{N,N′-Bis[1-(2-pyrid­yl)ethyl­idene]ethane-1,2-diamine-κ4N,N′,N′′,N′′′}bis­(thio­cyanato-κN)manganese(II)

Wang, F.-M.

doi:10.1107/S1600536810021550

metal-organic compounds

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Volume 66| Part 7| July 2010| Page m776

doi:10.1107/S1600536810021550

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{N,N′-Bis[1-(2-pyridyl)ethylidene]ethane-1,2-diamine-κ⁴N,N′,N′′,N′′′}bis(thiocyanato-κN)manganese(II)

Fu-Ming Wang ^a ^*

^aDepartment of Chemistry, Dezhou University, Dezhou Shandong 253023, People's Republic of China
^*Correspondence e-mail: wfm99999@126.com

(Received 6 June 2010; accepted 6 June 2010; online 16 June 2010)

The molecule of the title compound, [Mn(NCS)₂(C₁₆H₁₈N₄)], has crystallographic twofold rotation symmetry, with the Mn^II atom lying on the rotation axis. The Mn^II atom is six-coordinated by four N atoms of the Schiff base ligand and by two N atoms of two thiocyanate ligands, forming a distorted octahedral geometry.

Related literature

For background to Schiff base compounds, see: Ruck & Jacobsen (2002 ); Mukhopadhyay et al. (2003 ); Polt et al. (2003 ); Mukherjee et al. (2001 ). For complexes derived from N,N′-bis(1-(pyridin-2-yl)ethylidene)ethane-1,2-diamine, see: Gourbatsis et al. (1998 ); Louloudi et al. (1999 ); Karmakar et al. (2002 ); Banerjee et al. (2004 ). For related Mn^II complexes with Schiff bases, see: Louloudi et al. (1999); Sra et al. (2000 ); Karmakar et al. (2005 ); Deoghoria et al. (2005 ). For the synthesis of the Schiff base, see: Gourbatsis et al. (1990 ).

Experimental

Crystal data

[Mn(NCS)₂(C₁₆H₁₈N₄)]
M_r = 437.44
Monoclinic, C 2/c
a = 12.570 (4) Å
b = 16.341 (5) Å
c = 9.962 (3) Å
β = 90.857 (4)°
V = 2045.9 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.86 mm⁻¹
T = 298 K
0.17 × 0.15 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.867, T_max = 0.881
4479 measured reflections
2173 independent reflections
1590 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.093
S = 1.02
2173 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—N3	2.127 (2)
Mn1—N2	2.263 (2)
Mn1—N1	2.376 (2)

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810021550/ci5097sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810021550/ci5097Isup2.hkl

checkCIF report

Comment top

Metal complexes with Schiff bases have been known since 1840. The Schiff bases and their complexes have played an important role in the development of coordination chemistry, biological and material sciences (Ruck & Jacobsen, 2002; Mukhopadhyay et al., 2003; Polt et al., 2003; Mukherjee et al., 2001). A few complexes derived from N,N'-bis(1-(pyridin-2-yl)ethylidene)ethane-1,2-diamine have been reported (Gourbatsis et al., 1998; Louloudi et al., 1999; Karmakar et al., 2002; Banerjee et al., 2004). In this paper, the title new Mn(II) complex is reported.

The title compound possesses a crystallographic twofold rotation axis symmetry, Fig. 1. The Mn^II atom is six-coordinated by four N atoms of the Schiff base ligand N,N'-bis(1-(pyridin-2-yl)ethylidene)ethane-1,2-diamine, and by two N atoms from two thiocyanate ligands, forming a distorted octahedral geometry. The coordinate bond lengths (Table 1) are comparable with those observed in other similar manganese(II) complexes with Schiff bases (Louloudi et al., 1999; Sra et al., 2000; Karmakar et al., 2005; Deoghoria et al., 2005).

Related literature top

For background to Schiff base compounds, see: Ruck & Jacobsen (2002); Mukhopadhyay et al. (2003); Polt et al. (2003); Mukherjee et al. (2001). For complexes derived from N,N'-bis(1-(pyridin-2-yl)ethylidene)ethane-1,2-diamine, see: Gourbatsis et al. (1998); Louloudi et al. (1999); Karmakar et al. (2002); Banerjee et al. (2004). For related Mn^II complexes with Schiff bases, see: Louloudi et al. (1999); Sra et al. (2000); Karmakar et al. (2005); Deoghoria et al. (2005). For the synthesis of the Schiff base, see: Gourbatsis et al. (1990).

Experimental top

The Schiff base ligand N,N'-bis(1-(pyridin-2-yl)ethylidene)ethane-1,2-diamine was synthesized according to the literature method (Gourbatsis et al., 1990). To a stirred methanol solution of the Schiff base ligand (1.0 mmol, 0.266 g) was added a methanol solution of manganese acetate (1.0 mmol, 0.245 g) and ammonium thiocyanate (1.0 mmol, 0.076 g). The mixture was boiled under reflux for 2 h, then cooled to room temperature. Brown block-like single crystals, suitable for X-ray diffraction, were formed after slow evaporation of the solution in air for a few days.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Unlabelled atoms are related to labelled atoms by the symmetry operation (1 - x, y, 1/2 - z).

