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The title compound, [Nd2(C5H6O4)2(C8H4O4)(H2O)4]·17H2O, obtained via hydro­thermal reaction of Nd2O3 with glutaric acid and terephthalic acid, assembles as a three-dimensional open framework with ten-coordinate Nd–O polyhedra. The asymmetric part of the unit cell contains half a glutarate anion, a quarter of a terephthalate dianion, half an NdIII cation, one coordinated water mol­ecule and 4.25 solvent water mol­ecules. Each [NdO10] coordination polyhedron is comprised of six O atoms originating from four glutarate anions, two others from a terephthalate carboxyl­ate group, which coordinates in a bidentate fashion, and two from water mol­ecules. The Nd—O distances range from 2.4184 (18) to 2.7463 (18) Å. The coordination polyhedra are inter­connected by the glutarate anions, extending as a two-dimensional layer throughout the bc plane. Individual two-dimensional layers are inter­linked via terephthalate anions along the a axis. This arrangement results in rectangular-shaped cavities with inter­stices of approximately 3.5 × 6 × 6.5 Å (approximately 140 Å3), which are occupied by water mol­ecules. The NdIII cations, terephthalate anions, glutarate anions and one of the inter­stitial water mol­ecules are located on special crystallographic positions. The Nd–terephthalate–Nd units are located across twofold rotation axes parallel to [100], with the NdIII cations located directly on these axes. In addition, the terephthalate anion is bis­ected by a crystallographic mirror plane perpendicular to that axis, thus creating an inversion centre in the middle of the aromatic ring. The glutarate ligand is bis­ected by a crystallographic mirror plane perpendicular to (001). One of the solvent water mol­ecules lies on a site of 2/m symmetry, and the symmetry-imposed disorder of its H atoms extends to the H atoms of the other four solvent water mol­ecules, which are disordered over two equally occupied and mutually exclusive sets of positions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110044872/gd3367sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110044872/gd3367Isup2.hkl
Contains datablock I

CCDC reference: 809998

Comment top

The synthesis of metal–organic frameworks (MOFs) has received increased consideration in recent years (Bradshaw et al., 2005; Kawano et al., 2007) because of their applications in diverse areas, e.g. gas storage (Eddaoudi et al., 2002; Férey et al., 2005; Liu et al., 2007), drug delivery (Horcajada et al., 2008, 2006; Vallet-Regi et al., 2007) and electronics (Férey et al., 2007), and also for the possible advancement of magnetic (Dietzel et al., 2005; Kahn & Martinez, 1998), sensing (Chen et al., 2008; Wong et al., 2006) and catalytic (Gándara et al., 2008; Müller et al., 2008) systems. Terephthalic acid (TP) has become a very popular spacer ligand often used in MOFs, since it confers a high level of rigidity on the resulting compounds. In a recent paper, we compared a number of lanthanide terephthalates with some of their already known counterparts, pointing out that the carboxylate groups experience an increased out-of-plane torsion for compounds of lanthanides with smaller ionic radii. For instance, [Nd2(TP)3(H2O)4] exhibits maximum torsion angles between 25.1 and 25.5° (Zehnder et al., 2010). The Tb analogue experiences larger torsion angles of up to 28° (Reinecke et al., 1999), while the Er counterpart, with the smallest ion radius, shows the highest degree of torsion at 29.7° (Pan et al., 2001; Zehnder et al., 2010).

The combination of aliphatic dicarboxylates with more rigid building blocks, such as aromatic systems with two or more carboxylate groups, has led to the creation of stable framework structures with larger channels or solvent-filled voids (Borkowski & Cahill, 2004; He et al., 2006; Serpaggi & Férey, 1998; Vaidhyanathan et al., 2001) and to the development of unique network topologies (Li et al., 2009; Wang et al., 2009). The title compound, (I), represents another excellent example in this regard. To our knowledge, the single-crystal X-ray structural characterization of a lanthanide bis-glutarate terephthalate is unprecedented. Here, we describe the synthesis and characterization of (I), a lanthanide mixed-ligand complex incorporating two different organic components.

