Search tips
Search criteria 


Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): m1104–m1105.
Published online 2010 August 18. doi:  10.1107/S1600536810031818
PMCID: PMC3008011

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


The title three-dimensional coordination network, {[Nd(C4H4N2O2)4](ClO4)3}n, is isostructural to that of other lanthanides. The Nd+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 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 Dy, Ho, Er coordination networks, see: Quinn-Elmore et al. (2010 [triangle]); Buchner et al. (2010a [triangle],b [triangle]), respectively. For a lanthanum 4,4′-bipyridine N,N′-dioxide coordination network of similar topology, see: Long et al. (2001 [triangle]). For additional discussions on Ln 3+ (Ln = lanthanide) coordination networks with aromatic N,N′-dioxide ligands, see: Cardoso et al. (2001 [triangle]); Hill et al. (2005 [triangle]). For background information on the applications of coordination networks, see: Roswell & Yaghi (2004 [triangle]); Rosi et al. (2003 [triangle]); Seo et al. (2000 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1104-scheme1.jpg


Crystal data

  • [Nd(C4H4N2O2)4](ClO4)3
  • M r = 890.96
  • Tetragonal, An external file that holds a picture, illustration, etc.
Object name is e-66-m1104-efi1.jpg
  • a = 15.3804 (4) Å
  • c = 22.9843 (12) Å
  • V = 5437.1 (3) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 2.32 mm−1
  • T = 100 K
  • 0.23 × 0.23 × 0.18 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.593, T max = 0.659
  • 30711 measured reflections
  • 2086 independent reflections
  • 1842 reflections with I > 2σ(I)
  • R int = 0.024


  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.106
  • S = 1.10
  • 2086 reflections
  • 110 parameters
  • H-atom parameters constrained
  • Δρmax = 2.27 e Å−3
  • Δρmin = −1.95 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/S1600536810031818/zl2298sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810031818/zl2298Isup2.hkl

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


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


The synthesis of lanthanide coordination networks has been of recent interest due to the potential of the flexible coordination sphere of the Ln+3 metal ions to produce coordination networks with new, unusual, or high connectivity topologies (Hill et al. 2005, Long et al. 2001, and Sun et al. 2004). Coordination networks with both a high connectivity topology and an open framework have potential for applications in areas such as absorption, ion exchange, or catalysis (Roswell et al. 2004, Rosi et al. 2003, and Seo et al. 2000). Aromatic N,N'-dioxide ligands have been attractive candidates for use with Ln+3 cations as the O-donor atoms of the ligand are complementary to the hard acid character of the lanthanide cations (Cardoso et al. 2001, Hill et al. 2005, Long et al. 2001, and Sun et al. 2004).

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 (this publication), Dy (Quinn-Elmore et al. 2010), 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 asymmetric unit of the title compound contains one quarter of a Nd+3 cation, half of two coordinated pyrazine N,N'-dioxide ligands, a quarter of one perchlorate anion, and a half of another perchlorate anion (Figure 1). The Nd+3 cation lies on a fourfold roto-inversion axis. One ligand (O1, N1, C1, C2) is located around an inversion center, and there is a twofold rotation axis at the center of the other (O2, N2, C3, C4). Both chlorine atoms of the perchlorate anions lie on special positions. Cl1 lies on a fourfold roto-inversion axis, and Cl2 is located on a twofold rotation axis. The high atomic displacement parameters for O4 and O5 bonded to Cl2, and the residual electron density around Cl2 indicate that this perchlorate anion is disordered; however, the disorder does not appear discreet. Only O4 and O5 are easily found in positions that agree with the site symmetry of the anion, therefore only one position was modeled.

The Nd+3 cation is coordinated in a distorted square anti-prismatic fashion by eight O atoms from bridging pyrazine N,N'-dioxide ligands forming a three-dimensional coordination network. The network topology is similar to that which is seen in {[La(4,4'-bipyridine N,N'-dioxide)4](CF3SO3)3.4.2CH3OH}n in that in can be considered as being composed of two sets of intersecting (4,4) nets (Long et al. 2001). The nets are perpendicular to one another, but they are canted. One set of nets lies parallel to the (1 0 0) plane, and the other set lies parallel to the (0 1 0) plane (Figure 2).