{N,N'-Bis[1-(2-pyridyl)ethylidene]ethane-1,2-diamine- κ⁴N,N',N'',N'''}bis(thiocyanato- κN)manganese(II) top

Crystal data top

[Mn(NCS)₂(C₁₆H₁₈N₄)]	F(000) = 900
M_r = 437.44	D_x = 1.420 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1222 reflections
a = 12.570 (4) Å	θ = 2.6–25.3°
b = 16.341 (5) Å	µ = 0.86 mm⁻¹
c = 9.962 (3) Å	T = 298 K
β = 90.857 (4)°	Block, brown
V = 2045.9 (10) Å³	0.17 × 0.15 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2173 independent reflections
Radiation source: fine-focus sealed tube	1590 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scan	θ_max = 27.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→12
T_min = 0.867, T_max = 0.881	k = −20→20
4479 measured reflections	l = −12→10

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0354P)² + 1.1621P] where P = (F_o² + 2F_c²)/3
2173 reflections	(Δ/σ)_max = 0.001
124 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Mn(NCS)₂(C₁₆H₁₈N₄)]	V = 2045.9 (10) Å³
M_r = 437.44	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.570 (4) Å	µ = 0.86 mm⁻¹
b = 16.341 (5) Å	T = 298 K
c = 9.962 (3) Å	0.17 × 0.15 × 0.15 mm
β = 90.857 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2173 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1590 reflections with I > 2σ(I)
T_min = 0.867, T_max = 0.881	R_int = 0.023
4479 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.02	Δρ_max = 0.26 e Å⁻³
2173 reflections	Δρ_min = −0.35 e Å⁻³
124 parameters

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 > 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	U_iso*/U_eq
Mn1	0.5000	0.28864 (3)	0.2500	0.04525 (18)
N1	0.42596 (16)	0.32743 (14)	0.03855 (19)	0.0533 (5)
N2	0.44344 (15)	0.17790 (12)	0.13277 (18)	0.0471 (5)
N3	0.63772 (18)	0.34541 (15)	0.1706 (2)	0.0648 (6)
S1	0.82249 (6)	0.38624 (6)	0.04009 (8)	0.0872 (3)
C1	0.4168 (2)	0.40396 (19)	−0.0058 (3)	0.0700 (8)
H1	0.4354	0.4463	0.0523	0.084*
C2	0.3812 (2)	0.4238 (2)	−0.1337 (3)	0.0770 (9)
H2	0.3750	0.4781	−0.1605	0.092*
C3	0.3554 (2)	0.3616 (2)	−0.2193 (3)	0.0774 (9)
H3	0.3325	0.3729	−0.3065	0.093*
C4	0.3636 (2)	0.28185 (19)	−0.1753 (3)	0.0658 (8)
H4	0.3455	0.2388	−0.2323	0.079*
C5	0.39910 (18)	0.26645 (16)	−0.0454 (2)	0.0492 (6)
C6	0.40708 (18)	0.18264 (16)	0.0130 (2)	0.0482 (6)
C7	0.3715 (2)	0.11213 (18)	−0.0729 (3)	0.0731 (8)
H7A	0.4227	0.1028	−0.1418	0.110*
H7B	0.3036	0.1246	−0.1134	0.110*
H7C	0.3654	0.0639	−0.0184	0.110*
C8	0.4512 (2)	0.10020 (15)	0.2047 (2)	0.0563 (7)
H8A	0.4556	0.0555	0.1410	0.068*
H8B	0.3881	0.0922	0.2580	0.068*
C9	0.7137 (2)	0.36210 (16)	0.1152 (2)	0.0515 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0431 (3)	0.0515 (3)	0.0411 (3)	0.000	0.0002 (2)	0.000
N1	0.0524 (12)	0.0574 (14)	0.0500 (12)	0.0008 (10)	−0.0029 (9)	0.0033 (10)
N2	0.0468 (11)	0.0525 (13)	0.0418 (11)	0.0001 (9)	−0.0008 (9)	−0.0012 (9)
N3	0.0507 (13)	0.0863 (17)	0.0575 (13)	−0.0072 (12)	0.0016 (10)	0.0114 (12)
S1	0.0612 (5)	0.1388 (9)	0.0619 (5)	−0.0238 (5)	0.0102 (4)	0.0159 (5)
C1	0.081 (2)	0.0640 (19)	0.0650 (17)	0.0042 (16)	−0.0056 (15)	0.0044 (15)
C2	0.080 (2)	0.078 (2)	0.0727 (19)	0.0090 (17)	−0.0060 (17)	0.0206 (17)
C3	0.069 (2)	0.104 (3)	0.0589 (17)	−0.0006 (18)	−0.0151 (15)	0.0212 (18)
C4	0.0610 (17)	0.084 (2)	0.0523 (15)	−0.0075 (15)	−0.0149 (12)	0.0052 (15)
C5	0.0352 (12)	0.0679 (17)	0.0444 (13)	−0.0030 (11)	−0.0011 (10)	0.0014 (12)
C6	0.0387 (13)	0.0629 (16)	0.0430 (13)	−0.0037 (11)	0.0018 (10)	−0.0049 (11)
C7	0.086 (2)	0.077 (2)	0.0553 (16)	−0.0141 (17)	−0.0139 (15)	−0.0073 (14)
C8	0.0657 (17)	0.0558 (16)	0.0475 (14)	−0.0064 (13)	−0.0019 (11)	0.0004 (11)
C9	0.0520 (15)	0.0619 (17)	0.0405 (12)	−0.0004 (13)	−0.0061 (11)	0.0071 (11)

