metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Poly[[tetra­kis­(μ2-pyrazine N,N′-dioxide-κ2O:O′)holmium(III)] tris­­(perchlorate)]

aAllegheny College, 520 North Main St., Meadville, PA 16335, USA
*Correspondence e-mail: jknaust@allegheny.edu

(Received 3 August 2010; accepted 8 August 2010; online 18 August 2010)

The title three-dimensional coordination network, {[Ho(C4H4N2O2)4](ClO4)3}n, is isostructural to that of other lanthanides. The Ho+3 cation lies on a fourfold roto-inversion axis. It is coordinated in a distorted square anti-prismatic 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) (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[Sun, H. L., Gao, S., Ma, B. Q., Chang, F. & Fu, W. F. (2004). Microporous Mesoporous Mater. 73 89-95.]). For the isostructural Nd, Dy and Er coordination networks, see: Quinn-Elmore et al. (2010a[Quinn-Elmore, B. G., Buchner, J. D., Beach, K. B. & Knaust, J. M. (2010a). Acta Cryst. E66, m1104-m1105.],b[Quinn-Elmore, B. G., Buchner, J. D., Beach, K. B. & Knaust, J. M. (2010b). Acta Cryst. E66, m1106-m1107.]); Buchner et al. (2010[Buchner, J. D., Quinn-Elmore, B. G., Beach, K. B. & Knaust, J. M. (2010). Acta Cryst. E66, m1110-m1111.]), respectively. Detailed background to this study is described in the first article of this series by Quinn-Elmore et al. (2010a[Quinn-Elmore, B. G., Buchner, J. D., Beach, K. B. & Knaust, J. M. (2010a). Acta Cryst. E66, m1104-m1105.]).

[Scheme 1]

Experimental

Crystal data
  • [Ho(C4H4N2O2)4](ClO4)3

  • Mr = 911.65

  • Tetragonal, I 41 /a c d

  • a = 15.2302 (4) Å

  • c = 22.6334 (12) Å

  • V = 5250.0 (3) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 3.43 mm−1

  • T = 100 K

  • 0.37 × 0.32 × 0.17 mm

Data collection
  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.292, Tmax = 0.558

  • 10709 measured reflections

  • 1906 independent reflections

  • 1585 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.103

  • S = 1.04

  • 1906 reflections

  • 110 parameters

  • H-atom parameters constrained

  • Δρmax = 3.23 e Å−3

  • Δρmin = −1.76 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2⋯O2i 0.95 2.52 3.285 (4) 138
C2—H2⋯O5 0.95 2.40 3.161 (7) 137
C3—H3⋯O1 0.95 2.60 3.323 (4) 134
C3—H3⋯O3 0.95 2.46 3.230 (4) 138
C4—H4⋯O3ii 0.95 2.36 3.234 (4) 153
Symmetry codes: (i) [-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [-y+{\script{3\over 4}}, x-{\script{1\over 4}}, -z+{\script{1\over 4}}].

Data collection: SMART (Bruker, 2007[Bruker (2007). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2007[Bruker (2007). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: X-SEED.

Supporting information


Comment top

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. 2010a), Dy (Quinn-Elmore et al. 2010b), Ho (this publication), and Er (Buchner et al. 2010), 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 the first article of this series by Quinn-Elmore et al. (2010a).

Related literature top

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

Experimental top

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 Ho(ClO4)3 (0.160 ml of a 0.0860 M solution, 0.0139 mmol) was diluted with methanol (0.840 ml)and CH2Cl2 (2.5 ml). The pyrazine N,N'-dioxide solution was layered over the Ho(ClO4)3 solution, and the two solutions were allowed to slowly mix. Orange plate-like crystals formed upon the slow evaporation of the resultant solution.

Refinement top

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).

Structure description top

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. 2010a), Dy (Quinn-Elmore et al. 2010b), Ho (this publication), and Er (Buchner et al. 2010), 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 the first article of this series by Quinn-Elmore et al. (2010a).

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

Computing details top

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

Figures top
[Figure 1] Fig. 1. The coordination environment of the Ho+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) -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.
Poly[[tetrakis(µ2-pyrazine N,N'-dioxide-κ2O:O')holmium(III)] tris(perchlorate)] top
Crystal data top
[Ho(C4H4N2O2)4](ClO4)3Dx = 2.307 Mg m3
Mr = 911.65Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/acdCell parameters from 4928 reflections
Hall symbol: -I 4bd 2cθ = 2.6–30.5°
a = 15.2302 (4) ŵ = 3.43 mm1
c = 22.6334 (12) ÅT = 100 K
V = 5250.0 (3) Å3Plate, orange
Z = 80.37 × 0.32 × 0.17 mm
F(000) = 3568
Data collection top
Bruker SMART APEX CCD
diffractometer
1906 independent reflections
Radiation source: fine-focus sealed tube1585 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω scansθmax = 30.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 721
Tmin = 0.292, Tmax = 0.558k = 2021
10709 measured reflectionsl = 2728
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0554P)2 + 37.1849P]
where P = (Fo2 + 2Fc2)/3
1906 reflections(Δ/σ)max < 0.001
110 parametersΔρmax = 3.23 e Å3
0 restraintsΔρmin = 1.76 e Å3
Crystal data top
[Ho(C4H4N2O2)4](ClO4)3Z = 8
Mr = 911.65Mo Kα radiation
Tetragonal, I41/acdµ = 3.43 mm1
a = 15.2302 (4) ÅT = 100 K
c = 22.6334 (12) Å0.37 × 0.32 × 0.17 mm
V = 5250.0 (3) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer
1906 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1585 reflections with I > 2σ(I)
Tmin = 0.292, Tmax = 0.558Rint = 0.025
10709 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.103H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0554P)2 + 37.1849P]
where P = (Fo2 + 2Fc2)/3
1906 reflectionsΔρmax = 3.23 e Å3
110 parametersΔρmin = 1.76 e Å3
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
Ho10.50000.25000.37500.00486 (12)
Cl10.50000.25000.12500.0107 (4)
Cl20.72659 (6)0.02341 (6)0.12500.0279 (3)
O10.59106 (13)0.21881 (15)0.29529 (10)0.0149 (4)
O20.53202 (15)0.39424 (13)0.34396 (10)0.0145 (4)
O30.57646 (17)0.24391 (17)0.16195 (12)0.0249 (6)
O40.6466 (4)0.0166 (5)0.1510 (4)0.137 (3)
O50.7914 (4)0.0059 (4)0.1660 (4)0.126 (3)
N10.66932 (17)0.23422 (18)0.27425 (13)0.0135 (5)
N20.52691 (17)0.44463 (16)0.29771 (12)0.0125 (5)
C10.70854 (19)0.17233 (19)0.24034 (14)0.0149 (6)
H10.68000.11780.23360.018*
C20.78932 (19)0.18805 (19)0.21558 (14)0.0145 (6)
H20.81630.14480.19140.017*
C30.5262 (2)0.41170 (19)0.24238 (14)0.0149 (6)
H30.52590.34990.23660.018*
C40.5259 (2)0.46676 (19)0.19448 (15)0.0150 (6)
H40.52490.44300.15570.018*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ho10.00537 (13)0.00537 (13)0.0038 (2)0.00033 (6)0.0000.000
Cl10.0132 (5)0.0132 (5)0.0058 (10)0.0000.0000.000
Cl20.0261 (4)0.0261 (4)0.0315 (8)0.0103 (5)0.0037 (3)0.0037 (3)
O10.0093 (9)0.0224 (11)0.0129 (11)0.0028 (8)0.0047 (8)0.0037 (8)
O20.0242 (11)0.0106 (9)0.0088 (12)0.0021 (8)0.0029 (8)0.0043 (7)
O30.0177 (12)0.0432 (16)0.0138 (14)0.0043 (9)0.0044 (10)0.0029 (10)
O40.066 (4)0.116 (5)0.228 (8)0.013 (3)0.098 (5)0.016 (5)
O50.078 (4)0.094 (4)0.205 (9)0.002 (3)0.059 (5)0.072 (5)
N10.0112 (11)0.0188 (11)0.0106 (15)0.0002 (9)0.0020 (9)0.0003 (10)
N20.0147 (11)0.0114 (10)0.0114 (14)0.0003 (9)0.0016 (9)0.0027 (9)
C10.0151 (13)0.0162 (13)0.0132 (16)0.0013 (10)0.0014 (10)0.0032 (11)
C20.0139 (13)0.0183 (13)0.0113 (16)0.0003 (10)0.0014 (10)0.0023 (11)
C30.0195 (14)0.0112 (12)0.0140 (17)0.0018 (10)0.0018 (12)0.0000 (10)
C40.0192 (13)0.0123 (12)0.0137 (16)0.0003 (11)0.0005 (11)0.0007 (10)
Geometric parameters (Å, º) top
Ho1—O1i2.325 (2)Cl2—O5vi1.381 (6)
Ho1—O1ii2.325 (2)O1—N11.305 (3)
Ho1—O12.325 (2)O2—N21.300 (3)
Ho1—O1iii2.325 (2)N1—C11.354 (4)
Ho1—O2i2.357 (2)N1—C2vii1.361 (4)
Ho1—O2ii2.357 (2)N2—C31.349 (4)
Ho1—O22.357 (2)N2—C4viii1.361 (4)
Ho1—O2iii2.357 (2)C1—C21.373 (4)
Cl1—O31.437 (3)C1—H10.9500
Cl1—O3iv1.437 (3)C2—N1vii1.361 (4)
Cl1—O3iii1.437 (3)C2—H20.9500
Cl1—O3v1.437 (3)C3—C41.371 (4)
Cl2—O4vi1.357 (4)C3—H30.9500
Cl2—O41.357 (4)C4—N2viii1.361 (4)
Cl2—O51.381 (6)C4—H40.9500
O1i—Ho1—O1ii78.19 (11)O3iv—Cl1—O3iii109.81 (11)
O1i—Ho1—O1147.80 (10)O3—Cl1—O3v109.81 (11)
O1ii—Ho1—O1111.01 (12)O3iv—Cl1—O3v108.8 (2)
O1i—Ho1—O1iii111.01 (12)O3iii—Cl1—O3v109.80 (11)
O1ii—Ho1—O1iii147.80 (10)O4vi—Cl2—O4109.0 (6)
O1—Ho1—O1iii78.19 (11)O4vi—Cl2—O5114.2 (4)
O1i—Ho1—O2i80.55 (8)O4—Cl2—O5109.6 (5)
O1ii—Ho1—O2i72.64 (7)O4vi—Cl2—O5vi109.6 (5)
O1—Ho1—O2i73.60 (7)O4—Cl2—O5vi114.2 (4)
O1iii—Ho1—O2i138.15 (7)O5—Cl2—O5vi100.2 (8)
O1i—Ho1—O2ii72.64 (7)N1—O1—Ho1142.32 (19)
O1ii—Ho1—O2ii80.55 (8)N2—O2—Ho1141.03 (18)
O1—Ho1—O2ii138.15 (7)O1—N1—C1119.0 (3)
O1iii—Ho1—O2ii73.60 (7)O1—N1—C2vii121.2 (3)
O2i—Ho1—O2ii145.32 (11)C1—N1—C2vii119.8 (3)
O1i—Ho1—O273.60 (7)O2—N2—C3121.9 (2)
O1ii—Ho1—O2138.15 (7)O2—N2—C4viii118.8 (3)
O1—Ho1—O280.55 (8)C3—N2—C4viii119.3 (3)
O1iii—Ho1—O272.64 (7)N1—C1—C2120.3 (3)
O2i—Ho1—O272.73 (11)N1—C1—H1119.8
O2ii—Ho1—O2118.32 (11)C2—C1—H1119.8
O1i—Ho1—O2iii138.15 (7)N1vii—C2—C1119.8 (3)
O1ii—Ho1—O2iii73.60 (7)N1vii—C2—H2120.1
O1—Ho1—O2iii72.64 (7)C1—C2—H2120.1
O1iii—Ho1—O2iii80.55 (8)N2—C3—C4120.4 (3)
O2i—Ho1—O2iii118.32 (11)N2—C3—H3119.8
O2ii—Ho1—O2iii72.73 (11)C4—C3—H3119.8
O2—Ho1—O2iii145.33 (11)N2viii—C4—C3120.3 (3)
O3—Cl1—O3iv109.80 (11)N2viii—C4—H4119.9
O3—Cl1—O3iii108.8 (2)C3—C4—H4119.9
Symmetry codes: (i) y+1/4, x1/4, z+3/4; (ii) y+3/4, x+3/4, z+3/4; (iii) x+1, y+1/2, z; (iv) y+3/4, x1/4, z+1/4; (v) y+1/4, x+3/4, z+1/4; (vi) y+3/4, x3/4, z+1/4; (vii) x+3/2, y+1/2, z+1/2; (viii) x, y+1, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O2vii0.952.523.285 (4)138
C2—H2···O50.952.403.161 (7)137
C3—H3···O10.952.603.323 (4)134
C3—H3···O30.952.463.230 (4)138
C4—H4···O3iv0.952.363.234 (4)153
Symmetry codes: (iv) y+3/4, x1/4, z+1/4; (vii) x+3/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Ho(C4H4N2O2)4](ClO4)3
Mr911.65
Crystal system, space groupTetragonal, I41/acd
Temperature (K)100
a, c (Å)15.2302 (4), 22.6334 (12)
V3)5250.0 (3)
Z8
Radiation typeMo Kα
µ (mm1)3.43
Crystal size (mm)0.37 × 0.32 × 0.17
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.292, 0.558
No. of measured, independent and
observed [I > 2σ(I)] reflections
10709, 1906, 1585
Rint0.025
(sin θ/λ)max1)0.714
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.103, 1.04
No. of reflections1906
No. of parameters110
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0554P)2 + 37.1849P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)3.23, 1.76

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O2i0.952.523.285 (4)138.0
C2—H2···O50.952.403.161 (7)137.3
C3—H3···O10.952.603.323 (4)133.6
C3—H3···O30.952.463.230 (4)138.0
C4—H4···O3ii0.952.363.234 (4)152.6
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) y+3/4, x1/4, z+1/4.
 

Acknowledgements

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.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2007). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBuchner, J. D., Quinn-Elmore, B. G., Beach, K. B. & Knaust, J. M. (2010). Acta Cryst. E66, m1110–m1111.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationQuinn-Elmore, B. G., Buchner, J. D., Beach, K. B. & Knaust, J. M. (2010a). Acta Cryst. E66, m1104–m1105.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationQuinn-Elmore, B. G., Buchner, J. D., Beach, K. B. & Knaust, J. M. (2010b). Acta Cryst. E66, m1106–m1107.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSun, H. L., Gao, S., Ma, B. Q., Chang, F. & Fu, W. F. (2004). Microporous Mesoporous Mater. 73 89–95.  Web of Science CSD CrossRef CAS Google Scholar

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