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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): m1106–m1107.
Published online 2010 August 18. doi:  10.1107/S160053681003182X
PMCID: PMC3007906

Poly[[tetra­kis­(μ2-pyrazine N,N′-dioxide-κ2 O:O′)dysprosium(III)] tris­(perchlorate)]

Abstract

The title three-dimensional coordination network, {[Dy(C4H4N2O2)4](ClO4)3}n, is isostructural of other lanthanides. The Dy+3 cation lies on a fourfold roto-inversion axis. It is coordinated in a distorted square-anti­prismatic fashion by eight O atoms from bridging pyrazine N,N′-dioxide ligands. There are two unique pyrazine N,N′-dioxide ligands. One ring is located around an inversion center, and there is a a twofold rotation axis at the center of the other ring. There are also two unique perchlorate anions. One is centered on a twofold rotation axis and the other on a fourfold roto-inversion axis. The perchlorate anions are located in channels that run perpendicular to (001) and (110) and inter­act with the coordination network through C—H(...)O hydrogen bonds.

Related literature

For the isostructural La, Ce, Pr, Sm, Eu, Gd, Tb and Y coordination networks, see: Sun et al. (2004 [triangle]). For the isostructural Nd, Ho and Er coordination networks, see: Quinn-Elmore et al. (2010 [triangle]); Buchner et al. (2010a [triangle],b [triangle]), respectively. Detailed background to this study is given in the first article of this series by Quinn-Elmore et al. (2010 [triangle]).

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Object name is e-66-m1106-scheme1.jpg

Experimental

Crystal data

  • [Dy(C4H4N2O2)4](ClO4)3
  • M r = 909.22
  • Tetragonal, An external file that holds a picture, illustration, etc.
Object name is e-66-m1106-efi21.jpg
  • a = 15.2553 (4) Å
  • c = 22.6667 (12) Å
  • V = 5275.1 (3) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 3.25 mm−1
  • T = 100 K
  • 0.34 × 0.27 × 0.20 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.374, T max = 0.532
  • 8476 measured reflections
  • 1800 independent reflections
  • 1493 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.096
  • S = 0.99
  • 1800 reflections
  • 110 parameters
  • H-atom parameters constrained
  • Δρmax = 2.68 e Å−3
  • Δρmin = −1.48 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT-Plus (Bruker, 2007 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: X-SEED.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681003182X/zl2299sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681003182X/zl2299Isup2.hkl

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

Acknowledgments

The authors are thankful to Allegheny College for providing funding in support of this research. The diffractometer was funded by the NSF (grant No. 0087210), the Ohio Board of Regents (grant No. CAP-491) and by Youngstown State University. The authors would like to acknowledge Youngstown State University and the STaRBURSTT CyberInstrumentation Consortium for assistance with the crystallography.

supplementary crystallographic information

Comment

The description of the structure of the title compound is part of a series of consecutive papers on three-dimensional coordination networks of the type {[Ln(C4H4N2O2)4](ClO4)3}n, with Ln = Nd (Quinn-Elmore et al. 2010), Dy (this publication), Ho (Buchner et al. 2010a) and Er (Buchner et al. 2010b), respectively. All four compounds are also isostructural to the previously reported La, Ce, Pr, Sm, Eu, Gd, Tb and Y coordination networks (Sun et al. 2004). The background to this study is given in ther first article of this series by Quinn-Elmore et al. (2010).

Experimental

Pyrazine N,N'-dioxide (0.025 g, 0.223 mmol) was dissolved in deionized water (1.5 ml) and methanol (1.5 ml). An aqueous solution of Dy(ClO4)3 (0.320 ml of a 0.0868 M solution, 0.028 mmol) was diluted with methanol (0.680 ml) and CH2Cl2 (2.5 ml). The pyrazine N,N'-dioxide solution was layered over the Dy(ClO4)3 solution, and the two solutions were allowed to slowly mix. Colorless block-like crystals formed upon the slow evaporation of the resultant solution.

Refinement

All H atoms were positioned geometrically and refined using a riding model with C—H = 0.95Å and with Uiso(H) = 1.2 times Ueq(C).

Figures

Fig. 1.
The coordination environment of the Dy+3 cation in title compound with atom labels and 50% probability displacement ellipsoids. Hydrogen atoms have been omitted for clarity. Symmetry codes: (i) y + 1/4, x - 1/4, -z + 3/4; (ii) -y + 3/4, -x + 3/4, -z + ...

