Diaqua­bis­(seleno­cyanato-κN)bis­(pyrimidine-κN)manganese(II)

Abstract

In the crystal structure of the title compound, [Mn(NCSe)₂(C₄H₄N₂)₂(H₂O)₂], the manganese(II) cation is coordinated by two N-bonded pyrimidine ligands, two N-bonded seleno­cyanate anions and two O-bonded water mol­ecules in a distorted octa­hedral coordination mode. The asymmetric unit consists of one manganese(II) cation, located on a centre of inversion, as well as one seleno­cyanate anion, one water mol­ecule and one pyrimidine ligand in general positions. The crystal structure consists of discrete building blocks of composition [Mn(NCSe)₂(pyrimidine)₂(H₂O)₂], which are connected into layers parallel to (101) by strong water–pyrimidine O—H⋯N hydrogen bonds.

Related literature

For a related pyrimidine structure, see: Lipkowski & Soldatov (1993 ▶). For general background to the use of thermal decomposition reactions for the discovery and preparation of new ligand-deficient coordination polymers with defined magnetic properties, see: Wriedt & Näther (2009a ▶,b ▶); Wriedt et al. (2009a ▶,b ▶).

Experimental

Crystal data

• [Mn(CNSe)₂(C₄H₄N₂)₂(H₂O)₂]

• M _r = 461.12

• Monoclinic,

• a = 9.2402 (7) Å

• b = 9.6012 (6) Å

• c = 10.2099 (8) Å

• β = 111.505 (8)°

• V = 842.74 (11) ų

• Z = 2

• Mo Kα radiation

• μ = 5.11 mm⁻¹

• T = 170 K

• 0.10 × 0.07 × 0.04 mm

Data collection

• Stoe IPDS-1 diffractometer

• Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T _min = 0.653, T _max = 0.818

• 9472 measured reflections

• 2024 independent reflections

• 1795 reflections with I > 2σ(I)

• R _int = 0.043

Refinement

• R[F ² > 2σ(F ²)] = 0.026

• wR(F ²) = 0.064

• S = 1.03

• 2024 reflections

• 98 parameters

• H-atom parameters constrained

• Δρ_max = 0.50 e Å⁻³

• Δρ_min = −0.51 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2008 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Mn1—O1	2.1582 (14)
Mn1—N11	2.1840 (19)
Mn1—N1	2.3328 (18)

O1—Mn1—O1i	180.0
O1—Mn1—N11	90.29 (7)
O1i—Mn1—N11	89.71 (7)
O1—Mn1—N1i	90.44 (6)
N11—Mn1—N1i	93.23 (7)
N11i—Mn1—N1i	86.77 (7)
O1—Mn1—N1	89.56 (6)

Symmetry code: (i) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H2O1⋯N2ii	0.84	1.93	2.748 (2)	164

Symmetry code: (ii) .

supplementary crystallographic information

Comment

Recently, we have shown that thermal decomposition reactions are an elegante route for the discovering and preparation of new ligand-deficient coordination polymers with defined magnetic properties (Wriedt & Näther, 2009a, 2009b; Wriedt, Sellmer & Näther, 2009a, 2009b). In our ongoing investigation on the synthesis, structures and properties of such compounds based on paramagnetic transition metal pseudo-halides and N-donor ligands, we have reacted manganese(II) dichloride, potassium selenocyanate and pyrimidine in water. In this reaction single crystals were obtained, which were identified as the title compound by single-crystal X-ray diffraction.

The title compound of composition [Mn(NCSe)₂(H₂O)₂(pyrimidine)₂] (Fig. 1) represents a discrete coordination complex, in which the manganese(II) cation is coordinated by two selenocyanato anions, two water molecules and two pyrimidine ligands in an octahedral coordination mode. The MnN₄O₂ octahedron is slightly distorted with two long Mn–N_pyrimidine distances of 2.3328 (18) Å, two short Mn–NCSe distances of 2.1840 (9) Å and two short Mn—OH₂ distances of 2.1582 (14) Å, while the angles around the metal center range between 86.77 (7)–93.23 (7) and 180° (Tab. 1). The coordination of the metal center is similar to that in a related structure (Lipkowski & Soldatov, 1993). In the crystal structure the single complexes are connected via strong N_pyrimidine···H_water hydrogen bonds into layers (see Tab. 2), which are located in the crystallographic a/c-plane (Fig. 2 and 3). The shortest intra- and interlayer Mn···Mn distances amount to 7.2911 (5) and 9.3672 (5) Å, respectively.

