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

Quinn-Elmore, B.G.; Buchner, J.D.; Beach, K.B.; Knaust, J.M.

doi:10.1107/S1600536810031818

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 9| September 2010| Pages m1104-m1105

https://doi.org/10.1107/S1600536810031818

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

Benjamin G. Quinn-Elmore,^a James D. Buchner,^a Keith B. Beach ^a and Jacqueline M. Knaust ^a ^*

^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, {[Nd(C₄H₄N₂O₂)₄](ClO₄)₃}_n, is isostructural to that of other lanthanides. The Nd⁺³cation 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 ). For the isostructural Dy, Ho, Er coordination networks, see: Quinn-Elmore et al. (2010 ); Buchner et al. (2010a ,b ), respectively. For a lanthanum 4,4′-bipyridine N,N′-dioxide coordination network of similar topology, see: Long et al. (2001 ). For additional discussions on Ln³⁺ (Ln = lanthanide) coordination networks with aromatic N,N′-dioxide ligands, see: Cardoso et al. (2001 ); Hill et al. (2005 ). For background information on the applications of coordination networks, see: Roswell & Yaghi (2004 ); Rosi et al. (2003 ); Seo et al. (2000 ).

Experimental

Crystal data

[Nd(C₄H₄N₂O₂)₄](ClO₄)₃
M_r = 890.96
Tetragonal, I 4₁ /a c d
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 ) T_min = 0.593, T_max = 0.659
30711 measured reflections
2086 independent reflections
1842 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.106
S = 1.10
2086 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 2.27 e Å⁻³
Δρ_min = −1.95 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.95	2.55	3.326 (3)	139
C2—H2⋯O5	0.95	2.43	3.194 (7)	137
C3—H3⋯O1	0.95	2.59	3.331 (3)	135
C3—H3⋯O3	0.95	2.51	3.260 (3)	136
C4—H4⋯O3ⁱⁱ	0.95	2.41	3.289 (3)	154
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 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810031818/zl2298sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810031818/zl2298Isup2.hkl

checkCIF report

Comment top

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⁺³cation 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⁺³cation 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).

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 Dy, Ho, Er coordination networks, see: Quinn-Elmore et al. (2010); Buchner et al. (2010a,b), respectively. For a lanthanum 4,4'-bipyridine N,N'-dioxide coordination network of similar topology, see: Long et al. (2001). For additional discussions on Ln⁺³ coordination networks with aromatic N,N'-dioxide ligands, see: Cardoso et al. (2001); Hill et al. (2005). For background information on the applications of coordination networks, see: Roswell et al. (2004); Rosi et al. (2003); Seo et al. (2000).

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 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.

Structure description top

For the isostructural La, Ce, Pr, Sm, Eu, Gd, Tb and Y coordination networks, see: Sun et al. (2004). For the isostructural Dy, Ho, Er coordination networks, see: Quinn-Elmore et al. (2010); Buchner et al. (2010a,b), respectively. For a lanthanum 4,4'-bipyridine N,N'-dioxide coordination network of similar topology, see: Long et al. (2001). For additional discussions on Ln⁺³ coordination networks with aromatic N,N'-dioxide ligands, see: Cardoso et al. (2001); Hill et al. (2005). For background information on the applications of coordination networks, see: Roswell et al. (2004); Rosi et al. (2003); Seo et al. (2000).

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

	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) -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.
	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, -z+1/4;; (vi) y+3/4, x-3/4, -z+1/4; (vii) -x+3/2, -y+1/2, -z+1/2 Color scheme: Nd: green, C: grey, H: white, N:blue, O: red, Cl: yellow.
	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, H: white, N:blue, O: red, anions containing Cl1: orange, and anions containing Cl2: aqua.
	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 clarity. Color scheme: Nd: green, C: grey, H: white, N:blue, O: red, anions containing Cl1: orange, and anions containing Cl2: aqua.

