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Acta Cryst. (2007). E63, m1775-m1776    [ doi:10.1107/S1600536807025561 ]

Di-[mu]-acetato-bis[triaquabis(thiocyanato-[kappa]N)(4-methylpyridine N-oxide-[kappa]O)samarium(III)]

S.-G. Zhang and J.-M. Shi

Abstract top

In the title binuclear complex, [Sm2([mu]-C2H3O2)2(NCS)4(C6H7NO)2(H2O)6], which possesses a crystallographically imposed centre of symmetry, four thiocyanate, two 4-methylpyridine N-oxide and six water molecules function as terminal ligands, whereas two acetate anions bridge the two SmIII ions. The crystal packing exhibits an extensive three-dimensional network of intermolecular O-H...S and O-H...O hydrogen bonds.

Comment top

Acetate, thiocyanate and pyridine N-oxide (or its derivatives) are very useful bridging ligands and many multi-nuclear complexes have been synthesized using these ligands (Panagiotopoulos et al., 1995; Zhang et al., 2006). Some of these complexes display interesting physical properties. We are interested in compounds containing the three types of ligands and hence we have synthesize the title complex, (I), whose crystal structure is reported here.

The asymmetric unit and symmetry-related fragments of (I) are shown in Fig. 1. In the binuclear structure each SmIII ion is coordinated by nine atoms and Table 1 shows the relative coordinated bond lengths and associated angles, and the distance between Sm1 to Sm1i is 4.5032 (5) Å. Atoms Sm1, O2, Sm1i, O2i [symmetry code: (i) -x + 2, -y,-z + 1] are strictly coplanar and form a parallelogram by virtue of the crystallographic inversion center which is at the middle of the parallelogram. The hydrogen bonds (Table 2) from O atom and S1 atom made the binuclear units connect each other and form the supermolecular two-dimensional sheets on ac plane, and the hydrogen bonds dealing with S2 atom made the sheets pile up along b axis and led to the formation of the supermolecular three-dimensional structure.

Related literature top

For the crystal structures of related complexes, see: Panagiotopoulos et al. (1995); Zhang et al. (2006).

Experimental top

Sm(ClO4)3.6H2O (0.3128 g, 0.562 mmol), NaSCN (0.0926 g, 1.14 mmol), 4-methylpyridine N-oxide (0.0637 g, 0.584 mmol) and Na(CH3COO) (0.0480 g, 0.585 mmol) were dissolved in 5 ml of water, respectively, and then the four kinds of solutions were mixed together and stirred for a few minutes. The colourless transparent single crystals were obtained after allowing the solution to stand for two weeks at room temperature.

Refinement top

The H atoms from H2O were found in a difference Fourier map, and placed in idealized positions with O—H = 0.884–0.899 Å. The C-bound H atoms were placed in calculated positions, C—H = 0.93–0.96 Å. All H atoms were refined as riding, with Uiso(H) = 1.2–1.5Ueq(C,O).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing the atom numbering scheme with displacement ellipsoids drawn at the 30% probability level [symmetry code: (i) -x + 2, -y, -z + 1].
Di-µ-acetato-bis[triaquabis(thiocyanato-κN)(4-methylpyridine N-oxide-κO)samarium(III)] top
Crystal data top
[Sm2(C2H3O2)2(NCS)4(C6H7NO)2(H2O)6]F(000) = 956
Mr = 977.46Dx = 1.877 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5767 reflections
a = 9.0451 (12) Åθ = 2.6–27.1°
b = 15.997 (2) ŵ = 3.66 mm−1
c = 12.1753 (16) ÅT = 298 K
β = 100.910 (2)°Prism, colourless
V = 1729.9 (4) Å30.26 × 0.11 × 0.09 mm
Z = 2
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3736 independent reflections
Radiation source: fine-focus sealed tube3447 reflections with I > 2σ(I)
graphiteRint = 0.027
φ and ω scansθmax = 27.1°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→11
Tmin = 0.449, Tmax = 0.734k = −20→19
10164 measured reflectionsl = −14→15
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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.035P)2 + 0.8001P]
where P = (Fo2 + 2Fc2)/3
3736 reflections(Δ/σ)max = 0.002
201 parametersΔρmax = 0.57 e Å−3
9 restraintsΔρmin = −1.28 e Å−3
Crystal data top
[Sm2(C2H3O2)2(NCS)4(C6H7NO)2(H2O)6]V = 1729.9 (4) Å3
Mr = 977.46Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.0451 (12) ŵ = 3.66 mm−1
b = 15.997 (2) ÅT = 298 K
c = 12.1753 (16) Å0.26 × 0.11 × 0.09 mm
β = 100.910 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3736 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3447 reflections with I > 2σ(I)
Tmin = 0.449, Tmax = 0.734Rint = 0.027
10164 measured reflectionsθmax = 27.1°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.068Δρmax = 0.57 e Å−3
S = 1.06Δρmin = −1.28 e Å−3
3736 reflectionsAbsolute structure: ?
201 parametersFlack parameter: ?
9 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.

