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Acta Cryst. (2007). E63, m1763    [ doi:10.1107/S1600536807025457 ]

Di-[mu]-acetato-bis[triaquabis(thiocyanato-[kappa]N)(pyridine N-oxide-[kappa]O)neodymium(III)]

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

Abstract top

The title binuclear complex, [Nd2([mu]-C2H3O2)2(NCS)4(C5H5NO)2(H2O)6], lies about an inversion centre at the centroid of the four-membered Nd2O2 ring, with the two acetate ions acting as bridging ligands. A monodentate pyridine N-oxide ligand, two terminal thiocyanate groups and three water molecules complete the coordination environments of each nine-coordinate NdIII atom. O-H...O, O-H...N and O-H...S hydrogen bonds link the molecules into a three-dimensional network.

Comment top

Acetate, thiocyanate and pyridine N-oxide or its derivatives are all known to function as bridging ligands (Kato et al., 1964; Zhang et al., 2006), and we are interested in complexes with mixed bridge ligands which led to the synthesis of the title complex (I) and we report its structure here, Fig. 1. In the binuclear structure acetate acts as a bridging ligand, whereas thiocyanate, water and pyridine N-oxide only function as terminal ligands. The Nd and bridging acetate O atoms form a four-membered ring by virtue of the crystallographic inversion center which is at the centroid of the ring. The distance between the bridged Nd(III) ions is 4.4167 (7) Å, and atoms Nd1, Nd1i, O3 and O3i are strictly coplanar (i = -x + 2, -y + 2, -z + 1). An extensive set of O—H···O, O—H···N and O—H···S hydrogen bonds (Table 1) connect the binuclear units into a three-dimensional supermolecular structure.

Related literature top

For related structures, see: Kato et al. (1964); Zhang et al. (2006).

Experimental top

Nd(ClO4)3.6H2O (0.2891 g, 0.525 mmol), NaSCN (0.0872 g, 1.08 mmol), pyridine N-oxide (0.0502 g, 0.528 mmol) and Na(CH3COO) (0.0435 g, 0.530 mmol) were each dissolved in 5 ml of water. The solutions were then mixed together and stirred for a few minutes. Colourless transparent single crystals were obtained on 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 fixed with d(O—H) = 0.8200–0.8502 Å, Uiso(H) = 1.5eq(O). Other H atoms were placed in calculated positions, and refined as riding, with C—H = 0.93 Å, Uiso(H) = 1.2eq(C) for the pyridine ring; C—H = 0.96 Å, Uiso(H) = 1.5eq(C) for the methyl groups.

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. Binuclear structure of (I) showing the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) -x + 2, -y + 2, -z + 1].
Di-µ-acetato-bis[triaquabis(thiocyanato-κN)(pyridine N-oxide-κO)neodymium(III)] top
Crystal data top
[Nd2(C2H3O2)2(NCS)4(C5H5NO)2(H2O)6]F(000) = 916
Mr = 937.18Dx = 1.891 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3146 reflections
a = 9.1588 (15) Åθ = 2.2–26.8°
b = 16.185 (3) ŵ = 3.43 mm−1
c = 11.3892 (18) ÅT = 298 K
β = 102.813 (2)°Prism, colourless
V = 1646.3 (5) Å30.56 × 0.07 × 0.06 mm
Z = 2
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2900 independent reflections
Radiation source: fine-focus sealed tube2545 reflections with I > 2σ(I)
graphiteRint = 0.029
φ and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.249, Tmax = 0.821k = −19→17
6827 measured reflectionsl = −13→13
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0303P)2 + 1.869P]
where P = (Fo2 + 2Fc2)/3
2900 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 1.39 e Å−3
9 restraintsΔρmin = −0.95 e Å−3
Crystal data top
[Nd2(C2H3O2)2(NCS)4(C5H5NO)2(H2O)6]V = 1646.3 (5) Å3
Mr = 937.18Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.1588 (15) ŵ = 3.43 mm−1
b = 16.185 (3) ÅT = 298 K
c = 11.3892 (18) Å0.56 × 0.07 × 0.06 mm
β = 102.813 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2900 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2545 reflections with I > 2σ(I)
Tmin = 0.249, Tmax = 0.821Rint = 0.029
6827 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.071Δρmax = 1.39 e Å−3
S = 1.02Δρmin = −0.95 e Å−3
2900 reflectionsAbsolute structure: ?
191 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
Nd10.81351 (3)0.914089 (14)0.50289 (2)0.02859 (10)
S20.9773 (2)0.60651 (9)0.60836 (14)0.0636 (5)
S10.4319 (2)0.85963 (10)0.77853 (17)0.0731 (5)
C60.8144 (5)1.0972 (3)0.5558 (4)0.0324 (11)
O30.9353 (3)1.07210 (19)0.5326 (3)0.0367 (8)
N10.9405 (4)0.9164 (2)0.8172 (3)0.0355 (9)
O60.5523 (4)0.9109 (2)0.3919 (3)0.0516 (10)
H90.47610.92100.42050.077*
H80.52650.90770.31560.077*
O10.9538 (4)0.9411 (2)0.7079 (3)0.0465 (9)
O20.7084 (3)1.0477 (2)0.5525 (3)0.0384 (8)
O50.7805 (5)0.8141 (2)0.3268 (3)0.0626 (11)
H100.72600.83230.26200.094*
H110.83070.77280.31330.094*
N30.6407 (5)0.8676 (3)0.6364 (4)0.0471 (11)
N20.9058 (6)0.7726 (3)0.5737 (5)0.0645 (14)
C90.9357 (6)0.7034 (4)0.5892 (4)0.0447 (13)
C21.0314 (6)0.8571 (3)0.8735 (5)0.0514 (14)
H21.09960.83150.83580.062*
C70.7971 (7)1.1846 (4)0.5870 (7)0.076 (2)
H7A0.69631.19420.59480.114*
H7B0.81861.21940.52460.114*
H7C0.86531.19720.66180.114*
C11.0225 (7)0.8348 (4)0.9877 (6)0.0655 (18)
H11.08550.79391.02810.079*
O40.7882 (4)0.9858 (2)0.3048 (3)0.0408 (8)
H70.71581.01700.29400.061*
H60.86921.00940.29930.061*
C30.8400 (6)0.9531 (3)0.8683 (5)0.0438 (12)
H30.77710.99360.82680.053*
C40.8298 (7)0.9311 (4)0.9810 (5)0.0622 (18)
H40.75950.95651.01670.075*
