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Acta Cryst. (2007). E63, m2579    [ doi:10.1107/S1600536807045370 ]

(1-{(E)-2-[(2E,3Z)-4-Oxidopent-3-en-2-ylideneamino]ethyliminomethyl}naphthalen-2-olato)manganese(II) methanol solvate

B. Xu, J.-W. Ran and Y.-H. Li

Abstract top

In the title compound, [Mn(C18H18N2O2)]·CH3OH, the Mn atom is coordinated by two N atoms and two O atoms from the asymmetrical Schiff base ligand 1-[2-(4-oxidopent-3-en-2-ylideneamino)ethyliminomethyl]naphthalen-2-olate in an approximately square-planar configuration. There is an O-H...O hydrogen-bond interaction between the complex and the methanol solvent molecule.

Comment top

Complexes synthesized from manganese and Schiff base ligand have been of great interest for many years. They are very important in the development of coordination chemistry. As an extension of the research on the structural characterization of Mn compounds, we report here the crystal structure of a new mononuclear manganese(II) complex.

The title compound is an electronically neutral mononuclear manganese(II) complex. The MnII ion in the compound is four coordinated by two N atoms and two O atoms from the asymmetrical tetradentate Schiff base ligand H2hemn (H2hemn= 1-((E)-(2-((E)-((Z)-4-hydroxypent-3-en-2-ylidene)amino)\ ethylimino)methyl)naphthalen-2-ol) in an approximately square-planar geometry. The Mn—N2 bond distance (1.812 (6) Å) is shorter than Mn—N1(1.836 (5) Å) and the other two Mn—O bonds distance (Mn—O1=1.835 (5) Å, Mn—O2=1.829 (4) Å). There is O—H···O hydrogen bond interaction between the complex and the methanol solvent molecule (Table 1).

Related literature top

Complexes with a similar ligand were reported by Yan et al. (2006); in those complexes the ligand was synthesized from the reaction of ethylenediamine, acetylacetone and salicylaldehyde.

Experimental top

1. Synthesis of the ligand H2hemn

To a 250 ml 3-neck round-bottom flask containing a solution of ethylenediamine (0.1 mol, 6.01 g) in ethanol (60 ml) at 50 °C, was added dropwise a solution of acetylacetone (0.1 mol, 10.01 g) in ethanol (60 ml). After the mixture was stirred at 50 °C for 4 h. A suspension of 2-hydroxy-1-naphthaldehyde (0.1 mol, 17.22 g) in ethanol (50 ml) was added into the flask. The resulted mixture was continued being stirred for another 4 h and then cooled down and the crude product was precipitated. The crude product was collected by filtration, washed with ethanol and vacuum dried overnight. The brown product H2hemn was used without further purification.

2. Synthesis of the complex

To a solution of MnCl2·4H2O (1 mmol, 197 mg) in methanol (40 ml) was added ligand H2hemn (1 mmol, 298 mg). After the resulted brown mixture was stirred at room temperature for 48 h, a brown turbid solution was obtained. The solution was filtered and slow evaporation of the solvent from the filtrate afforded dark brown crystals after 30 d.

Refinement top

Methyl H atoms and hydroxyl H atom were placed in calculated positions with C—H = 0.96 Å and O—H = 0.82 Å, and torsion angles were refined, Uiso(H) = 1.5Ueq(C,O). Other H atoms were placed in calculated positions with C—H = 0.93 (aromatic) or 0.97 Å (methylene) and refined in riding mode, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The atom-numbering scheme of the title complex. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted.
[Figure 2] Fig. 2. The packed diagram for the title compound, viewed down the b axis with hydrogen bonds drawn as dashed lines. H atoms have been omitted.
(1-{(E)-2-[(2E,3Z)-4-Oxidopent-3-en-2- ylideneamino]ethyliminomethyl}naphthalen-2-olato)manganese(II) methanol solvate top
Crystal data top
[Mn(C18H18N2O2)]·CH4OF000 = 796
Mr = 381.33Dx = 1.431 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abθ = 1.9–25.0º
a = 7.3800 (16) ŵ = 0.77 mm−1
b = 10.8935 (14) ÅT = 298 (2) K
c = 22.01 (2) ÅBlock, dark brown
V = 1769.6 (18) Å30.48 × 0.32 × 0.29 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3122 independent reflections
Radiation source: fine-focus sealed tube1863 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.081
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.709, Tmax = 0.808k = −12→12
9257 measured reflectionsl = −12→26
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.050  w = 1/[σ2(Fo2) + (0.0806P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.152(Δ/σ)max = 0.001
S = 0.91Δρmax = 0.29 e Å−3
3122 reflectionsΔρmin = −0.29 e Å−3
227 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1306 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: −0.14 (4)
Crystal data top
[Mn(C18H18N2O2)]·CH4OV = 1769.6 (18) Å3
Mr = 381.33Z = 4
Orthorhombic, P212121Mo Kα
a = 7.3800 (16) ŵ = 0.77 mm−1
b = 10.8935 (14) ÅT = 298 (2) K
c = 22.01 (2) Å0.48 × 0.32 × 0.29 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3122 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1863 reflections with I > 2σ(I)
Tmin = 0.709, Tmax = 0.808Rint = 0.081
9257 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.152Δρmax = 0.29 e Å−3
S = 0.91Δρmin = −0.29 e Å−3
3122 reflectionsAbsolute structure: Flack (1983), 1306 Friedel pairs
227 parametersFlack parameter: −0.14 (4)
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.