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
xyzUiso*/Ueq
O20.9416 (3)−0.07880 (15)0.5244 (2)0.0362 (6)
Sm10.806933 (17)0.086888 (10)0.509341 (13)0.02443 (7)
O40.7952 (2)0.02100 (14)0.32466 (18)0.0323 (5)
H100.7299−0.01770.29250.049*
H110.8848−0.00110.32120.049*
N10.9373 (3)0.07642 (17)0.7955 (2)0.0306 (6)
O50.7100 (2)−0.05216 (15)0.5392 (2)0.0331 (5)
O10.9396 (3)0.04823 (17)0.69183 (19)0.0391 (6)
N30.6276 (3)0.1216 (2)0.6366 (3)0.0446 (8)
C80.8150 (4)−0.1040 (2)0.5394 (3)0.0283 (7)
O30.7847 (3)0.19595 (16)0.3566 (2)0.0460 (7)
H70.74050.17890.28790.069*
H80.83830.23910.34140.069*
C70.5460 (4)0.1247 (2)0.6986 (3)0.0341 (7)
C11.0394 (4)0.1337 (2)0.8404 (3)0.0389 (8)
H11.10540.15630.79840.047*
C50.8410 (5)0.0694 (2)0.9602 (3)0.0432 (9)
H50.77050.04800.99930.052*
C100.9366 (4)0.2917 (2)0.6101 (3)0.0382 (8)
C30.9481 (5)0.1260 (2)1.0121 (3)0.0434 (9)
C60.8381 (4)0.0448 (2)0.8523 (3)0.0375 (8)
H60.76700.00610.81870.045*
C21.0452 (5)0.1585 (2)0.9491 (3)0.0435 (9)
H21.11620.19800.98060.052*
N20.8969 (4)0.2242 (2)0.5898 (3)0.0535 (9)
S10.43595 (12)0.12573 (7)0.79119 (9)0.0475 (3)
S20.99454 (17)0.38766 (8)0.63505 (10)0.0637 (3)
O60.5521 (3)0.09437 (17)0.4048 (2)0.0448 (7)
H120.52910.09530.33020.067*
H130.46420.08220.42460.067*
C90.7879 (5)−0.1937 (2)0.5573 (5)0.0588 (12)
H9A0.6817−0.20460.54120.088*
H9B0.8279−0.20810.63370.088*
H9C0.8367−0.22660.50860.088*
C40.9579 (7)0.1507 (3)1.1326 (3)0.0727 (15)
H4A1.06160.15211.16950.109*
H4B0.90440.11061.16900.109*
H4C0.91390.20501.13630.109*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0236 (13)0.0450 (15)0.0414 (14)−0.0097 (10)0.0099 (10)−0.0056 (11)
Sm10.01875 (10)0.02561 (11)0.02988 (11)−0.00155 (6)0.00701 (7)−0.00335 (6)
O40.0243 (12)0.0361 (13)0.0362 (12)0.0029 (10)0.0047 (9)−0.0075 (10)
N10.0266 (15)0.0358 (16)0.0292 (14)0.0054 (11)0.0046 (11)−0.0044 (11)
O50.0252 (12)0.0286 (13)0.0468 (14)0.0006 (10)0.0106 (10)0.0021 (11)
O10.0342 (13)0.0556 (17)0.0266 (12)0.0100 (12)0.0035 (10)−0.0128 (11)
N30.0327 (17)0.058 (2)0.0454 (18)0.0062 (15)0.0121 (14)−0.0104 (16)
C80.0235 (17)0.0291 (17)0.0329 (16)−0.0043 (12)0.0071 (13)−0.0037 (13)
O30.0601 (18)0.0334 (14)0.0464 (15)−0.0098 (12)0.0150 (13)0.0047 (11)
C70.0272 (18)0.0320 (18)0.0424 (19)0.0024 (14)0.0053 (15)−0.0110 (15)