C50.9224 (8)0.8719 (5)1.0422 (6)0.077 (2)
H50.91690.85711.12000.092*
C80.5514 (5)0.8627 (3)0.6923 (4)0.0358 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Nd10.02128 (15)0.03128 (15)0.03543 (16)0.00006 (10)0.01103 (11)0.00093 (11)
S20.0951 (13)0.0463 (9)0.0496 (9)0.0206 (8)0.0162 (9)0.0095 (7)
S10.0744 (12)0.0619 (10)0.1033 (13)0.0212 (8)0.0629 (11)0.0405 (10)
C60.023 (3)0.032 (3)0.044 (3)0.0065 (19)0.012 (2)−0.003 (2)
O30.0235 (17)0.0415 (19)0.048 (2)0.0027 (14)0.0133 (15)0.0014 (15)
N10.030 (2)0.041 (2)0.035 (2)−0.0081 (18)0.0058 (18)0.0038 (18)
O60.0186 (17)0.090 (3)0.048 (2)−0.0006 (17)0.0123 (16)−0.013 (2)
O10.037 (2)0.070 (2)0.0341 (18)−0.0149 (18)0.0091 (16)0.0106 (17)
O20.0251 (18)0.0377 (19)0.057 (2)−0.0008 (15)0.0186 (16)−0.0071 (16)
O50.072 (3)0.051 (2)0.059 (2)0.020 (2)0.002 (2)−0.015 (2)
N30.041 (3)0.054 (3)0.049 (3)−0.005 (2)0.015 (2)0.008 (2)
N20.075 (4)0.051 (3)0.072 (3)0.018 (3)0.026 (3)0.020 (3)
C90.043 (3)0.055 (4)0.037 (3)0.007 (3)0.009 (2)0.009 (3)
C20.045 (3)0.049 (3)0.061 (4)0.007 (3)0.013 (3)0.007 (3)
C70.049 (4)0.043 (4)0.144 (7)−0.008 (3)0.036 (4)−0.025 (4)
C10.062 (4)0.064 (4)0.063 (4)−0.005 (3)−0.003 (3)0.026 (3)
O40.0265 (18)0.048 (2)0.048 (2)−0.0047 (15)0.0069 (15)0.0086 (16)
C30.033 (3)0.049 (3)0.050 (3)−0.001 (2)0.010 (2)−0.004 (3)
C40.052 (4)0.092 (5)0.049 (4)−0.014 (3)0.025 (3)−0.013 (3)
C50.075 (5)0.110 (6)0.046 (4)−0.032 (5)0.017 (4)0.016 (4)
C80.035 (3)0.037 (3)0.036 (3)−0.002 (2)0.010 (2)0.007 (2)
Geometric parameters (Å, °) top
Nd1—O3i2.433 (3)O6—H80.8502
Nd1—O12.441 (3)O5—H100.8473
Nd1—O62.446 (3)O5—H110.8439
Nd1—O22.483 (3)N3—C81.145 (6)
Nd1—O42.502 (3)N2—C91.157 (7)
Nd1—N22.511 (5)C2—C11.369 (8)
Nd1—N32.540 (4)C2—H20.9300
Nd1—O52.542 (4)C7—H7A0.9600
Nd1—O32.781 (3)C7—H7B0.9600
S2—C91.617 (6)C7—H7C0.9600
S1—C81.626 (5)C1—C51.357 (10)
C6—O21.253 (5)C1—H10.9300
C6—O31.261 (5)O4—H70.8200
C6—C71.476 (7)O4—H60.8492
O3—Nd1i2.433 (3)C3—C41.354 (8)
N1—C31.333 (6)C3—H30.9300
N1—C21.338 (6)C4—C51.365 (10)
N1—O11.339 (5)C4—H40.9300
O6—H90.8483C5—H50.9300
O3i—Nd1—O179.97 (11)Nd1i—O3—Nd1115.65 (11)
O3i—Nd1—O6140.26 (11)C3—N1—C2121.8 (5)
O1—Nd1—O6138.13 (12)C3—N1—O1119.2 (4)
O3i—Nd1—O2112.74 (10)C2—N1—O1119.0 (4)
O1—Nd1—O276.98 (12)Nd1—O6—H9126.2
O6—Nd1—O275.61 (11)Nd1—O6—H8123.2
O3i—Nd1—O473.13 (10)H9—O6—H8109.8
O1—Nd1—O4134.66 (11)N1—O1—Nd1134.3 (3)
O6—Nd1—O470.08 (11)C6—O2—Nd1103.1 (3)
O2—Nd1—O480.67 (11)Nd1—O5—H10114.2
O3i—Nd1—N282.75 (14)Nd1—O5—H11132.3
O1—Nd1—N277.77 (15)H10—O5—H11110.8
O6—Nd1—N2111.58 (16)C8—N3—Nd1165.9 (4)
O2—Nd1—N2147.25 (14)C9—N2—Nd1169.4 (5)
O4—Nd1—N2132.08 (14)N2—C9—S2179.0 (5)
O3i—Nd1—N3149.81 (12)N1—C2—C1118.9 (6)
O1—Nd1—N375.30 (12)N1—C2—H2120.5
O6—Nd1—N368.60 (13)C1—C2—H2120.5
O2—Nd1—N378.31 (13)C6—C7—H7A109.5
O4—Nd1—N3137.05 (12)C6—C7—H7B109.5
N2—Nd1—N375.37 (16)H7A—C7—H7B109.5
O3i—Nd1—O583.04 (12)C6—C7—H7C109.5
O1—Nd1—O5144.44 (13)H7A—C7—H7C109.5
O6—Nd1—O569.37 (12)H7B—C7—H7C109.5
O2—Nd1—O5138.57 (12)C5—C1—C2120.5 (6)
O4—Nd1—O567.24 (12)C5—C1—H1119.8
N2—Nd1—O569.24 (15)C2—C1—H1119.8
N3—Nd1—O5107.62 (14)Nd1—O4—H7109.4
O3i—Nd1—O364.35 (12)Nd1—O4—H6111.6
O1—Nd1—O366.88 (11)H7—O4—H6113.8
O6—Nd1—O3113.70 (11)N1—C3—C4119.8 (6)
O2—Nd1—O348.43 (10)N1—C3—H3120.1
O4—Nd1—O368.72 (10)C4—C3—H3120.1
N2—Nd1—O3134.63 (15)C3—C4—C5120.2 (6)
N3—Nd1—O3119.09 (12)C3—C4—H4119.9
O5—Nd1—O3130.97 (12)C5—C4—H4119.9
O2—C6—O3119.9 (4)C1—C5—C4118.9 (6)
O2—C6—C7119.8 (4)C1—C5—H5120.6
O3—C6—C7120.3 (4)C4—C5—H5120.6
C6—O3—Nd1i155.7 (3)N3—C8—S1176.2 (5)
C6—O3—Nd188.6 (3)
O2—C6—O3—Nd1i174.7 (5)O1—Nd1—O2—C669.5 (3)
C7—C6—O3—Nd1i−5.3 (11)O6—Nd1—O2—C6−142.5 (3)
O2—C6—O3—Nd1−1.7 (4)O4—Nd1—O2—C6−70.8 (3)
C7—C6—O3—Nd1178.4 (5)N2—Nd1—O2—C6109.9 (4)
O3i—Nd1—O3—C6178.3 (3)N3—Nd1—O2—C6146.9 (3)
O1—Nd1—O3—C6−92.0 (3)O5—Nd1—O2—C6−109.6 (3)
O6—Nd1—O3—C642.2 (3)O3—Nd1—O2—C6−1.0 (3)
O2—Nd1—O3—C61.0 (3)O3i—Nd1—N3—C8129.8 (16)
O4—Nd1—O3—C697.5 (3)O1—Nd1—N3—C893.8 (16)
N2—Nd1—O3—C6−133.8 (3)O6—Nd1—N3—C8−64.6 (16)
N3—Nd1—O3—C6−35.6 (3)O2—Nd1—N3—C814.4 (16)
O5—Nd1—O3—C6124.8 (3)O4—Nd1—N3—C8−47.9 (17)
O3i—Nd1—O3—Nd1i0.0N2—Nd1—N3—C8174.7 (17)
O1—Nd1—O3—Nd1i89.71 (15)O5—Nd1—N3—C8−123.1 (16)
O6—Nd1—O3—Nd1i−136.12 (13)O3—Nd1—N3—C841.5 (17)
O2—Nd1—O3—Nd1i−177.4 (2)O3i—Nd1—N2—C9−102 (3)
O4—Nd1—O3—Nd1i−80.88 (14)O1—Nd1—N2—C9177 (3)
N2—Nd1—O3—Nd1i47.9 (2)O6—Nd1—N2—C940 (3)
N3—Nd1—O3—Nd1i146.10 (14)O2—Nd1—N2—C9137 (3)
O5—Nd1—O3—Nd1i−53.50 (19)O4—Nd1—N2—C9−42 (3)
C3—N1—O1—Nd1−79.8 (5)N3—Nd1—N2—C999 (3)
C2—N1—O1—Nd1102.1 (5)O5—Nd1—N2—C9−17 (3)
O3i—Nd1—O1—N1−146.6 (4)O3—Nd1—N2—C9−144 (3)
O6—Nd1—O1—N146.9 (5)Nd1—N2—C9—S230 (34)
O2—Nd1—O1—N197.1 (4)C3—N1—C2—C1−1.2 (8)
O4—Nd1—O1—N1159.5 (4)O1—N1—C2—C1176.9 (5)
N2—Nd1—O1—N1−61.9 (4)N1—C2—C1—C50.4 (9)
N3—Nd1—O1—N116.0 (4)C2—N1—C3—C40.9 (8)
O5—Nd1—O1—N1−83.9 (5)O1—N1—C3—C4−177.2 (5)
O3—Nd1—O1—N1147.2 (4)N1—C3—C4—C50.2 (9)
O3—C6—O2—Nd11.9 (5)C2—C1—C5—C40.7 (10)
C7—C6—O2—Nd1−178.1 (5)C3—C4—C5—C1−1.0 (10)
O3i—Nd1—O2—C6−3.6 (3)Nd1—N3—C8—S1−75 (8)
Symmetry codes: (i) −x+2, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H6···O1i0.851.832.675 (5)178
O6—H9···O2ii0.851.852.686 (4)167
O6—H8···S2iii0.852.313.162 (4)175
O5—H10···S2iii0.852.733.534 (4)159
O5—H11···S1iv0.842.403.236 (4)169
O4—H7···S1ii0.822.453.220 (4)157
O4—H6···N1i0.852.703.484 (5)155
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x−1/2, −y+3/2, z−1/2; (iv) x+1/2, −y+3/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H6···O1i0.851.832.675 (5)178
O6—H9···O2ii0.851.852.686 (4)167
O6—H8···S2iii0.852.313.162 (4)175
O5—H10···S2iii0.852.733.534 (4)159
O5—H11···S1iv0.842.403.236 (4)169
O4—H7···S1ii0.822.453.220 (4)157
O4—H6···N1i0.852.703.484 (5)155
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x−1/2, −y+3/2, z−1/2; (iv) x+1/2, −y+3/2, z−1/2.
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.

Kato, M., Jonassen, H. B. & Fanning, J. C. (1964). Chem. Rev. 64, 99–128.

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, m3398–m3400.