14H8N2O4)(C5H5N)6].2C5H5N. The complex molecule of (I) lies on an inversion center (Fig. 1). The 1,2-disalicyloylhydrazine molecule acts as a hexadentate tetravalent anionic ligand linking two NiII atoms. The iminophenolate group (O2 and N1) and the iminoacyl group (O1i and N1; symmetry code: (i) 1 - x, -y, -z) of the ligand are coordinated to the Ni1 atom to form six-membered and five-membered chelating rings, respectively, with a dihedral angle of 1.7 (4)°. Besides the above three atoms coordinated to the Ni1 atom, there are other three pyridine N atoms bonded to the Ni1 atom. So the coordination geometry of the Ni1 atom can be described as an N4O2 octahedron. As shown in Table 1, the axial Ni—N distances are longer than the equatorial Ni—N and Ni—O distances, which shows the NiII atom in a distorted octahedral geometry. This typical Jahn-Teller elongation has been observed in the other complexes (Kwak et al., 2000).

Related literature top

For related literature, see: Chen & Liu (2005); Dou et al. (2006); Kwak et al. (2000).

Experimental top

A solution of Ni(CH3CO2)2.H2O (0.100 g, 0.4 mmol) in methanol (10 ml) was added to the mixture of 1,2-disalicyloylhydrazine (0.054 g, 0.2 mmol) and sodium hydroxide (0.032 g, 0.8 mmol) in pyridine (10 ml). A red solution was generated after stirring for 2 h at room temperature. The solution was allowed to stand for 2 weeks, whereupon red needle crystals were obtained (0.070 g, yield 34%).