C10.033 (2)0.047 (2)0.0371 (19)−0.0063 (16)0.0087 (15)−0.0063 (16)
C50.045 (2)0.044 (2)0.045 (2)0.0064 (18)0.0211 (18)0.0085 (17)
C100.038 (2)0.042 (2)0.0319 (18)−0.0025 (16)0.0010 (15)−0.0086 (15)
C30.062 (3)0.035 (2)0.0339 (19)0.0112 (18)0.0124 (18)−0.0001 (15)
C60.0327 (19)0.036 (2)0.044 (2)−0.0011 (15)0.0068 (15)0.0009 (16)
C20.051 (2)0.040 (2)0.038 (2)−0.0063 (18)0.0048 (17)−0.0068 (16)
N20.057 (2)0.041 (2)0.062 (2)−0.0124 (17)0.0105 (18)−0.0147 (17)
S10.0469 (6)0.0438 (6)0.0595 (6)−0.0067 (4)0.0302 (5)−0.0165 (5)
S20.0994 (10)0.0416 (6)0.0495 (6)−0.0245 (6)0.0127 (6)−0.0128 (5)
O60.0218 (13)0.072 (2)0.0411 (15)0.0032 (12)0.0088 (11)0.0116 (12)
C90.041 (2)0.032 (2)0.106 (4)−0.0019 (17)0.020 (2)0.009 (2)
C40.122 (5)0.061 (3)0.038 (2)0.014 (3)0.023 (3)−0.005 (2)
Geometric parameters (Å, °) top
O2—C81.259 (4)C7—S11.639 (4)
Sm1—O2i2.390 (2)C1—C21.374 (5)
Sm1—O22.908 (3)C1—H10.9300
Sm1—O2i2.390 (2)C5—C61.367 (5)
Sm1—O12.398 (2)C5—C31.388 (6)
Sm1—O62.416 (3)C5—H50.9300
Sm1—O52.443 (2)C10—N21.150 (5)
Sm1—O42.467 (2)C10—S21.632 (4)
Sm1—N22.479 (3)C3—C21.372 (5)
Sm1—N32.508 (3)C3—C41.506 (5)
Sm1—O32.530 (3)C6—H60.9300
O4—H100.8934C2—H20.9300
O4—H110.8932O6—H120.8937
N1—C61.332 (4)O6—H130.8948
N1—C11.341 (5)C9—H9A0.9600
N1—O11.344 (3)C9—H9B0.9600
O5—C81.260 (4)C9—H9C0.9600
N3—C71.153 (4)C4—H4A0.9600
C8—C91.479 (5)C4—H4B0.9600
O3—H70.8987C4—H4C0.9600
O3—H80.8839
C8—O2—Sm1i158.2 (2)C1—N1—O1118.7 (3)
C8—O2—Sm185.3 (2)C8—O5—Sm1107.9 (2)
Sm1i—O2—Sm1116.07 (9)N1—O1—Sm1133.61 (19)
O2i—Sm1—O179.62 (9)C7—N3—Sm1169.5 (3)
O2i—Sm1—O6139.14 (9)O2—C8—O5119.7 (3)
O1—Sm1—O6139.55 (9)O2—C8—C9120.8 (3)
O2i—Sm1—O5110.87 (8)O5—C8—C9119.5 (3)
O1—Sm1—O576.00 (9)Sm1—O3—H7115.8
O6—Sm1—O577.88 (8)Sm1—O3—H8136.3
O2i—Sm1—O472.46 (8)H7—O3—H8101.9
O1—Sm1—O4131.46 (8)N3—C7—S1177.0 (4)
O6—Sm1—O470.66 (8)N1—C1—C2119.2 (3)
O5—Sm1—O477.99 (8)N1—C1—H1120.4
O2i—Sm1—N282.18 (10)C2—C1—H1120.4
O1—Sm1—N278.06 (11)C6—C5—C3120.7 (4)
O6—Sm1—N2111.92 (11)C6—C5—H5119.7
O5—Sm1—N2148.01 (11)C3—C5—H5119.7
O4—Sm1—N2133.87 (10)N2—C10—S2178.2 (4)
O2i—Sm1—N3149.98 (10)C2—C3—C5117.2 (3)
O1—Sm1—N375.73 (9)C2—C3—C4121.3 (4)
O6—Sm1—N369.53 (10)C5—C3—C4121.4 (4)
O5—Sm1—N379.49 (10)N1—C6—C5119.9 (4)
O4—Sm1—N3137.40 (9)N1—C6—H6120.1