Compound (I) crystallizes in the orthorhombic crystal system in space group Cmcm and it assembles as a three-dimensional open framework. In this framework, the NdIII cations, terephthalate anions, glutarate anions and one of the solvent water molecules are all located on special crystallographic positions. The Nd–terephthalate–Nd units are located on crystallographic twofold axes parallel to [100], with the NdIII cations located directly on these axes. In addition, the terephthalate anion is bisected by a crystallographic mirror plane perpendicular to that axis, thus creating an inversion centre in the middle of the aromatic ring. The glutarate ligand is bisected by a crystallographic mirror plane perpendicular to (001).

Each central NdIII cation is coordinated by ten O atoms, forming [NdO10] coordination polyhedra with the geometric shape of a bi-capped square anti-prism. Individual polyhedra are stacked on top of each other. They share edges via two O atoms (O3) and form infinite chains running along the b axis in a staggered formation. The coordinating O atoms originate from two water molecules (O4), four glutarate carboxylate groups (six O atoms, two O2 and four O3) and one terephthalate carboxylate group (O1). Each terephthalate anion connects two [NdO10] polyhedra along the a axis in a bidentate fashion. Along the b axis, the [NdO10] polyhedra form AB layers as they alternate their orientation by 180°. As a result, terephthalate anions alternate with coordinated water molecules along the b direction (Fig. 2). Each glutarate carboxylate group connects two [NdO10] coordination polyhedra, with one O atom (O2) coordinating in µ1 fashion to a central NdIII cation. The second O atom of each glutarate carboxylate group (O3) connects in µ2 fashion to two adjacent NdIII central cations. All corresponding Nd1—O bond distances are summarized in Table 1. The glutarate anions infinitely link the NdIII cations along the c axis. Simultaneously, they connect adjacent NdIII metal centres along the b axis, creating highly interconnected two-dimensional layers of NdIII cations and glutarate anions (Fig. 3). These layers are tied together by the terephthalate anions along the a axis.

The combination of two glutarate anions and one terephthalate anion per pair of NdIII cations results in the formation of larger rectangular channels that stretch infinitely along the c axis. These channels have an approximate size of 3.5 Å × 6 Å. This arrangement of terephthalate and glutarate anions also results in the formation of nearly square-shaped infinite channels stretching along the b axis, with side lengths of approximately 6.5 × 6 Å. These channels bisect the other channels in a perpendicular fashion, creating rectangular interstices of approximately 140 Å3. These interstices are occupied by water molecules, which are connected to the framework backbone and each other through O—H···O hydrogen-bonding interactions (Table 2). Fig. 4 shows how the two coordinated water molecules of one [NdO10] polyhedron connect via O—H···O hydrogen bonds (1.93 Å) to the carboxylate O atoms of the terephthalate anions that belong to the two adjacent coordination polyhedra. Additionally, these water molecules connect via O—H···O hydrogen bonds (1.91 Å) to the interstitial water molecules within the channels. The hydrogen-bonding interactions between the interstitial water molecules themselves are disordered, due to one of the water O atoms (O6) being located at the centre of the unit cell at (x, y, z) = (1/2, 1/2, 1/2) on a special position that does not agree with the point symmetry of a water molecule. Two sets of half-occupied water H atoms were thus refined (see Refinement section for details). These water molecules connect via hydrogen bonds with H···O bond distances in the range 1.89-1.93 Å (Table 2).

The terephthalate anions hardly experience any tension [torsion?], as their carboxylate groups are aligned in-plane with the conjugated π system, and they show only minor out-of-plane torsions not exceeding 3.4°. This is supported by the fact that most of the bond angles involving the sp3 C atoms in the glutarate anions are very close to the tetrahedral angle (108.7–109.1°) and only the C—C—C angles are slightly stretched, to 112.7 and 114.1°. The resulting solvent-accessible areas are significantly larger than in the regular lanthanide terephthalates. Therefore, we expect that the interstices in related structures can be tuned by replacing the glutaric acid units with longer or shorter aliphatic dicarboxylates, such as adipates, pimelates, suberates etc.