The title compound forms five unique C—H···O hydrogen bonds (Figure 3). There are two unique hydrogen bonds between pyrazine N,N'-dioxide ligands and another three hydrogen bonds between the perchlorate anions and pyrazine N,N'-dioxide ligands. The non-disordered perchlorate anion (Cl1 and O3) forms two unique hydrogen bonds with pyrazine N,N'-dioxide ligands resulting in a total of eight hydrogen bonds per ion with the network, but the disordered perchlorate (Cl2, O4, and O5) forms only one unique hydrogen bond with pyrazine N,N'-dioxide ligands resulting in a total of only two hydrogen bonds per ion with the network. As seen in the packing diagrams, the perchlorate anions are located in two sets of channels (Figures 4 and 5). In channels that run perpendicular to the (0 0 1) plane only anions containing Cl2 are present. (Figure 4), but in the channels that run perpendiclar to the (1 1 0) plane the anions containing Cl1 and Cl2 alternate (Figure 5).


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 Nd(ClO4)3 (0.240 ml of a 0.1167 M solution, 0.028 mmol) was diluted with methanol (0.760 ml) and CH2Cl2 (2.5 ml). The pyrazine N,N'-dioxide solution was layered over the Nd(ClO4)3 solution, and the two solutions were allowed to slowly mix. Rose colored block-like crystals formed upon the slow evaporation of the resultant solution.


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


Fig. 1.
The coordination environment of the Nd+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+3/4; (iii) ...
Fig. 2.
Schematic representation of the network topology seen in {[Nd(C4H4N2O2)4](ClO4)3}n. The net shown in red is parallel to the (1 0 0) plane, and the net shown in blue is parallel to the (0 1 0) plane.
Fig. 3.
C—H···O hydrogen bonding interactions between pyrazine N,N'-dioxide ligands and between perchlorate anions and pyrazine N,N'-dioxide ligands. Hydrogen bonds are shown as dashed lines. Symmetry codes: (iv) -y+3/4, x-1/4, ...
Fig. 4.
Packing of the title compound viewed perpendicular to the (0 0 1) with anions shown in ball and stick representation. In these channels there are only anions containing Cl2. Hydrogen atoms have been omitted for clarity. Color scheme: Nd: green, C: grey, ...
Fig. 5.
Packing of the title compound viewed perpendicular to the (1 1 0) plane with anions shown in ball and stick representation. The the perchlorate anions in these channels alternate between those containing Cl1 and Cl2. Hydrogen atoms have been omitted for ...

Crystal data

[Nd(C4H4N2O2)4](ClO4)3Dx = 2.177 Mg m3
Mr = 890.96Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/acdCell parameters from 15053 reflections
Hall symbol: -I 4bd 2cθ = 2.6–30.5°
a = 15.3804 (4) ŵ = 2.32 mm1
c = 22.9843 (12) ÅT = 100 K
V = 5437.1 (3) Å3Block, rose
Z = 80.23 × 0.23 × 0.18 mm
F(000) = 3512

Data collection

Bruker SMART APEX CCD diffractometer2086 independent reflections
Radiation source: fine-focus sealed tube1842 reflections with I > 2σ(I)
graphiteRint = 0.024
ω scansθmax = 30.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −21→21
Tmin = 0.593, Tmax = 0.659k = −21→21
30711 measured reflectionsl = −32→32


Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 1.10w = 1/[σ2(Fo2) + (0.0535P)2 + 38.356P] where P = (Fo2 + 2Fc2)/3
2086 reflections(Δ/σ)max < 0.001
110 parametersΔρmax = 2.27 e Å3
0 restraintsΔρmin = −1.95 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