Experimental

MnCl₂, KNCSe and pyrimidine were obtained from Alfa Aesar. 1 mmol (126 mg) MnCl₂, 2 mmol (288 mg) KNCSe, 0.25 mmol (20 mg) pyrimidine and 3 ml water were reacted in a closed snap-vail without stirring. After the mixture was standing for several days at room temperature colorless block shaped single crystals of the title compound were obtained in a mixture with unknown phases.

Refinement

All non-hydrogen atoms were refined anisotropic. The O—H-hydrogen atoms were located in difference map, where the bond lengths set to ideal values and were refined using a riding model. All other H atoms were located in difference map but were positioned with idealized geometry and were refined isotropic with U_eq(H) = 1.2 U_eq(C) of the parent atom using a riding model with C—H = 0.95 Å.

Figures

Fig. 1.

: Crystal structure of the discrete title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) -x+1, -y+2, -z+1.]

Fig. 2.

: Crystal structure of the title compound with view along the crystallographic b axis. The dashed lines indicate N···H—O hydrogen bonding.

Fig. 3.

: Packing of two single layers with view approximately along the crystallographic b axis. The dashed lines indicate N···H—O hydrogen bonding.

Crystal data

[Mn(CNSe)2(C4H4N2)2(H2O)2]	F(000) = 446
Mr = 461.12	Dx = 1.817 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9472 reflections
a = 9.2402 (7) Å	θ = 2.6–28.0°
b = 9.6012 (6) Å	µ = 5.11 mm−1
c = 10.2099 (8) Å	T = 170 K
β = 111.505 (8)°	Block, colourless
V = 842.74 (11) Å3	0.10 × 0.07 × 0.04 mm
Z = 2

Data collection

Stoe IPDS-1 diffractometer	2024 independent reflections
Radiation source: fine-focus sealed tube	1795 reflections with I > 2σ(I)
graphite	Rint = 0.043
Phi scans	θmax = 28.0°, θmin = 2.6°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −12→12
Tmin = 0.653, Tmax = 0.818	k = −12→12
9472 measured reflections	l = −13→13

Refinement

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)] = 0.026	H-atom parameters constrained
wR(F2) = 0.064	w = 1/[σ2(Fo2) + (0.0376P)2 + 0.3681P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.002
2024 reflections	Δρmax = 0.50 e Å−3
98 parameters	Δρmin = −0.51 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0110 (14)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.5000	1.0000	0.5000	0.01759 (12)
N1	0.4202 (2)	0.77991 (19)	0.54320 (18)	0.0208 (4)
N2	0.3036 (2)	0.5623 (2)	0.45030 (19)	0.0289 (4)
C1	0.3525 (3)	0.6901 (3)	0.4381 (2)	0.0265 (5)
H1	0.3380	0.7208	0.3456	0.032*
C2	0.3267 (3)	0.5183 (3)	0.5807 (2)	0.0298 (5)
H2	0.2947	0.4271	0.5938	0.036*
C3	0.3961 (3)	0.6023 (3)	0.6969 (2)	0.0299 (5)
H3	0.4128	0.5705	0.7894	0.036*
C4	0.4398 (3)	0.7336 (2)	0.6731 (2)	0.0261 (5)
H4	0.4856	0.7940	0.7511	0.031*
N11	0.7272 (2)	0.9064 (2)	0.5380 (2)	0.0300 (4)
C11	0.8449 (2)	0.8544 (2)	0.5539 (2)	0.0214 (4)
Se11	1.02886 (3)	0.77302 (3)	0.58075 (3)	0.02776 (10)
O1	0.42680 (19)	0.94905 (18)	0.27927 (15)	0.0283 (3)
H1O1	0.4782	0.9061	0.2392	0.042*
H2O1	0.3448	0.9730	0.2134	0.042*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Mn1	0.0178 (2)	0.0179 (2)	0.0143 (2)	0.00340 (15)	0.00258 (15)	−0.00073 (14)
N1	0.0200 (8)	0.0227 (9)	0.0175 (8)	−0.0008 (7)	0.0044 (7)	−0.0010 (6)
N2	0.0341 (10)	0.0270 (11)	0.0222 (9)	−0.0077 (8)	0.0061 (7)	−0.0039 (7)
C1	0.0300 (11)	0.0291 (12)	0.0185 (10)	−0.0042 (9)	0.0068 (8)	−0.0022 (8)
C2	0.0345 (12)	0.0246 (12)	0.0279 (11)	−0.0045 (9)	0.0086 (9)	0.0002 (9)
C3	0.0381 (12)	0.0285 (12)	0.0200 (10)	−0.0020 (10)	0.0070 (9)	0.0028 (9)
C4	0.0289 (11)	0.0253 (11)	0.0191 (9)	−0.0015 (9)	0.0030 (8)	−0.0021 (8)
N11	0.0230 (9)	0.0297 (11)	0.0367 (10)	0.0060 (8)	0.0101 (8)	0.0036 (8)
C11	0.0218 (9)	0.0218 (10)	0.0205 (9)	−0.0012 (8)	0.0078 (7)	0.0022 (7)
Se11	0.02287 (14)	0.02978 (16)	0.03597 (15)	0.00821 (9)	0.01709 (10)	0.00904 (9)
O1	0.0356 (8)	0.0300 (9)	0.0136 (6)	0.0116 (7)	0.0024 (6)	−0.0026 (6)

Geometric parameters (Å, °)

Mn1—O1	2.1582 (14)	C1—H1	0.9500
Mn1—O1i	2.1582 (14)	C2—C3	1.383 (3)
Mn1—N11	2.1840 (19)	C2—H2	0.9500
Mn1—N11i	2.1840 (19)	C3—C4	1.372 (3)
Mn1—N1i	2.3328 (18)	C3—H3	0.9500
Mn1—N1	2.3328 (18)	C4—H4	0.9500
N1—C1	1.340 (3)	N11—C11	1.153 (3)
N1—C4	1.347 (3)	C11—Se11	1.798 (2)
N2—C1	1.329 (3)	O1—H1O1	0.8400
N2—C2	1.337 (3)	O1—H2O1	0.8400
O1—Mn1—O1i	180.0	C1—N2—C2	116.70 (19)
O1—Mn1—N11	90.29 (7)	N2—C1—N1	126.4 (2)
O1i—Mn1—N11	89.71 (7)	N2—C1—H1	116.8
O1—Mn1—N11i	89.71 (7)	N1—C1—H1	116.8
O1i—Mn1—N11i	90.29 (7)	N2—C2—C3	121.7 (2)
N11—Mn1—N11i	180.0	N2—C2—H2	119.2
O1—Mn1—N1i	90.44 (6)	C3—C2—H2	119.2
O1i—Mn1—N1i	89.56 (6)	C4—C3—C2	117.2 (2)
N11—Mn1—N1i	93.23 (7)	C4—C3—H3	121.4
N11i—Mn1—N1i	86.77 (7)	C2—C3—H3	121.4
O1—Mn1—N1	89.56 (6)	N1—C4—C3	122.4 (2)
O1i—Mn1—N1	90.44 (6)	N1—C4—H4	118.8
N11—Mn1—N1	86.77 (7)	C3—C4—H4	118.8
N11i—Mn1—N1	93.23 (7)	C11—N11—Mn1	177.7 (2)
N1i—Mn1—N1	180.00 (9)	N11—C11—Se11	179.4 (2)
C1—N1—C4	115.56 (19)	Mn1—O1—H1O1	127.1
C1—N1—Mn1	121.24 (15)	Mn1—O1—H2O1	128.3
C4—N1—Mn1	123.19 (14)	H1O1—O1—H2O1	104.5

Symmetry codes: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2O1···N2ii	0.84	1.93	2.748 (2)	164

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