Refinement top

All H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) 1 - x, -y, -z.]
[µ-1,2-Disalicyloylhydrazine(2-)- κ3N,O,O':κ3N',O'',O''']bis[tripyridinenickel(II)] pyridine disolvate top
Crystal data top
[Ni2(C14H8N2O4)(C5H5N)6]·2C5H5NDx = 1.292 Mg m−3
Mr = 1018.44Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 3046 reflections
Hall symbol: -I 4adθ = 2.2–21.5°
a = 27.040 (2) ŵ = 0.77 mm−1
c = 14.3178 (18) ÅT = 298 K
V = 10468.6 (17) Å3Block, red
Z = 80.34 × 0.23 × 0.20 mm
F(000) = 4240
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		4609 independent reflections
Radiation source: fine-focus sealed tube2743 reflections with I > 2σ(I)
graphiteRint = 0.064
φ and ω scansθmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −13→32
Tmin = 0.779, Tmax = 0.861k = −32→30
21466 measured reflectionsl = −17→17
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.07P)2]
where P = (Fo2 + 2Fc2)/3
4609 reflections(Δ/σ)max < 0.001
316 parametersΔρmax = 0.31 e Å−3
102 restraintsΔρmin = −0.43 e Å−3
Crystal data top
[Ni2(C14H8N2O4)(C5H5N)6]·2C5H5NZ = 8
Mr = 1018.44Mo Kα radiation
Tetragonal, I41/aµ = 0.77 mm−1
a = 27.040 (2) ÅT = 298 K
c = 14.3178 (18) Å0.34 × 0.23 × 0.20 mm
V = 10468.6 (17) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		4609 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2743 reflections with I > 2σ(I)
Tmin = 0.779, Tmax = 0.861Rint = 0.064
21466 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.152Δρmax = 0.31 e Å−3
S = 1.02Δρmin = −0.43 e Å−3
4609 reflectionsAbsolute structure: ?
316 parametersFlack parameter: ?
102 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Ni10.547168 (18)0.061356 (19)0.07264 (4)0.0430 (2)
N10.50175 (11)0.00672 (11)0.0474 (2)0.0402 (8)
N20.49003 (13)0.11803 (14)0.0520 (3)0.0576 (9)
N30.61032 (12)0.01068 (13)0.0880 (3)0.0498 (9)
N40.59618 (12)0.12023 (12)0.0881 (2)0.0465 (9)
N50.7088 (6)0.3732 (4)0.3455 (7)0.175 (4)
O10.44541 (9)−0.05583 (9)0.07017 (18)0.0443 (7)
O20.53200 (10)0.05767 (9)0.2084 (2)0.0492 (7)
C10.47284 (14)−0.02083 (14)0.1014 (3)0.0384 (9)
C20.47115 (14)−0.00872 (14)0.2032 (3)0.0381 (9)
C30.49896 (14)0.02951 (14)0.2477 (3)0.0420 (10)
C40.48975 (16)0.03587 (16)0.3447 (3)0.0501 (11)
H40.50680.06070.37610.060*
C50.45740 (16)0.00756 (17)0.3939 (3)0.0533 (11)
H50.45280.01350.45720.064*
C60.43109 (17)−0.03022 (17)0.3502 (3)0.0565 (12)
H60.4094−0.05020.38360.068*
C70.43824 (14)−0.03701 (16)0.2565 (3)0.0468 (10)
H70.4203−0.06170.22660.056*
C80.4812 (2)0.1372 (2)−0.0297 (5)0.0941 (16)
H80.49770.1238−0.08070.113*
C90.4494 (2)0.1757 (3)−0.0462 (5)0.1082 (17)
H90.44580.1884−0.10620.130*
C100.4239 (2)0.1948 (2)0.0245 (5)0.1061 (17)
H100.40140.22040.01540.127*
C110.4319 (3)0.1754 (3)0.1097 (5)0.1206 (19)
H110.41490.18760.16130.145*
C120.4651 (2)0.1376 (2)0.1203 (5)0.1042 (17)
H120.47020.12510.18010.125*
C130.61964 (19)−0.02483 (18)0.0272 (4)0.0725 (15)
H130.5992−0.0278−0.02470.087*
C140.6578 (2)−0.0574 (2)0.0369 (5)0.0954 (19)
H140.6626−0.0819−0.00770.115*
C150.6881 (2)−0.0543 (3)0.1102 (6)0.101 (2)
H150.7142−0.07630.11760.121*
C160.6796 (2)−0.0176 (3)0.1742 (5)0.109 (2)
H160.6998−0.01400.22640.131*
C170.6407 (2)0.0136 (2)0.1591 (4)0.0812 (17)
H170.63540.03880.20230.097*
C180.62427 (18)0.13505 (18)0.0177 (4)0.0663 (14)
H180.62140.1184−0.03890.080*
C190.65742 (19)0.17364 (19)0.0229 (4)0.0746 (15)
H190.67600.1828−0.02890.090*
C200.66227 (19)0.19768 (18)0.1045 (4)0.0708 (15)
H200.68440.22390.11040.085*
C210.6339 (2)0.18282 (19)0.1793 (4)0.0796 (16)
H210.63650.19870.23680.096*
C220.60200 (19)0.14440 (18)0.1675 (3)0.0679 (14)
H220.58310.13450.21850.081*
C230.6591 (6)0.3744 (4)0.3440 (8)0.159 (4)
H230.64070.35140.37750.191*
C240.6371 (4)0.4087 (7)0.2945 (11)0.185 (6)
H240.60290.41190.29790.223*
C250.6630 (7)0.4396 (4)0.2384 (10)0.166 (6)
H250.64650.46140.19900.199*
C260.7111 (7)0.4387 (4)0.2398 (8)0.177 (5)
H260.72910.46090.20360.213*
C270.7346 (3)0.4057 (5)0.2934 (11)0.156 (4)
H270.76900.40530.29480.187*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0436 (3)0.0457 (3)0.0396 (3)−0.0082 (2)−0.0003 (2)−0.0042 (2)
N10.0420 (18)0.048 (2)0.0302 (17)−0.0042 (16)0.0010 (15)−0.0027 (15)
N20.056 (2)0.060 (2)0.058 (2)0.0037 (18)0.0054 (18)−0.0014 (18)
N30.047 (2)0.049 (2)0.053 (2)−0.0053 (17)−0.0005 (18)0.0004 (18)
N40.049 (2)0.044 (2)0.047 (2)−0.0061 (16)−0.0016 (17)−0.0021 (17)
N50.249 (13)0.146 (8)0.131 (8)0.039 (9)−0.048 (8)−0.037 (6)
O10.0460 (16)0.0466 (16)0.0402 (17)−0.0145 (13)0.0017 (12)−0.0025 (13)
O20.0572 (18)0.0501 (17)0.0403 (17)−0.0147 (15)0.0006 (13)−0.0016 (13)
C10.037 (2)0.041 (2)0.037 (2)0.0008 (18)0.0024 (17)0.0012 (18)
C20.039 (2)0.041 (2)0.034 (2)0.0028 (18)−0.0001 (17)0.0000 (17)
C30.041 (2)0.044 (2)0.041 (2)0.0062 (19)−0.0039 (19)−0.0007 (19)
C40.056 (3)0.055 (3)0.039 (3)0.002 (2)0.000 (2)−0.010 (2)
C50.057 (3)0.069 (3)0.034 (2)0.004 (2)0.006 (2)0.000 (2)
C60.055 (3)0.064 (3)0.050 (3)−0.006 (2)0.012 (2)0.003 (2)
C70.041 (2)0.055 (3)0.045 (3)−0.005 (2)0.0049 (19)−0.001 (2)
C80.105 (3)0.096 (3)0.081 (3)0.040 (3)0.003 (3)0.006 (3)
C90.119 (4)0.110 (4)0.096 (4)0.045 (3)−0.003 (3)0.010 (3)
C100.111 (4)0.104 (4)0.104 (4)0.046 (3)0.003 (3)0.010 (3)
C110.133 (4)0.125 (4)0.105 (4)0.058 (3)0.022 (3)0.004 (3)
C120.113 (4)0.114 (4)0.086 (4)0.056 (3)0.020 (3)0.013 (3)
C130.085 (4)0.067 (3)0.066 (4)0.023 (3)−0.008 (3)−0.007 (3)
C140.112 (5)0.091 (4)0.083 (5)0.044 (4)0.014 (4)0.005 (3)
C150.071 (4)0.114 (6)0.118 (6)0.035 (4)0.003 (4)0.026 (5)
C160.085 (5)0.109 (5)0.133 (7)0.011 (4)−0.054 (4)0.001 (5)
C170.075 (4)0.075 (4)0.093 (4)0.008 (3)−0.031 (3)−0.009 (3)
C180.070 (3)0.070 (3)0.059 (3)−0.021 (3)0.012 (3)−0.006 (3)
C190.070 (3)0.072 (4)0.082 (4)−0.025 (3)0.011 (3)0.002 (3)
C200.063 (3)0.055 (3)0.094 (4)−0.020 (3)−0.011 (3)0.004 (3)
C210.088 (4)0.071 (4)0.080 (4)−0.033 (3)−0.006 (3)−0.019 (3)
C220.076 (3)0.071 (3)0.056 (3)−0.028 (3)0.007 (3)−0.012 (3)
C230.184 (11)0.172 (11)0.121 (9)0.005 (10)0.069 (9)0.017 (7)
C240.128 (9)0.245 (17)0.184 (14)0.104 (11)−0.004 (8)−0.064 (11)
C250.223 (15)0.094 (7)0.181 (13)0.054 (9)−0.090 (12)−0.019 (7)
C260.257 (16)0.071 (6)0.204 (12)−0.036 (9)−0.035 (11)0.032 (6)
C270.131 (8)0.101 (7)0.235 (14)−0.010 (7)−0.024 (9)−0.058 (8)
Geometric parameters (Å, °) top
Ni1—N11.955 (3)C9—H90.9300
Ni1—O21.989 (3)C10—C111.346 (9)
Ni1—O1i2.060 (3)C10—H100.9300
Ni1—N42.083 (3)C11—C121.369 (8)
Ni1—N22.196 (4)C11—H110.9300
Ni1—N32.201 (3)C12—H120.9300
N1—C11.328 (5)C13—C141.363 (7)
N1—N1i1.409 (6)C13—H130.9300
N2—C121.300 (6)C14—C151.335 (8)
N2—C81.301 (6)C14—H140.9300
N3—C171.310 (6)C15—C161.371 (9)
N3—C131.320 (6)C15—H150.9300
N4—C221.320 (5)C16—C171.366 (8)
N4—C181.325 (5)C16—H160.9300
N5—C231.345 (11)C17—H170.9300
N5—C271.348 (11)C18—C191.378 (6)
O1—C11.283 (4)C18—H180.9300
O1—Ni1i2.060 (3)C19—C201.344 (7)
O2—C31.302 (4)C19—H190.9300
C1—C21.495 (5)C20—C211.378 (7)
C2—C71.399 (5)C20—H200.9300
C2—C31.428 (5)C21—C221.361 (6)
C3—C41.421 (5)C21—H210.9300
C4—C51.359 (5)C22—H220.9300
C4—H40.9300C23—C241.310 (11)
C5—C61.393 (6)C23—H230.9300
C5—H50.9300C24—C251.354 (12)
C6—C71.368 (6)C24—H240.9300
C6—H60.9300C25—C261.30 (3)
C7—H70.9300C25—H250.9300
C8—C91.371 (7)C26—C271.337 (10)
C8—H80.9300C26—H260.9300
C9—C101.329 (8)C27—H270.9300
N1—Ni1—O290.75 (11)C8—C9—H9120.4
N1—Ni1—O1i79.81 (11)C9—C10—C11117.1 (7)
O2—Ni1—O1i170.55 (10)C9—C10—H10121.4
N1—Ni1—N4175.46 (13)C11—C10—H10121.4
O2—Ni1—N493.76 (12)C10—C11—C12119.8 (7)
O1i—Ni1—N495.68 (12)C10—C11—H11120.1
N1—Ni1—N293.47 (13)C12—C11—H11120.1
O2—Ni1—N291.23 (13)N2—C12—C11124.1 (6)
O1i—Ni1—N289.17 (13)N2—C12—H12118.0
N4—Ni1—N285.91 (13)C11—C12—H12118.0
N1—Ni1—N392.03 (13)N3—C13—C14123.2 (5)
O2—Ni1—N391.77 (12)N3—C13—H13118.4
O1i—Ni1—N388.77 (12)C14—C13—H13118.4
N4—Ni1—N388.37 (12)C15—C14—C13120.3 (6)
N2—Ni1—N3173.70 (13)C15—C14—H14119.8
C1—N1—N1i112.1 (4)C13—C14—H14119.8
C1—N1—Ni1133.4 (3)C14—C15—C16117.9 (6)
N1i—N1—Ni1114.5 (3)C14—C15—H15121.1
C12—N2—C8114.8 (5)C16—C15—H15121.1
C12—N2—Ni1123.2 (4)C17—C16—C15118.1 (6)
C8—N2—Ni1121.9 (4)C17—C16—H16120.9
C17—N3—C13115.9 (4)C15—C16—H16120.9
C17—N3—Ni1121.8 (3)N3—C17—C16124.6 (6)
C13—N3—Ni1122.3 (3)N3—C17—H17117.7
C22—N4—C18115.9 (4)C16—C17—H17117.7
C22—N4—Ni1123.1 (3)N4—C18—C19124.1 (5)
C18—N4—Ni1121.0 (3)N4—C18—H18117.9
C23—N5—C27119.5 (9)C19—C18—H18117.9
C1—O1—Ni1i110.1 (2)C20—C19—C18118.5 (5)
C3—O2—Ni1126.4 (2)C20—C19—H19120.7
O1—C1—N1123.5 (4)C18—C19—H19120.7
O1—C1—C2118.9 (3)C19—C20—C21118.7 (5)
N1—C1—C2117.6 (3)C19—C20—H20120.6
C7—C2—C3119.2 (4)C21—C20—H20120.6
C7—C2—C1115.5 (3)C22—C21—C20118.6 (5)
C3—C2—C1125.3 (3)C22—C21—H21120.7
O2—C3—C4118.2 (4)C20—C21—H21120.7
O2—C3—C2126.3 (4)N4—C22—C21124.1 (5)
C4—C3—C2115.5 (4)N4—C22—H22117.9
C5—C4—C3123.4 (4)C21—C22—H22117.9
C5—C4—H4118.3C24—C23—N5118.7 (9)
C3—C4—H4118.3C24—C23—H23120.6
C4—C5—C6120.6 (4)N5—C23—H23120.6
C4—C5—H5119.7C23—C24—C25121.5 (10)
C6—C5—H5119.7C23—C24—H24119.3
C7—C6—C5117.8 (4)C25—C24—H24119.3
C7—C6—H6121.1C26—C25—C24119.8 (10)
C5—C6—H6121.1C26—C25—H25120.1
C6—C7—C2123.4 (4)C24—C25—H25120.1
C6—C7—H7118.3C25—C26—C27119.7 (9)
C2—C7—H7118.3C25—C26—H26120.1
N2—C8—C9124.9 (6)C27—C26—H26120.1
N2—C8—H8117.5C26—C27—N5120.4 (9)
C9—C8—H8117.5C26—C27—H27119.8
C10—C9—C8119.3 (7)N5—C27—H27119.8
C10—C9—H9120.4
Symmetry codes: (i) −x+1, −y, −z.
Table 1
Selected geometric parameters (Å) top
Ni1—N11.955 (3)Ni1—N42.083 (3)
Ni1—O21.989 (3)Ni1—N22.196 (4)
Ni1—O1i2.060 (3)Ni1—N32.201 (3)
Symmetry codes: (i) −x+1, −y, −z.
Acknowledgements top

The authors acknowledge the support of the National Natural Science Foundation of China (20671048).

references
References top

Chen, X. H. & Liu, S. X. (2005). Chin. J. Inorg. Chem. 21, 15–20.

Dou, J. M., Liu, M. L., Li, D. C. & Wang, D. Q. (2006). Eur. J. Inorg. Chem. 23, 4866–4871.

Kwak, B., Rhee, H. & Lah, M. S. (2000). Polyhedron, 19, 1985–1994.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Siemens (1996). SMART, SAINT and SHELXTL. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.