Nd10.50000.25000.37500.00589 (11)
Cl10.50000.25000.12500.0119 (3)
Cl20.72544 (6)−0.02456 (6)0.12500.0319 (3)
O10.59191 (12)0.21965 (14)0.29303 (8)0.0171 (4)
O20.53338 (14)0.39686 (12)0.34324 (8)0.0168 (4)
O30.57573 (16)0.24613 (16)0.16135 (10)0.0277 (5)
O40.6477 (5)−0.0172 (6)0.1497 (5)0.191 (4)
O50.7895 (5)−0.0023 (6)0.1623 (5)0.180 (5)
N10.66963 (15)0.23449 (15)0.27293 (10)0.0141 (4)
N20.52833 (15)0.44642 (14)0.29745 (9)0.0129 (4)
C10.70832 (17)0.17377 (17)0.23897 (11)0.0154 (5)
C20.78886 (16)0.18959 (17)0.21540 (11)0.0152 (5)
C30.52715 (18)0.41238 (16)0.24314 (11)0.0148 (5)
C40.52702 (18)0.46617 (16)0.19547 (11)0.0147 (5)

Atomic displacement parameters (Å2)

Nd10.00627 (13)0.00627 (13)0.00511 (16)−0.00034 (7)0.0000.000
Cl10.0146 (4)0.0146 (4)0.0065 (6)0.0000.0000.000
Cl20.0304 (4)0.0304 (4)0.0349 (6)−0.0118 (5)0.0035 (3)−0.0035 (3)
O10.0112 (8)0.0256 (10)0.0146 (8)−0.0032 (7)0.0052 (7)−0.0036 (7)
O20.0283 (10)0.0114 (8)0.0107 (8)−0.0031 (7)−0.0038 (7)0.0049 (6)
O30.0195 (11)0.0479 (15)0.0156 (10)0.0057 (9)−0.0054 (8)−0.0033 (8)
O40.085 (5)0.154 (7)0.335 (12)−0.015 (4)0.138 (7)−0.028 (7)
O50.091 (5)0.130 (6)0.317 (15)0.007 (4)−0.066 (7)−0.135 (8)
N10.0116 (10)0.0198 (10)0.0110 (9)−0.0011 (8)0.0022 (8)−0.0013 (8)
N20.0160 (10)0.0117 (9)0.0111 (9)0.0000 (8)−0.0017 (7)0.0028 (7)
C10.0149 (11)0.0172 (11)0.0140 (11)−0.0008 (9)0.0023 (8)−0.0029 (9)
C20.0135 (11)0.0188 (12)0.0132 (10)0.0000 (9)0.0013 (8)−0.0027 (9)
C30.0206 (12)0.0104 (10)0.0134 (11)−0.0018 (9)−0.0019 (9)0.0006 (8)
C40.0209 (12)0.0114 (10)0.0118 (10)−0.0002 (9)−0.0002 (9)0.0006 (8)

Geometric parameters (Å, °)