Crystal data

[Dy(C4H4N2O2)4](ClO4)3Dx = 2.290 Mg m3
Mr = 909.22Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/acdCell parameters from 4338 reflections
Hall symbol: -I 4bd 2cθ = 2.7–30.5°
a = 15.2553 (4) ŵ = 3.25 mm1
c = 22.6667 (12) ÅT = 100 K
V = 5275.1 (3) Å3Block, colourless
Z = 80.34 × 0.27 × 0.20 mm
F(000) = 3560

Data collection

Bruker SMART APEX CCD diffractometer1800 independent reflections
Radiation source: fine-focus sealed tube1493 reflections with I > 2σ(I)
graphiteRint = 0.018
ω scansθmax = 30.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −21→19
Tmin = 0.374, Tmax = 0.532k = −3→21
8476 measured reflectionsl = −20→25

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096H-atom parameters constrained
S = 0.99w = 1/[σ2(Fo2) + (0.0554P)2 + 37.1849P] where P = (Fo2 + 2Fc2)/3
1800 reflections(Δ/σ)max < 0.001
110 parametersΔρmax = 2.68 e Å3
0 restraintsΔρmin = −1.48 e Å3

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 (Å2)

xyzUiso*/Ueq
Dy10.50000.25000.37500.00560 (12)
Cl10.50000.25000.12500.0113 (4)
Cl20.72654 (6)−0.02346 (6)0.12500.0281 (3)
O10.59121 (12)0.21876 (14)0.29510 (10)0.0155 (4)
O20.53217 (14)0.39451 (12)0.34383 (10)0.0153 (4)
O30.57642 (16)0.24419 (16)0.16207 (12)0.0251 (6)
O40.6466 (4)−0.0162 (4)0.1506 (4)0.137 (3)
O50.7912 (4)−0.0056 (4)0.1658 (4)0.129 (3)
N10.66943 (16)0.23424 (16)0.27415 (13)0.0143 (5)
N20.52711 (16)0.44491 (15)0.29779 (12)0.0126 (5)
C10.70896 (18)0.17248 (18)0.24020 (14)0.0151 (6)
H10.68070.11790.23350.018*
C20.78920 (18)0.18838 (18)0.21566 (14)0.0150 (6)
H20.81610.14530.19140.018*
C30.5260 (2)0.41183 (17)0.24253 (15)0.0158 (6)
H30.52520.35010.23680.019*
C40.52588 (19)0.46669 (17)0.19470 (15)0.0152 (6)
H40.52500.44280.15600.018*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Dy10.00587 (12)0.00587 (12)0.0051 (2)−0.00030 (6)0.0000.000
Cl10.0138 (5)0.0138 (5)0.0061 (11)0.0000.0000.000
Cl20.0263 (4)0.0263 (4)0.0316 (9)−0.0106 (5)0.0033 (3)−0.0033 (3)
O10.0097 (8)0.0235 (10)0.0132 (12)−0.0029 (7)0.0045 (7)−0.0042 (8)
O20.0247 (10)0.0113 (8)0.0100 (13)−0.0020 (7)−0.0023 (8)0.0048 (7)
O30.0179 (11)0.0433 (15)0.0142 (15)0.0047 (9)−0.0040 (10)−0.0023 (9)
O40.066 (3)0.114 (5)0.230 (7)−0.010 (3)0.097 (5)−0.016 (5)
O50.076 (4)0.099 (4)0.212 (9)0.003 (3)−0.058 (5)−0.076 (5)
N10.0113 (10)0.0182 (10)0.0134 (16)−0.0011 (8)0.0010 (9)0.0001 (10)
N20.0149 (10)0.0121 (10)0.0108 (15)−0.0003 (8)−0.0013 (9)0.0018 (9)
C10.0154 (12)0.0159 (12)0.0142 (17)−0.0005 (9)0.0008 (10)−0.0029 (10)
C20.0137 (12)0.0182 (13)0.0130 (17)−0.0004 (9)0.0006 (10)−0.0040 (11)
C30.0193 (13)0.0110 (11)0.0169 (18)−0.0022 (10)−0.0026 (12)0.0005 (10)
C40.0205 (13)0.0116 (11)0.0135 (17)−0.0001 (10)0.0006 (11)0.0000 (10)

Geometric parameters (Å, °)