Poly[[tetrakis(µ₂-pyrazine N,N'-dioxide-κ²O:O')neodymium(III)] tris(perchlorate)] top

Crystal data top

[Nd(C₄H₄N₂O₂)₄](ClO₄)₃	D_x = 2.177 Mg m⁻³
M_r = 890.96	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/acd	Cell parameters from 15053 reflections
Hall symbol: -I 4bd 2c	θ = 2.6–30.5°
a = 15.3804 (4) Å	µ = 2.32 mm⁻¹
c = 22.9843 (12) Å	T = 100 K
V = 5437.1 (3) Å³	Block, rose
Z = 8	0.23 × 0.23 × 0.18 mm
F(000) = 3512

Data collection top

Bruker SMART APEX CCD diffractometer	2086 independent reflections
Radiation source: fine-focus sealed tube	1842 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 30.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −21→21
T_min = 0.593, T_max = 0.659	k = −21→21
30711 measured reflections	l = −32→32

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0535P)² + 38.356P] where P = (F_o² + 2F_c²)/3
2086 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 2.27 e Å⁻³
0 restraints	Δρ_min = −1.95 e Å⁻³

Crystal data top

[Nd(C₄H₄N₂O₂)₄](ClO₄)₃	Z = 8
M_r = 890.96	Mo Kα radiation
Tetragonal, I4₁/acd	µ = 2.32 mm⁻¹
a = 15.3804 (4) Å	T = 100 K
c = 22.9843 (12) Å	0.23 × 0.23 × 0.18 mm
V = 5437.1 (3) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	2086 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1842 reflections with I > 2σ(I)
T_min = 0.593, T_max = 0.659	R_int = 0.024
30711 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0535P)² + 38.356P] where P = (F_o² + 2F_c²)/3
2086 reflections	Δρ_max = 2.27 e Å⁻³
110 parameters	Δρ_min = −1.95 e Å⁻³

Special details top

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) top

	x	y	z	U_iso*/U_eq
Nd1	0.5000	0.2500	0.3750	0.00589 (11)
Cl1	0.5000	0.2500	0.1250	0.0119 (3)
Cl2	0.72544 (6)	−0.02456 (6)	0.1250	0.0319 (3)
O1	0.59191 (12)	0.21965 (14)	0.29303 (8)	0.0171 (4)
O2	0.53338 (14)	0.39686 (12)	0.34324 (8)	0.0168 (4)
O3	0.57573 (16)	0.24613 (16)	0.16135 (10)	0.0277 (5)
O4	0.6477 (5)	−0.0172 (6)	0.1497 (5)	0.191 (4)
O5	0.7895 (5)	−0.0023 (6)	0.1623 (5)	0.180 (5)
N1	0.66963 (15)	0.23449 (15)	0.27293 (10)	0.0141 (4)
N2	0.52833 (15)	0.44642 (14)	0.29745 (9)	0.0129 (4)
C1	0.70832 (17)	0.17377 (17)	0.23897 (11)	0.0154 (5)
H1	0.6797	0.1202	0.2315	0.018*
C2	0.78886 (16)	0.18959 (17)	0.21540 (11)	0.0152 (5)
H2	0.8155	0.1475	0.1910	0.018*
C3	0.52715 (18)	0.41238 (16)	0.24314 (11)	0.0148 (5)
H3	0.5264	0.3511	0.2380	0.018*
C4	0.52702 (18)	0.46617 (16)	0.19547 (11)	0.0147 (5)
H4	0.5260	0.4420	0.1574	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Nd1	0.00627 (13)	0.00627 (13)	0.00511 (16)	−0.00034 (7)	0.000	0.000
Cl1	0.0146 (4)	0.0146 (4)	0.0065 (6)	0.000	0.000	0.000
Cl2	0.0304 (4)	0.0304 (4)	0.0349 (6)	−0.0118 (5)	0.0035 (3)	−0.0035 (3)
O1	0.0112 (8)	0.0256 (10)	0.0146 (8)	−0.0032 (7)	0.0052 (7)	−0.0036 (7)
O2	0.0283 (10)	0.0114 (8)	0.0107 (8)	−0.0031 (7)	−0.0038 (7)	0.0049 (6)
O3	0.0195 (11)	0.0479 (15)	0.0156 (10)	0.0057 (9)	−0.0054 (8)	−0.0033 (8)
O4	0.085 (5)	0.154 (7)	0.335 (12)	−0.015 (4)	0.138 (7)	−0.028 (7)
O5	0.091 (5)	0.130 (6)	0.317 (15)	0.007 (4)	−0.066 (7)	−0.135 (8)
N1	0.0116 (10)	0.0198 (10)	0.0110 (9)	−0.0011 (8)	0.0022 (8)	−0.0013 (8)
N2	0.0160 (10)	0.0117 (9)	0.0111 (9)	0.0000 (8)	−0.0017 (7)	0.0028 (7)
C1	0.0149 (11)	0.0172 (11)	0.0140 (11)	−0.0008 (9)	0.0023 (8)	−0.0029 (9)
C2	0.0135 (11)	0.0188 (12)	0.0132 (10)	0.0000 (9)	0.0013 (8)	−0.0027 (9)
C3	0.0206 (12)	0.0104 (10)	0.0134 (11)	−0.0018 (9)	−0.0019 (9)	0.0006 (8)
C4	0.0209 (12)	0.0114 (10)	0.0118 (10)	−0.0002 (9)	−0.0002 (9)	0.0006 (8)