Geometric parameters (Å, º) top

Mn1—N3	2.127 (2)	C2—C3	1.363 (4)
Mn1—N3ⁱ	2.127 (2)	C2—H2	0.93
Mn1—N2	2.263 (2)	C3—C4	1.378 (4)
Mn1—N2ⁱ	2.263 (2)	C3—H3	0.93
Mn1—N1ⁱ	2.376 (2)	C4—C5	1.386 (3)
Mn1—N1	2.376 (2)	C4—H4	0.93
N1—C1	1.331 (3)	C5—C6	1.491 (4)
N1—C5	1.341 (3)	C6—C7	1.500 (3)
N2—C6	1.273 (3)	C7—H7A	0.96
N2—C8	1.461 (3)	C7—H7B	0.96
N3—C9	1.144 (3)	C7—H7C	0.96
S1—C9	1.617 (3)	C8—C8ⁱ	1.512 (5)
C1—C2	1.382 (4)	C8—H8A	0.97
C1—H1	0.93	C8—H8B	0.97

N3—Mn1—N3ⁱ	128.28 (13)	C1—C2—H2	120.9
N3—Mn1—N2	114.09 (8)	C2—C3—C4	119.4 (3)
N3ⁱ—Mn1—N2	106.83 (8)	C2—C3—H3	120.3
N3—Mn1—N2ⁱ	106.83 (8)	C4—C3—H3	120.3
N3ⁱ—Mn1—N2ⁱ	114.09 (8)	C3—C4—C5	119.3 (3)
N2—Mn1—N2ⁱ	73.78 (10)	C3—C4—H4	120.3
N3—Mn1—N1ⁱ	84.43 (8)	C5—C4—H4	120.3
N3ⁱ—Mn1—N1ⁱ	82.20 (8)	N1—C5—C4	121.5 (2)
N2—Mn1—N1ⁱ	141.89 (7)	N1—C5—C6	115.1 (2)
N2ⁱ—Mn1—N1ⁱ	68.89 (7)	C4—C5—C6	123.4 (2)
N3—Mn1—N1	82.20 (8)	N2—C6—C5	116.3 (2)
N3ⁱ—Mn1—N1	84.43 (8)	N2—C6—C7	126.0 (2)
N2—Mn1—N1	68.89 (7)	C5—C6—C7	117.7 (2)
N2ⁱ—Mn1—N1	141.89 (7)	C6—C7—H7A	109.5
N1ⁱ—Mn1—N1	149.06 (11)	C6—C7—H7B	109.5
C1—N1—C5	118.1 (2)	H7A—C7—H7B	109.5
C1—N1—Mn1	125.15 (18)	C6—C7—H7C	109.5
C5—N1—Mn1	116.51 (16)	H7A—C7—H7C	109.5
C6—N2—C8	122.2 (2)	H7B—C7—H7C	109.5
C6—N2—Mn1	122.72 (17)	N2—C8—C8ⁱ	109.89 (15)
C8—N2—Mn1	115.07 (14)	N2—C8—H8A	109.7
C9—N3—Mn1	166.9 (2)	C8ⁱ—C8—H8A	109.7
N1—C1—C2	123.5 (3)	N2—C8—H8B	109.7
N1—C1—H1	118.3	C8ⁱ—C8—H8B	109.7
C2—C1—H1	118.3	H8A—C8—H8B	108.2
C3—C2—C1	118.2 (3)	N3—C9—S1	178.7 (2)
C3—C2—H2	120.9

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Mn(NCS)₂(C₁₆H₁₈N₄)]
M_r	437.44
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	12.570 (4), 16.341 (5), 9.962 (3)
β (°)	90.857 (4)
V (Å³)	2045.9 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.86
Crystal size (mm)	0.17 × 0.15 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.867, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	4479, 2173, 1590
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.093, 1.02
No. of reflections	2173
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.35

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mn1—N3	2.127 (2)	Mn1—N1	2.376 (2)
Mn1—N2	2.263 (2)

Acknowledgements

This work was supported by Dezhou University, People's Republic of China.

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