Nd1—O1i2.4012 (18)Cl2—O5vi1.350 (7)
Nd1—O1ii2.4012 (18)O1—N11.302 (3)
Nd1—O12.4012 (18)O2—N21.302 (3)
Nd1—O1iii2.4012 (18)N1—C11.355 (3)
Nd1—O2i2.4286 (18)N1—C2vii1.358 (3)
Nd1—O2ii2.4286 (18)N2—C31.354 (3)
Nd1—O22.4286 (18)N2—C4viii1.354 (3)
Nd1—O2iii2.4287 (18)C1—C21.374 (3)
Cl1—O31.435 (2)C1—H10.9500
Cl1—O3iv1.435 (2)C2—N1vii1.358 (3)
Cl1—O3iii1.435 (2)C2—H20.9500
Cl1—O3v1.435 (2)C3—C41.373 (3)
Cl2—O4vi1.328 (5)C3—H30.9500
Cl2—O41.328 (5)C4—N2viii1.354 (3)
Cl2—O51.350 (7)C4—H40.9500
O1i—Nd1—O1ii76.62 (10)O3iv—Cl1—O3iii109.83 (10)
O1i—Nd1—O1147.62 (10)O3—Cl1—O3v109.83 (10)
O1ii—Nd1—O1112.75 (10)O3iv—Cl1—O3v108.76 (19)
O1i—Nd1—O1iii112.75 (10)O3iii—Cl1—O3v109.83 (10)
O1ii—Nd1—O1iii147.62 (10)O4vi—Cl2—O4109.6 (8)
O1—Nd1—O1iii76.63 (10)O4vi—Cl2—O5115.9 (6)
O1i—Nd1—O2i79.66 (7)O4—Cl2—O5111.4 (7)
O1ii—Nd1—O2i73.01 (7)O4vi—Cl2—O5vi111.4 (7)
O1—Nd1—O2i74.30 (6)O4—Cl2—O5vi115.9 (6)
O1iii—Nd1—O2i137.92 (6)O5—Cl2—O5vi91.8 (11)
O1i—Nd1—O2ii73.01 (7)N1—O1—Nd1141.71 (16)
O1ii—Nd1—O2ii79.66 (7)N2—O2—Nd1140.80 (15)
O1—Nd1—O2ii137.92 (6)O1—N1—C1119.1 (2)
O1iii—Nd1—O2ii74.30 (6)O1—N1—C2vii120.8 (2)
O2i—Nd1—O2ii145.02 (9)C1—N1—C2vii120.0 (2)
O1i—Nd1—O274.30 (6)O2—N2—C3121.3 (2)
O1ii—Nd1—O2137.92 (6)O2—N2—C4viii119.0 (2)
O1—Nd1—O279.66 (7)C3—N2—C4viii119.7 (2)
O1iii—Nd1—O273.01 (7)N1—C1—C2120.1 (2)
O2i—Nd1—O272.37 (10)N1—C1—H1120.0
O2ii—Nd1—O2118.92 (10)C2—C1—H1120.0
O1i—Nd1—O2iii137.92 (6)N1vii—C2—C1119.9 (2)
O1ii—Nd1—O2iii74.30 (6)N1vii—C2—H2120.1
O1—Nd1—O2iii73.01 (7)C1—C2—H2120.1
O1iii—Nd1—O2iii79.66 (7)N2—C3—C4120.2 (2)
O2i—Nd1—O2iii118.92 (10)N2—C3—H3119.9
O2ii—Nd1—O2iii72.37 (10)C4—C3—H3119.9
O2—Nd1—O2iii145.02 (9)N2viii—C4—C3120.1 (2)
O3—Cl1—O3iv109.83 (10)N2viii—C4—H4119.9
O3—Cl1—O3iii108.76 (19)C3—C4—H4119.9

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, °)

C2—H2···O2vii0.952.553.326 (3)139.
C2—H2···O50.952.433.194 (7)137.
C3—H3···O10.952.593.331 (3)135.
C3—H3···O30.952.513.260 (3)136.
C4—H4···O3iv0.952.413.289 (3)154.

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


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2298).


  • 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]
  • Cardoso, M. C. C., Zinner, L. B., Zukerman-Scheptor, J., Araújo Melo, D. M. & Vincentini, G. J. (2001). J. Alloys Compd, 323–324, 22–25.
  • Hill, R. J., Long, D. L., Champness, N. R., Hubberstry, P. & Schröder, M. (2005). Acc. Chem. Res.38, 335–348. [PubMed]
  • Long, D. L., Blake, A. J., Champness, N. R., Wilson, C. & Schröder, M. (2001). Angew. Chem. Int. Ed.40, 2444–2447. [PubMed]
  • Quinn-Elmore, B. G., Buchner, J. D., Beach, K. B. & Knaust, J. M. (2010). Acta Cryst. E66, m1106–m1107. [PMC free article] [PubMed]
  • Rosi, N. L., Eckert, J., Eddaoudi, M., Vodak, D. T., Kim, J., O’Keeffe, M. & Yaghi, O. M. (2003). Science, 300, 1127–1129. [PubMed]
  • Roswell, J. L. C. & Yaghi, O. M. (2004). Microporous Mesoporous Mater.73, 3–14.
  • Seo, J. S., Whang, D., Lee, H., un, S. I., Oh, J., Jin Jeon, Y. J. & Kim, K. (2000). Nature (London), 404, 982–986. [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