Experimental top

Neodymium oxide (Acros Organics, 99.90%) (0.25 g, 0.75 mmol), terephthalic acid (Aldrich) (0.25 g, 1.5 mmol) and glutaric acid (Eastman) (0.10 g, 0.75 mmol) were suspended in ~15 ml of deionized water and placed in a Teflon liner inside a Parr acid-digestion vessel (model 4744; 45 ml capacity). The vessel was sealed and placed in a conventional laboratory oven at 443 K for 5 d. At the end of the heating period, the vessel was removed from the hot oven and allowed to cool to room temperature on the laboratory bench before opening. A solid material was obtained, which was submerged in the mother liquor. The solid product was pale purple in colour. It was rinsed four times with deionized water in order to remove any soluble by-products. A large quantity of the product had formed crystals in the form of large rectangular blocks. Small amounts of the product were stored in a scintillation vial with small quantities of deionized water until a single crystal was chosen for X-ray structural analysis (yield 0.23 g, 0.21 mmol; 56%).

Spectroscopic analysis: FT–IR (KBr, ν, 4000–500 cm-1): 3454 (br), 3230 (sh) 3058 (w), 1608 (sh), 1596, (sh), 1549 (sh), 1540 (vs), 1516 (sh), 1504 (vs), 1418 (vs), 1403 (vs), 1310 (s), 1245 (sh), 1155 (m), 1101 (w), 1064 (w), 1050 (w), 1020 (m), 988 (w), 968 (w), 883 (m), 827 (m), 761 (sh), 750 (s), 576 (sh), 554 (sh), 528, (m), 509 (m). The FT–IR spectrum exhibits the strong bands one expects to see for the symmetric and asymmetric vibrations of terephthalate and glutarate (1700–1470 and 1460–1220 cm-1), as well as those of the interstitial water molecules (3300–3600 cm-1). The vibrations of the carboxylate groups can be observed at around 1600 cm-1. They are shifted to somewhat lower frequencies, which can be attributed to the coordination of the carboxylate groups to the NdIII atoms.

Analysis, calculated for (C18H58O33Nd2)Nd2(TP)(Glut)2(H2O)4.17H2O: C 19.82, H 5.36, N 0.00%; found: C 31.07, H 2.46, N 0.05%. Based on these data, we assume that we did not obtain a pure phase of this compound. The results would be close to the water-free compound, (C18H16O12Nd2)Nd2(TP)(Glut)2 (C 30.33, H 2.26%). This is rather unlikely, however, since we did not use high drying temperatures (<353 K), and the IR spectrum exhibits a broad band between 3400 and 3500 cm-1, which suggests the presence of water.

Refinement top

The H atoms of the interstitial water molecules located in the channels of the structure are disordered, due to hydrogen bonds across elements of symmetry that create mutually exclusive H-atom positions. The disorder orginates with the water molecule of atom O6 located at the centre of the unit cell at (x, y, z) = (1/2, 1/2, 1/2) on an inversion centre at the intersection of a mirror and a glide plane, and a two-fold rotation and a screw axis, a site symmetry that does not agree with the point symmetry of a water molecule. Atom O6 was thus refined as being bonded to one crystallographically independent H atom (located in a difference density Fourier map). Application of the site symmetry creates four equivalent H atoms, which were refined as half-occupied to form two differently oriented water molecules located at the site of O6. The disorder of the H atoms around O6 induces disorder of the H atoms bonded to atoms O5, O7, O8 and O9, the other interstitial water molecules. H atoms were tentatively located in difference density Fourier maps. In the initial refinement cycles, H-atom positions were restrained using O—H and H···O distance restraints based on hydrogen-bonding considerations, taking the disorder into account. In the final refinement cycles, water H atoms were set to ride on their carrier O atoms, with Uiso(H) = 1.5Ueq(O).