Geometric parameters (Å, º) top

Nd1—O1ⁱ	2.4012 (18)	Cl2—O5^vi	1.350 (7)
Nd1—O1ⁱⁱ	2.4012 (18)	O1—N1	1.302 (3)
Nd1—O1	2.4012 (18)	O2—N2	1.302 (3)
Nd1—O1ⁱⁱⁱ	2.4012 (18)	N1—C1	1.355 (3)
Nd1—O2ⁱ	2.4286 (18)	N1—C2^vii	1.358 (3)
Nd1—O2ⁱⁱ	2.4286 (18)	N2—C3	1.354 (3)
Nd1—O2	2.4286 (18)	N2—C4^viii	1.354 (3)
Nd1—O2ⁱⁱⁱ	2.4287 (18)	C1—C2	1.374 (3)
Cl1—O3	1.435 (2)	C1—H1	0.9500
Cl1—O3^iv	1.435 (2)	C2—N1^vii	1.358 (3)
Cl1—O3ⁱⁱⁱ	1.435 (2)	C2—H2	0.9500
Cl1—O3^v	1.435 (2)	C3—C4	1.373 (3)
Cl2—O4^vi	1.328 (5)	C3—H3	0.9500
Cl2—O4	1.328 (5)	C4—N2^viii	1.354 (3)
Cl2—O5	1.350 (7)	C4—H4	0.9500