N2—Sm1—N376.22 (12)C5—C6—H6120.1
O2i—Sm1—O381.78 (9)C3—C2—C1121.2 (4)
O1—Sm1—O3144.60 (9)C3—C2—H2119.4
O6—Sm1—O369.11 (9)C1—C2—H2119.4
O5—Sm1—O3139.15 (9)C10—N2—Sm1169.4 (3)
O4—Sm1—O368.97 (8)Sm1—O6—H12123.5
N2—Sm1—O369.75 (11)Sm1—O6—H13131.0
N3—Sm1—O3109.28 (10)H12—O6—H13103.3
O2i—Sm1—O263.93 (9)C8—C9—H9A109.5
O1—Sm1—O264.94 (8)C8—C9—H9B109.5
O6—Sm1—O2115.14 (8)H9A—C9—H9B109.5
O5—Sm1—O247.06 (7)C8—C9—H9C109.5
O4—Sm1—O267.26 (7)H9A—C9—H9C109.5
N2—Sm1—O2132.87 (10)H9B—C9—H9C109.5
N3—Sm1—O2118.38 (10)C3—C4—H4A109.5
O3—Sm1—O2130.46 (8)C3—C4—H4B109.5
Sm1—O4—H10127.3H4A—C4—H4B109.5
Sm1—O4—H11109.2C3—C4—H4C109.5
H10—O4—H11103.6H4A—C4—H4C109.5
C6—N1—C1121.8 (3)H4B—C4—H4C109.5
C6—N1—O1119.5 (3)
Symmetry codes: (i) −x+2, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O6—H12···S2ii0.892.353.240 (3)172
O3—H8···S1iii0.882.463.325 (3)168
O4—H10···S1iv0.892.393.279 (2)178
O6—H13···O5iv0.891.782.674 (3)177
O4—H11···O1i0.891.792.685 (3)177
O3—H7···S2ii0.902.833.643 (3)152
Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) −x+1, −y, −z+1; (i) −x+2, −y, −z+1.
Table 1
Selected geometric parameters (Å) top
Sm1—O2i2.390 (2)Sm1—O42.467 (2)
Sm1—O22.908 (3)Sm1—N22.479 (3)
Sm1—O12.398 (2)Sm1—N32.508 (3)
Sm1—O62.416 (3)Sm1—O32.530 (3)
Sm1—O52.443 (2)
Symmetry codes: (i) −x+2, −y, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O6—H12···S2ii0.892.353.240 (3)172
O3—H8···S1iii0.882.463.325 (3)168
O4—H10···S1iv0.892.393.279 (2)178
O6—H13···O5iv0.891.782.674 (3)177
O4—H11···O1i0.891.792.685 (3)177
O3—H7···S2ii0.902.833.643 (3)152
Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) −x+1, −y, −z+1; (i) −x+2, −y, −z+1.
Acknowledgements top

The authors thank the Natural Science Foundation of Shandong Province of China (grant No. Y2005B25).

references
References top

Bruker (1997). SMART (Version 5.6) and SAINT (Version 5.06a). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.

Panagiotopoulos, A., Zafiropoulos, T. F., Perlepes, S. P., Bakalbassis, E., Masson-Ramade, I., Kahn, O., Terzis, A. & Raptopoulou, C. P. (1995). Inorg. Chem. 34, 4918–4920.

Sheldrick, G. M. (1996). SADABS. Version 2.10. University of Göttingen, Germany.

Zhang, S.-G., Li, W.-N. & Shi, J.-M. (2006). Acta Cryst. E62, m3506–m3608.