Dy1—O1i2.333 (2)Cl2—O5vi1.380 (6)
Dy1—O1ii2.333 (2)O1—N11.306 (3)
Dy1—O12.333 (2)O2—N21.298 (3)
Dy1—O1iii2.333 (2)N1—C11.358 (4)
Dy1—O2i2.3665 (19)N1—C2vii1.358 (4)
Dy1—O2ii2.3665 (19)N2—C31.351 (4)
Dy1—O22.3665 (19)N2—C4viii1.359 (3)
Dy1—O2iii2.3665 (19)C1—C21.366 (4)
Cl1—O31.440 (2)C1—H10.9500
Cl1—O3iv1.440 (2)C2—N1vii1.358 (4)
Cl1—O3iii1.440 (2)C2—H20.9500
Cl1—O3v1.440 (2)C3—C41.370 (4)
Cl2—O4vi1.355 (4)C3—H30.9500
Cl2—O41.355 (4)C4—N2viii1.359 (3)
Cl2—O51.380 (6)C4—H40.9500
O1i—Dy1—O1ii78.16 (11)O3iv—Cl1—O3iii109.92 (11)
O1i—Dy1—O1147.81 (10)O3—Cl1—O3v109.92 (11)
O1ii—Dy1—O1111.03 (11)O3iv—Cl1—O3v108.6 (2)
O1i—Dy1—O1iii111.03 (11)O3iii—Cl1—O3v109.91 (11)
O1ii—Dy1—O1iii147.81 (10)O4vi—Cl2—O4109.3 (6)
O1—Dy1—O1iii78.16 (11)O4vi—Cl2—O5114.0 (4)
O1i—Dy1—O2i80.49 (7)O4—Cl2—O5109.9 (5)
O1ii—Dy1—O2i72.64 (7)O4vi—Cl2—O5vi109.9 (5)
O1—Dy1—O2i73.66 (7)O4—Cl2—O5vi114.0 (4)
O1iii—Dy1—O2i138.16 (7)O5—Cl2—O5vi99.7 (8)
O1i—Dy1—O2ii72.64 (7)N1—O1—Dy1142.21 (18)
O1ii—Dy1—O2ii80.49 (7)N2—O2—Dy1141.19 (17)
O1—Dy1—O2ii138.16 (7)O1—N1—C1119.1 (2)
O1iii—Dy1—O2ii73.66 (7)O1—N1—C2vii121.3 (2)
O2i—Dy1—O2ii145.25 (11)C1—N1—C2vii119.5 (2)
O1i—Dy1—O273.66 (7)O2—N2—C3121.7 (2)
O1ii—Dy1—O2138.16 (7)O2—N2—C4viii119.2 (3)
O1—Dy1—O280.49 (7)C3—N2—C4viii119.1 (3)
O1iii—Dy1—O272.64 (7)N1—C1—C2120.4 (3)
O2i—Dy1—O272.71 (10)N1—C1—H1119.8
O2ii—Dy1—O2118.40 (10)C2—C1—H1119.8
O1i—Dy1—O2iii138.16 (7)N1vii—C2—C1120.1 (3)
O1ii—Dy1—O2iii73.66 (7)N1vii—C2—H2120.0
O1—Dy1—O2iii72.64 (7)C1—C2—H2120.0
O1iii—Dy1—O2iii80.49 (7)N2—C3—C4120.4 (2)
O2i—Dy1—O2iii118.40 (10)N2—C3—H3119.8
O2ii—Dy1—O2iii72.71 (10)C4—C3—H3119.8
O2—Dy1—O2iii145.25 (11)N2viii—C4—C3120.5 (3)
O3—Cl1—O3iv109.91 (11)N2viii—C4—H4119.8
O3—Cl1—O3iii108.6 (2)C3—C4—H4119.8

Symmetry codes: (i) y+1/4, x−1/4, −z+3/4; (ii) −y+3/4, −x+3/4, −z+3/4; (iii) −x+1, −y+1/2, z; (iv) −y+3/4, x−1/4, −z+1/4; (v) y+1/4, −x+3/4, −z+1/4; (vi) y+3/4, x−3/4, −z+1/4; (vii) −x+3/2, −y+1/2, −z+1/2; (viii) x, −y+1, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···O2vii0.952.523.293 (4)138.
C2—H2···O50.952.403.168 (6)137.
C3—H3···O10.952.603.329 (4)134.
C3—H3···O30.952.473.234 (4)138.
C4—H4···O3iv0.952.373.245 (4)153.

Symmetry codes: (vii) −x+3/2, −y+1/2, −z+1/2; (iv) −y+3/4, x−1/4, −z+1/4.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2299).

References

  • Barbour, L. J. (2001). J. Supramol. Chem, 1, 189–191.
  • Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). SMART and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Buchner, J. D., Quinn-Elmore, B. G., Beach, K. B. & Knaust, J. M. (2010a). Acta Cryst. E66, m1108–m1109. [PMC free article] [PubMed]
  • Buchner, J. D., Quinn-Elmore, B. G., Beach, K. B. & Knaust, J. M. (2010b). Acta Cryst. E66, m1110–m1111. [PMC free article] [PubMed]
  • Quinn-Elmore, B. G., Buchner, J. D., Beach, K. B. & Knaust, J. M. (2010). Acta Cryst. E66, m1104–m1105. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sun, H. L., Gao, S., Ma, B. Q., Chang, F. & Fu, W. F. (2004). Microporous Mesoporous Mater.73 89-95.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography