[(2-Pyrid­yl)methanol-κ2N,O]bis­(thio­cyanato-κN)manganese(II)

Gao, Q.; Bao, Q.; Rong, R.

doi:10.1107/S1600536810034483

metal-organic compounds

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Volume 66| Part 10| October 2010| Page m1203

doi:10.1107/S1600536810034483

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[(2-Pyridyl)methanol-κ²N,O]bis(thiocyanato-κN)manganese(II)

Qihe Gao,^a Qianqian Bao ^a ^* and Rong Rong ^b

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China, and ^bDepartment of Chemistry, Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan University, Kunming 650091, People's Republic of China
^*Correspondence e-mail: chmsunbw@seu.edu.cn

(Received 10 August 2010; accepted 26 August 2010; online 4 September 2010)

In the title complex, [Mn(NCS)₂(C₆H₇NO)₂], the Mn^II atom shows site symmetry 2. The distorted octahedral environment of Mn^II is defined by two N atoms [Mn—N = 2.217 (4) and 2.132 (5) Å] and one O atom [Mn—O 2.305 (4) Å]. There are intermolecular O—H⋯S hydrogen bonds and intermolecular π–π stacking interactions between adjacent (2-pyridyl)methanolate ligands [centroid–centroid distance = 3.5569 (7) Å], leading to a chain structure running along [100].

Related literature

For background to metallacrowns, see: Mezei et al. (2007 ); Lah & Pecoraro (1989 ). For manganese clusters, see: Christou et al. (2000 ). For 2-(hydroxymethyl)pyridine, see: Shieh et al. (1997 ). For bond lengths and angles in related structures, see: Ito & Onaka (2004 ).

Experimental

Crystal data

[Mn(NCS)₂(C₆H₇NO)₂]
M_r = 389.35
Orthorhombic, P b c n
a = 11.4759 (12) Å
b = 8.398 (1) Å
c = 17.9451 (18) Å
V = 1729.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 298 K
0.48 × 0.45 × 0.40 mm

Data collection

Rigaku SCXmini CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.641, T_max = 0.687
7935 measured reflections
1521 independent reflections
1214 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.135
S = 1.35
1521 reflections
105 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯S1ⁱ	0.82	2.49	3.297 (4)	167
Symmetry code: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810034483/bg2365sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810034483/bg2365Isup2.hkl

checkCIF report

Comment top

Some metallacrowns show diverse molecular architectures, selective recognition of ions and intramolecular magnetic exchange interactions (Lah & Pecoraro (1989); Mezei et al.2007). Among all metallacrowns, manganese clusters have been frequently investigated in recent years, because of their behavior in single molecule magnets(SMMs), which show magnetic hysteresis arising from slow magnetization reversal due to a high energy barrier (Christou et al. 2000). Pyridine derivatives with two ortho-substituents have recently been revised as an important supporting ligands of multiple metal-metal bonds and/or linear metal-metal bonded arrays which are composed by more than three metal atoms. 2-(hydroxymethyl)pyridine(Hhmp) is one of the preferred achelate ligands, because the alkoxide arm often supports ferromagnetic coupling between the metal atoms. Many nuclear manganese clusters based on hmp- have been obtained. It was clearly revealed that the Hhmp can function as a chelating ligand for a single manganese ion. In order to construct new structures based on manganese ions, we chose 2-(hydroxymethyl)pyridine (Hhmp) as a pyridine ligand (Shieh et al. 1997). Herein, we report a symmetric manganese complex, [Mn(Hhmp)₂(SCN)₂]. The compound presents a a Mn^II center on a two fold axis bisecting the distorted octahedral environment provided by one Hhmp, one SCN- and their symmetry related counterparts. A molecular view of the complex is shown in Fig.1. The Mn^II center is surrounded by two nitrogens from the SCN– anions (Mn—N2: 2.132 (5) Å), and two nitrogens and two oxygens from the chelating Hhmp ligands (Mn—N1: 2.217 (4), Mn—O1: 2.305 (4) Å) to form the distorted octahedral geometry. Distances and angles within the coordination environment of Mn^II are similar to those reported in Ito & Onaka (2004). Non bonding interactions include an intermolecular O—H···S hydrogen bond (Table 1) and a weak aromatic p···p stacking linking adjacent bpy ligand rings at (x, y, z) and (1/2-x, -1/2+y, z) (centroid-centroid distance: 3.557 (8)Å). These interactions define a 1D structure running along [100] (Fig.2).

Related literature top

For background to metallacrowns, see: Mezei et al. (2007); Lah & Pecoraro (1989). For manganese clusters, see: Christou et al. (2000). For 2-(hydroxymethyl)pyridine, see: Shieh et al. (1997). For bond lengths and angles in related structures, see: Ito & Onaka (2004).

Experimental top

All chemicals used (reagent grade) were commercially available. The reaction of MnCl₂^.4H₂O, Hhmp, KSCN and triethylamine in a 2:5:5:1 molar ratio in MeCN/CH₃CN (1:2, v/v) gave a dark solution with stirring. The resulting solution was continuously stirred for a moment, and then filtered. The filtrate was slowly evaporated at room temperature over several days, and dark quadrangle crystals suitable for X-ray analysis were obtained.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-numbering scheme and all hydrogen atoms. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code A: 2 - x, -y, 1 - z]
	Fig. 2. Crystal packing of the compound (1). Hydrogen bonds are shown as dashed lines.

[(2-Pyridyl)methanol-κ²N,O]bis(thiocyanato- κN)manganese(II) top

Crystal data top

[Mn(NCS)₂(C₆H₇NO)₂]	F(000) = 796
M_r = 389.35	D_x = 1.495 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 3027 reflections
a = 11.4759 (12) Å	θ = 2.3–25.0°
b = 8.398 (1) Å	µ = 1.02 mm⁻¹
c = 17.9451 (18) Å	T = 298 K
V = 1729.5 (3) Å³	Prism, dark brown
Z = 4	0.48 × 0.45 × 0.40 mm

Data collection top

Rigaku model name? CCD area-detector diffractometer	1521 independent reflections
Radiation source: fine-focus sealed tube	1214 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 8.192 pixels mm^-1	θ_max = 25.0°, θ_min = 2.3°
ϕ and ω scans	h = −8→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→9
T_min = 0.641, T_max = 0.687	l = −18→21
7935 measured reflections

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.35	w = 1/[σ²(F_o²) + (0.0123P)² + 5.1205P] where P = (F_o² + 2F_c²)/3
1521 reflections	(Δ/σ)_max < 0.001
105 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[Mn(NCS)₂(C₆H₇NO)₂]	V = 1729.5 (3) Å³
M_r = 389.35	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 11.4759 (12) Å	µ = 1.02 mm⁻¹
b = 8.398 (1) Å	T = 298 K
c = 17.9451 (18) Å	0.48 × 0.45 × 0.40 mm

Data collection top

Rigaku model name? CCD area-detector diffractometer	1521 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1214 reflections with I > 2σ(I)
T_min = 0.641, T_max = 0.687	R_int = 0.046
7935 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.35	Δρ_max = 0.33 e Å⁻³
1521 reflections	Δρ_min = −0.56 e Å⁻³
105 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	0.20604 (14)	0.2500	0.0459 (3)
S1	0.30922 (15)	−0.1799 (2)	0.08535 (9)	0.0699 (5)
N1	0.3448 (4)	0.2711 (5)	0.3170 (2)	0.0517 (12)
N2	0.4118 (5)	0.0404 (6)	0.1798 (3)	0.0635 (14)
O1	0.5552 (4)	0.3948 (5)	0.3363 (2)	0.0623 (11)
H1	0.6229	0.3775	0.3485	0.093*
C1	0.4838 (5)	0.3959 (8)	0.4006 (3)	0.0641 (17)
H1A	0.4863	0.5002	0.4238	0.077*
H1B	0.5124	0.3185	0.4363	0.077*
C2	0.3599 (5)	0.3560 (7)	0.3791 (3)	0.0528 (14)
C3	0.2673 (7)	0.4019 (8)	0.4232 (3)	0.0710 (19)
H3	0.2802	0.4609	0.4663	0.085*
C4	0.1568 (6)	0.3600 (9)	0.4032 (4)	0.077 (2)
H4	0.0935	0.3889	0.4326	0.092*
C5	0.1405 (6)	0.2744 (9)	0.3388 (4)	0.0731 (19)
H5	0.0658	0.2465	0.3234	0.088*
C6	0.2357 (5)	0.2308 (7)	0.2976 (3)	0.0600 (15)
H6	0.2243	0.1710	0.2546	0.072*
C7	0.3687 (5)	−0.0499 (7)	0.1405 (3)	0.0469 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0442 (6)	0.0468 (6)	0.0466 (6)	0.000	0.0000 (5)	0.000
S1	0.0688 (10)	0.0746 (11)	0.0664 (10)	−0.0037 (9)	−0.0120 (8)	−0.0178 (9)
N1	0.053 (3)	0.055 (3)	0.047 (3)	0.005 (2)	0.003 (2)	0.006 (2)
N2	0.061 (3)	0.057 (3)	0.073 (3)	0.002 (3)	−0.010 (3)	−0.012 (3)
O1	0.056 (2)	0.074 (3)	0.057 (2)	−0.006 (2)	−0.003 (2)	−0.009 (2)
C1	0.068 (4)	0.078 (4)	0.046 (3)	0.014 (4)	−0.005 (3)	−0.007 (3)
C2	0.064 (4)	0.055 (3)	0.040 (3)	0.016 (3)	0.001 (3)	0.007 (3)
C3	0.091 (5)	0.076 (4)	0.047 (3)	0.023 (4)	0.007 (3)	0.007 (3)
C4	0.070 (5)	0.094 (5)	0.067 (4)	0.029 (4)	0.024 (4)	0.022 (4)
C5	0.052 (4)	0.090 (5)	0.077 (5)	0.014 (4)	0.007 (3)	0.024 (4)
C6	0.055 (4)	0.066 (4)	0.060 (4)	0.002 (3)	−0.001 (3)	0.011 (3)
C7	0.039 (3)	0.050 (3)	0.052 (3)	0.009 (3)	0.001 (3)	0.004 (3)

Geometric parameters (Å, º) top

Mn1—N2	2.132 (5)	C1—C2	1.511 (8)
Mn1—N2ⁱ	2.132 (5)	C1—H1A	0.9700
Mn1—N1ⁱ	2.217 (4)	C1—H1B	0.9700
Mn1—N1	2.217 (4)	C2—C3	1.379 (8)
Mn1—O1	2.305 (4)	C3—C4	1.365 (10)
Mn1—O1ⁱ	2.305 (4)	C3—H3	0.9300
S1—C7	1.624 (6)	C4—C5	1.373 (10)
N1—C2	1.335 (7)	C4—H4	0.9300
N1—C6	1.343 (7)	C5—C6	1.368 (8)
N2—C7	1.148 (7)	C5—H5	0.9300
O1—C1	1.415 (6)	C6—H6	0.9300
O1—H1	0.8200

N2—Mn1—N2ⁱ	98.5 (3)	O1—C1—C2	109.6 (4)
N2—Mn1—N1ⁱ	102.81 (18)	O1—C1—H1A	109.7
N2ⁱ—Mn1—N1ⁱ	95.73 (19)	C2—C1—H1A	109.7
N2—Mn1—N1	95.73 (19)	O1—C1—H1B	109.7
N2ⁱ—Mn1—N1	102.81 (18)	C2—C1—H1B	109.7
N1ⁱ—Mn1—N1	151.5 (2)	H1A—C1—H1B	108.2
N2—Mn1—O1	167.46 (18)	N1—C2—C3	121.9 (6)
N2ⁱ—Mn1—O1	85.49 (17)	N1—C2—C1	117.0 (5)
N1ⁱ—Mn1—O1	88.50 (15)	C3—C2—C1	121.1 (6)
N1—Mn1—O1	71.76 (16)	C4—C3—C2	119.5 (6)
N2—Mn1—O1ⁱ	85.49 (17)	C4—C3—H3	120.3
N2ⁱ—Mn1—O1ⁱ	167.46 (18)	C2—C3—H3	120.3
N1ⁱ—Mn1—O1ⁱ	71.76 (16)	C3—C4—C5	118.9 (6)
N1—Mn1—O1ⁱ	88.50 (15)	C3—C4—H4	120.5
O1—Mn1—O1ⁱ	93.1 (2)	C5—C4—H4	120.5
C2—N1—C6	118.1 (5)	C6—C5—C4	119.0 (7)
C2—N1—Mn1	118.7 (4)	C6—C5—H5	120.5
C6—N1—Mn1	123.2 (4)	C4—C5—H5	120.5
C7—N2—Mn1	177.1 (5)	N1—C6—C5	122.6 (6)
C1—O1—Mn1	113.1 (3)	N1—C6—H6	118.7
C1—O1—H1	109.5	C5—C6—H6	118.7
Mn1—O1—H1	108.5	N2—C7—S1	179.0 (5)

N2—Mn1—N1—C2	168.6 (4)	Mn1—O1—C1—C2	−34.4 (6)
N2ⁱ—Mn1—N1—C2	68.5 (4)	C6—N1—C2—C3	0.2 (8)
N1ⁱ—Mn1—N1—C2	−60.7 (4)	Mn1—N1—C2—C3	179.4 (4)
O1—Mn1—N1—C2	−12.3 (4)	C6—N1—C2—C1	178.4 (5)
O1ⁱ—Mn1—N1—C2	−106.0 (4)	Mn1—N1—C2—C1	−2.3 (7)
N2—Mn1—N1—C6	−12.1 (5)	O1—C1—C2—N1	24.8 (7)
N2ⁱ—Mn1—N1—C6	−112.3 (4)	O1—C1—C2—C3	−156.9 (5)
N1ⁱ—Mn1—N1—C6	118.5 (4)	N1—C2—C3—C4	0.0 (9)
O1—Mn1—N1—C6	166.9 (5)	C1—C2—C3—C4	−178.2 (6)
O1ⁱ—Mn1—N1—C6	73.2 (4)	C2—C3—C4—C5	−0.8 (10)
N2—Mn1—O1—C1	30.2 (10)	C3—C4—C5—C6	1.4 (10)
N2ⁱ—Mn1—O1—C1	−79.2 (4)	C2—N1—C6—C5	0.5 (9)
N1ⁱ—Mn1—O1—C1	−175.1 (4)	Mn1—N1—C6—C5	−178.7 (5)
N1—Mn1—O1—C1	25.9 (4)	C4—C5—C6—N1	−1.3 (10)
O1ⁱ—Mn1—O1—C1	113.3 (4)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···S1ⁱⁱ	0.82	2.49	3.297 (4)	167

Symmetry code: (ii) x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Mn(NCS)₂(C₆H₇NO)₂]
M_r	389.35
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	298
a, b, c (Å)	11.4759 (12), 8.398 (1), 17.9451 (18)
V (Å³)	1729.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.48 × 0.45 × 0.40

Data collection
Diffractometer	Rigaku model name? CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.641, 0.687
No. of measured, independent and observed [I > 2σ(I)] reflections	7935, 1521, 1214
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.135, 1.35
No. of reflections	1521
No. of parameters	105
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.56

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···S1ⁱ	0.82	2.49	3.297 (4)	166.8

Symmetry code: (i) x+1/2, y+1/2, −z+1/2.

References

Christou, G., Gatteschi, D. & Hendrickson, D. N. (2000). MRS Bull. 25, 66–66. CrossRef CAS Google Scholar
Ito, M. & Onaka, S. (2004). Inorg. Chim. Acta, 357, 1039–1046. Web of Science CSD CrossRef CAS Google Scholar
Lah, M. S. & Pecoraro, V. L. (1989). J. Am. Chem. Soc. 111, 7258–7259. CSD CrossRef CAS Web of Science Google Scholar
Mezei, G., Zeleski, Z. M. & Pecoraro, V. L. (2007). Chem. Rev. 107, 4933–5033. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shieh, S. J., Chou, C. C. & Lee, C. C. (1997). Angew. Chem. Int. Ed. 36 , 56–59. CrossRef CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1203

doi:10.1107/S1600536810034483

Open

access