Carbon-bound H atoms were placed in calculated positions, with C—H = 0.95 Å for aromatic H atoms and 0.99 Å for methylene H atoms, and with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 (Bruker, 2009); data reduction: APEX2 (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008), CrystalMaker for Mac (Palmer, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the ??% probability level [Please complete]. Only the positions of one of the two alternative sets of disordered water H atoms are shown for clarity. Atoms Nd1 and O6 occupy sites of 2 and 2/m symmetry, respectively. [Symmetry codes: (i) x, -y + 1, -z + 1; (ii) -x, y, z; (iii) x, y, -z + 1/2; (iv) -x + 1/2, -y + 1/2, -z + 1; (v) -x + 1/2, y + 1/2, z.]
[Figure 2] Fig. 2. The packing of the [NdO10] polyhedra in (I), viewed along the b axis, showing interstitial water molecules. Light-grey spheres denote carboxylate O atoms from terephthalate anions, medium-grey spheres carboxylate O atoms from glutarate anions, dark-grey spheres water molecules, grey polyhedra [NdO10] units and small black spheres C atoms.
[Figure 3] Fig. 3. The arrangement of the glutarate anions in (I). Light-grey spheres denote carboxylate O atoms (O1) from terephthalate anions, medium-grey spheres carboxylate O atoms from glutarate anions (O2, O3), dark-grey spheres O atoms from water molecules (O4), grey polyhedra [NdO10] units, small white spheres H atoms and small black spheres C atoms.
[Figure 4] Fig. 4. O—H···O hydrogen-bonding interactions (black-and-white dashed lines) between coordinated and interstitial water molecules in (I). Light-grey spheres denote carboxylate O atoms (O1) from terephthalate anions, medium-grey spheres carboxylate O atoms from glutarate anions (O2, O3), dark-grey spheres O atoms from water molecules (O4), grey polyhedra [NdO10] units, small white spheres H atoms and small black spheres C atoms.
Poly[[tetraaquadi-µ4-glutarato-µ2-terephthalato-dineodymium(III)] heptadecahydrate] top
Crystal data top
[Nd2(C5H6O4)2(C8H4O4)(H2O)4]·17H2OF(000) = 2200
Mr = 1091.12Dx = 1.775 Mg m3
Orthorhombic, CmcmMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2c 2Cell parameters from 9970 reflections
a = 24.0265 (16) Åθ = 2.5–31.1°
b = 8.7253 (6) ŵ = 2.62 mm1
c = 19.4746 (13) ÅT = 100 K
V = 4082.6 (5) Å3Plate, pink
Z = 40.31 × 0.29 × 0.10 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3403 independent reflections
Radiation source: fine-focus sealed tube2941 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ω scansθmax = 31.5°, θmin = 1.7°
Absorption correction: multi-scan
(APEX2; Bruker, 2009)
h = 3434
Tmin = 0.622, Tmax = 0.746k = 1212
36277 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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0401P)2 + 34.0861P]
where P = (Fo2 + 2Fc2)/3
3403 reflections(Δ/σ)max < 0.001
125 parametersΔρmax = 2.45 e Å3
0 restraintsΔρmin = 0.84 e Å3
Crystal data top
[Nd2(C5H6O4)2(C8H4O4)(H2O)4]·17H2OV = 4082.6 (5) Å3
Mr = 1091.12Z = 4
Orthorhombic, CmcmMo Kα radiation
a = 24.0265 (16) ŵ = 2.62 mm1
b = 8.7253 (6) ÅT = 100 K
c = 19.4746 (13) Å0.31 × 0.29 × 0.10 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3403 independent reflections
Absorption correction: multi-scan
(APEX2; Bruker, 2009)
2941 reflections with I > 2σ(I)
Tmin = 0.622, Tmax = 0.746Rint = 0.026
36277 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0401P)2 + 34.0861P]
where P = (Fo2 + 2Fc2)/3
3403 reflectionsΔρmax = 2.45 e Å3
125 parametersΔρmin = 0.84 e Å3
Special details top

Experimental. For the IR and elemental analysis a small sample of the product was dried at temperatures not exceeding 80°C. The dry sample was homogenized using a mortar and pestle and then characterized via FT–IR spectroscopy and elemental analysis. The IR spectrum was collected on a Perkin–Elmer Spectrum 100 FT–IR Spectrometer using KBr pellets. Spectral resolution was 4 cm-1, and the data set included 64 scans.