O1ⁱ—Nd1—O1ⁱⁱ	76.62 (10)	O3^iv—Cl1—O3ⁱⁱⁱ	109.83 (10)
O1ⁱ—Nd1—O1	147.62 (10)	O3—Cl1—O3^v	109.83 (10)
O1ⁱⁱ—Nd1—O1	112.75 (10)	O3^iv—Cl1—O3^v	108.76 (19)
O1ⁱ—Nd1—O1ⁱⁱⁱ	112.75 (10)	O3ⁱⁱⁱ—Cl1—O3^v	109.83 (10)
O1ⁱⁱ—Nd1—O1ⁱⁱⁱ	147.62 (10)	O4^vi—Cl2—O4	109.6 (8)
O1—Nd1—O1ⁱⁱⁱ	76.63 (10)	O4^vi—Cl2—O5	115.9 (6)
O1ⁱ—Nd1—O2ⁱ	79.66 (7)	O4—Cl2—O5	111.4 (7)
O1ⁱⁱ—Nd1—O2ⁱ	73.01 (7)	O4^vi—Cl2—O5^vi	111.4 (7)
O1—Nd1—O2ⁱ	74.30 (6)	O4—Cl2—O5^vi	115.9 (6)
O1ⁱⁱⁱ—Nd1—O2ⁱ	137.92 (6)	O5—Cl2—O5^vi	91.8 (11)
O1ⁱ—Nd1—O2ⁱⁱ	73.01 (7)	N1—O1—Nd1	141.71 (16)
O1ⁱⁱ—Nd1—O2ⁱⁱ	79.66 (7)	N2—O2—Nd1	140.80 (15)
O1—Nd1—O2ⁱⁱ	137.92 (6)	O1—N1—C1	119.1 (2)
O1ⁱⁱⁱ—Nd1—O2ⁱⁱ	74.30 (6)	O1—N1—C2^vii	120.8 (2)
O2ⁱ—Nd1—O2ⁱⁱ	145.02 (9)	C1—N1—C2^vii	120.0 (2)
O1ⁱ—Nd1—O2	74.30 (6)	O2—N2—C3	121.3 (2)
O1ⁱⁱ—Nd1—O2	137.92 (6)	O2—N2—C4^viii	119.0 (2)
O1—Nd1—O2	79.66 (7)	C3—N2—C4^viii	119.7 (2)
O1ⁱⁱⁱ—Nd1—O2	73.01 (7)	N1—C1—C2	120.1 (2)
O2ⁱ—Nd1—O2	72.37 (10)	N1—C1—H1	120.0
O2ⁱⁱ—Nd1—O2	118.92 (10)	C2—C1—H1	120.0
O1ⁱ—Nd1—O2ⁱⁱⁱ	137.92 (6)	N1^vii—C2—C1	119.9 (2)
O1ⁱⁱ—Nd1—O2ⁱⁱⁱ	74.30 (6)	N1^vii—C2—H2	120.1
O1—Nd1—O2ⁱⁱⁱ	73.01 (7)	C1—C2—H2	120.1
O1ⁱⁱⁱ—Nd1—O2ⁱⁱⁱ	79.66 (7)	N2—C3—C4	120.2 (2)
O2ⁱ—Nd1—O2ⁱⁱⁱ	118.92 (10)	N2—C3—H3	119.9
O2ⁱⁱ—Nd1—O2ⁱⁱⁱ	72.37 (10)	C4—C3—H3	119.9
O2—Nd1—O2ⁱⁱⁱ	145.02 (9)	N2^viii—C4—C3	120.1 (2)
O3—Cl1—O3^iv	109.83 (10)	N2^viii—C4—H4	119.9
O3—Cl1—O3ⁱⁱⁱ	108.76 (19)	C3—C4—H4	119.9

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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2^vii	0.95	2.55	3.326 (3)	139
C2—H2···O5	0.95	2.43	3.194 (7)	137
C3—H3···O1	0.95	2.59	3.331 (3)	135
C3—H3···O3	0.95	2.51	3.260 (3)	136
C4—H4···O3^iv	0.95	2.41	3.289 (3)	154

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

Experimental details

Crystal data
Chemical formula	[Nd(C₄H₄N₂O₂)₄](ClO₄)₃
M_r	890.96
Crystal system, space group	Tetragonal, I4₁/acd
Temperature (K)	100
a, c (Å)	15.3804 (4), 22.9843 (12)
V (Å³)	5437.1 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.32
Crystal size (mm)	0.23 × 0.23 × 0.18

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.593, 0.659
No. of measured, independent and observed [I > 2σ(I)] reflections	30711, 2086, 1842
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.106, 1.10
No. of reflections	2086
No. of parameters	110
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0535P)² + 38.356P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	2.27, −1.95

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···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.95	2.55	3.326 (3)	139.3
C2—H2···O5	0.95	2.43	3.194 (7)	137.4
C3—H3···O1	0.95	2.59	3.331 (3)	135.2
C3—H3···O3	0.95	2.51	3.260 (3)	136.3
C4—H4···O3ⁱⁱ	0.95	2.41	3.289 (3)	153.6

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

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