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 > 2σ(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
xyzUiso*/Ueq
Mn10.56596 (12)0.66361 (7)0.47664 (4)0.0444 (3)
N10.5557 (7)0.8306 (5)0.4659 (3)0.0621 (13)
N20.5466 (8)0.6932 (5)0.5574 (3)0.0653 (15)
O10.6034 (6)0.6254 (4)0.3964 (2)0.0703 (14)
C10.6364 (10)0.6470 (7)0.2897 (3)0.091 (2)
H1A0.76420.63250.28560.136*
H1B0.59720.70250.25840.136*
H1C0.57230.57070.28580.136*
O20.5492 (7)0.4972 (4)0.48610 (18)0.0685 (12)
O30.3061 (10)0.4431 (6)0.3797 (3)0.140 (3)
H40.36920.45010.41020.210*
C20.5976 (10)0.7030 (7)0.3516 (3)0.070 (2)
C30.5641 (10)0.8231 (6)0.3573 (3)0.0754 (19)
H20.55510.86860.32160.090*
C40.5406 (9)0.8882 (6)0.4136 (4)0.070 (2)
C50.4973 (10)1.0246 (6)0.4112 (4)0.104 (3)
H4A0.58801.06940.43320.155*
H4B0.38081.03890.42920.155*
H4C0.49581.05140.36970.155*
C60.5291 (10)0.9018 (6)0.5220 (4)0.077 (2)
H5A0.40230.92310.52690.093*
H5B0.59970.97680.52070.093*
C70.5913 (10)0.8210 (6)0.5734 (3)0.076 (2)
H6A0.72090.82970.57940.091*
H6B0.53050.84410.61080.091*
C80.5105 (8)0.6148 (6)0.6014 (3)0.0626 (19)
H70.50630.64500.64090.075*
C90.4781 (8)0.4893 (6)0.5928 (3)0.0618 (18)
C100.4983 (9)0.4373 (6)0.5344 (3)0.067 (2)
C110.4626 (12)0.3081 (6)0.5271 (3)0.090 (2)
H100.47870.27190.48930.108*
C120.4054 (13)0.2374 (6)0.5749 (4)0.092 (3)
H110.37570.15550.56830.111*
C130.3906 (11)0.2869 (7)0.6343 (4)0.078 (2)
C140.4268 (10)0.4126 (7)0.6430 (3)0.0694 (18)
C150.4008 (10)0.4593 (8)0.7031 (3)0.087 (2)
H140.42120.54170.71190.105*
C160.3433 (11)0.3769 (11)0.7489 (4)0.110 (3)
H150.32620.40740.78790.132*
C170.3113 (14)0.2542 (10)0.7389 (5)0.110 (3)
H160.27120.20310.77000.132*
C180.3400 (11)0.2108 (8)0.6825 (5)0.097 (3)
H170.32560.12730.67530.116*
C190.3463 (13)0.3403 (9)0.3519 (5)0.148 (4)
H18A0.37350.35710.31000.222*
H18B0.24510.28520.35420.222*
H18C0.44980.30340.37100.222*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0396 (4)0.0422 (4)0.0515 (5)−0.0011 (4)0.0017 (5)−0.0022 (5)
N10.047 (3)0.056 (3)0.083 (4)−0.006 (3)0.003 (4)−0.002 (3)
N20.053 (3)0.068 (4)0.075 (4)−0.004 (3)0.000 (3)−0.008 (3)
O10.081 (4)0.059 (3)0.071 (3)−0.004 (2)0.004 (3)0.006 (2)
C10.094 (6)0.097 (6)0.081 (5)0.010 (5)0.016 (4)0.011 (5)
O20.088 (3)0.054 (2)0.064 (3)0.005 (3)0.011 (3)−0.002 (2)
O30.144 (6)0.110 (5)0.166 (6)0.018 (4)−0.034 (5)−0.036 (5)
C20.062 (5)0.074 (5)0.075 (5)−0.009 (4)0.009 (4)0.004 (4)
C30.073 (5)0.057 (4)0.097 (5)−0.003 (5)0.000 (5)0.012 (4)
C40.041 (4)0.058 (4)0.111 (6)−0.008 (3)0.003 (5)0.014 (4)
C50.075 (6)0.064 (5)0.172 (9)0.000 (4)0.011 (6)0.028 (6)
C60.062 (5)0.056 (4)0.113 (6)−0.008 (3)0.015 (5)−0.017 (5)
C70.066 (5)0.075 (5)0.086 (5)−0.015 (5)0.006 (4)−0.024 (4)
C80.051 (4)0.077 (5)0.060 (4)0.000 (3)−0.002 (3)0.002 (4)
C90.056 (5)0.063 (4)0.067 (4)0.006 (3)0.004 (3)0.004 (4)
C100.077 (5)0.047 (4)0.077 (5)0.008 (3)−0.002 (4)0.004 (4)
C110.112 (7)0.076 (5)0.083 (5)0.008 (4)0.014 (6)−0.004 (4)
C120.111 (7)0.055 (4)0.111 (7)0.001 (5)0.023 (6)0.023 (5)
C130.070 (6)0.074 (5)0.090 (6)0.012 (4)0.016 (4)0.019 (5)
C140.054 (4)0.082 (5)0.073 (5)0.011 (5)0.004 (4)0.012 (4)
C150.072 (6)0.118 (7)0.071 (5)0.010 (5)−0.004 (4)0.014 (5)
C160.077 (6)0.184 (11)0.069 (6)0.024 (7)0.004 (5)0.031 (7)
C170.105 (8)0.106 (8)0.120 (9)0.017 (6)0.008 (7)0.039 (7)
C180.086 (6)0.085 (6)0.118 (7)0.013 (5)0.013 (6)0.029 (6)
C190.152 (10)0.120 (8)0.172 (9)0.031 (8)0.003 (8)−0.078 (8)
Geometric parameters (Å, °) top
Mn1—N21.812 (6)C6—H5B0.9700
Mn1—O21.829 (4)C7—H6A0.9700
Mn1—O11.835 (5)C7—H6B0.9700
Mn1—N11.836 (5)C8—C91.401 (8)
N1—C41.316 (8)C8—H70.9300
N1—C61.470 (8)C9—C101.412 (9)
N2—C81.319 (7)C9—C141.436 (8)
N2—C71.475 (8)C10—C111.441 (9)
O1—C21.300 (7)C11—C121.370 (9)
C1—C21.521 (10)C11—H100.9300
C1—H1A0.9600C12—C131.418 (10)
C1—H1B0.9600C12—H110.9300
C1—H1C0.9600C13—C181.396 (10)
O2—C101.303 (7)C13—C141.408 (10)
O3—C191.311 (9)C14—C151.432 (9)
O3—H40.8200C15—C161.414 (10)
C2—C31.338 (8)C15—H140.9300
C3—C41.439 (9)C16—C171.375 (11)
C3—H20.9300C16—H150.9300
C4—C51.520 (8)C17—C181.346 (11)
C5—H4A0.9600C17—H160.9300
C5—H4B0.9600C18—H170.9300
C5—H4C0.9600C19—H18A0.9600
C6—C71.506 (9)C19—H18B0.9600
C6—H5A0.9700C19—H18C0.9600
N2—Mn1—O293.4 (2)C6—C7—H6A110.2
N2—Mn1—O1174.9 (2)N2—C7—H6B110.2
O2—Mn1—O183.98 (18)C6—C7—H6B110.2
N2—Mn1—N186.9 (2)H6A—C7—H6B108.5
O2—Mn1—N1173.7 (2)N2—C8—C9124.5 (6)
O1—Mn1—N196.2 (2)N2—C8—H7117.8
C4—N1—C6118.1 (6)C9—C8—H7117.8
C4—N1—Mn1126.0 (5)C8—C9—C10119.8 (6)
C6—N1—Mn1114.8 (4)C8—C9—C14120.6 (6)
C8—N2—C7118.7 (6)C10—C9—C14119.6 (6)
C8—N2—Mn1128.5 (4)O2—C10—C9124.9 (6)
C7—N2—Mn1112.7 (4)O2—C10—C11116.8 (6)
C2—O1—Mn1125.3 (4)C9—C10—C11118.3 (7)
C2—C1—H1A109.5C12—C11—C10121.3 (7)
C2—C1—H1B109.5C12—C11—H10119.3
H1A—C1—H1B109.5C10—C11—H10119.3
C2—C1—H1C109.5C11—C12—C13121.2 (7)
H1A—C1—H1C109.5C11—C12—H11119.4
H1B—C1—H1C109.5C13—C12—H11119.4
C10—O2—Mn1127.5 (4)C18—C13—C14121.6 (8)
C19—O3—H4109.5C18—C13—C12119.7 (8)
O1—C2—C3124.8 (6)C14—C13—C12118.7 (7)
O1—C2—C1114.5 (6)C13—C14—C15116.5 (7)
C3—C2—C1120.7 (7)C13—C14—C9120.7 (7)
C2—C3—C4125.8 (7)C15—C14—C9122.7 (7)
C2—C3—H2117.1C16—C15—C14118.2 (8)
C4—C3—H2117.1C16—C15—H14120.9
N1—C4—C3120.6 (6)C14—C15—H14120.9
N1—C4—C5120.9 (8)C17—C16—C15123.7 (9)
C3—C4—C5118.4 (7)C17—C16—H15118.2
C4—C5—H4A109.5C15—C16—H15118.2
C4—C5—H4B109.5C18—C17—C16117.5 (10)
H4A—C5—H4B109.5C18—C17—H16121.2
C4—C5—H4C109.5C16—C17—H16121.2
H4A—C5—H4C109.5C17—C18—C13122.3 (9)
H4B—C5—H4C109.5C17—C18—H17118.8
N1—C6—C7106.4 (5)C13—C18—H17118.8
N1—C6—H5A110.4O3—C19—H18A109.5
C7—C6—H5A110.4O3—C19—H18B109.5
N1—C6—H5B110.4H18A—C19—H18B109.5
C7—C6—H5B110.4O3—C19—H18C109.5
H5A—C6—H5B108.6H18A—C19—H18C109.5
N2—C7—C6107.6 (6)H18B—C19—H18C109.5
N2—C7—H6A110.2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H4···O20.822.203.008 (9)171
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H4···O20.822.203.008 (9)171
Acknowledgements top

The work was supported by the Hundreds of Talents Program of the Chinese Academy of Sciences (2005012) and the Science Foundation of Qinghai Province, China (2006-G-105).

references
References top

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

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

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

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

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

Yan, X. Y., Wang, B., Ma, H. Z. & Gao, F. Q. (2006). Chem. Res. Appl. 18, 261–264.