We used the following abbreviations to describe the observed vibration modes: very strong (vs), strong (s), medium (m), weak (w), shoulder (sh), and broad (br).

Elemental analysis was performed with an Exeter Analytical CE7 440 CHN/O/S Analyzer

Refinement. Water H atoms are disordered due to hydrogen bonds across of inversion centres that create mutually exclusive H atom positions. Water H atoms were positioned based on hydrogen bonding interactions taking the disorder into account and were in the initial refinement cycles restrained by the hydrogen bonding considerations. Due to the presence of large electron density in the s, see below, water H atoms were in the final cycles set to ride on their carrier oxygen atoms. Four significant residual electron densities (the four largest residual densities of the structure) are found within the water filled voids. They seem to be not associated with the water molecules. Their positions and densities are: Q1 1 0.500000 0.546900 0.363200 10.500000 0.050000 2.45 Q2 1 0.500000 - 0.147200 0.320900 10.500000 0.050000 2.33 Q3 1 0.398500 0.415300 0.323800 11.000000 0.050000 2.31 Q4 1 0.401000 0.006500 0.321400 11.000000 0.050000 1.99

Attempts to refine them as disordered water molecules did not result in any meaningful structural model. They might be associated with small amounts of sodium cations (NaCl was used in the synthesis). When including the peaks as partially occupied sodium Q1 did refine to be 10% occupied with the others even less and the model was thus left unchanged.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.12042 (15)0.50000.50000.0088 (6)
C20.05825 (15)0.50000.50000.0096 (6)
C30.02879 (11)0.6259 (3)0.47534 (15)0.0162 (5)
H30.04840.71260.45840.019*
C40.21562 (10)0.2921 (3)0.38026 (12)0.0092 (4)
C50.20634 (12)0.2034 (3)0.31492 (12)0.0136 (5)
H5E0.16700.17020.31320.016*
H5D0.22980.11000.31600.016*
C60.21956 (17)0.2928 (4)0.25000.0144 (7)
H6C0.19790.38930.25000.017*
H6B0.25950.32020.25000.017*
Nd10.241932 (7)0.50000.50000.00599 (7)
O10.14651 (7)0.6184 (2)0.48046 (10)0.0117 (3)
O20.20864 (8)0.4355 (2)0.38114 (9)0.0119 (3)
O30.23046 (8)0.2230 (2)0.43457 (9)0.0104 (3)
O40.32697 (8)0.4102 (2)0.43621 (10)0.0150 (4)
H4A0.35440.46470.42540.022*
H4B0.33950.32350.44680.022*
O50.41973 (12)0.5811 (4)0.40505 (18)0.0450 (7)
H5A0.42420.66440.38420.068*
H5B0.44440.55910.43390.068*0.50
H5C0.43340.50490.38480.068*0.50
O60.50000.50000.50000.0308 (12)
H6A0.48310.51820.46310.046*0.50
O70.44265 (12)0.3405 (4)0.32086 (16)0.0421 (7)
H7A0.41630.27770.32460.063*0.50
H7B0.42940.41550.34230.063*0.50
H7C0.47720.32630.32300.063*0.50
H7D0.44060.34980.27800.063*0.50
O80.37827 (12)0.0869 (3)0.32019 (12)0.0363 (6)
H8A0.39440.17030.32850.054*0.50
H8B0.35550.03440.34290.054*
H8C0.37600.08410.27720.054*0.50
O90.44279 (12)0.8299 (3)0.32306 (15)0.0380 (6)
H9A0.42670.91390.33000.057*
H9B0.47740.84230.32510.057*0.50
H9C0.44200.82680.27990.057*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0077 (14)0.0090 (14)0.0097 (14)0.0000.0000.0019 (10)
C20.0078 (14)0.0099 (15)0.0109 (15)0.0000.0000.0014 (10)
C30.0122 (12)0.0126 (11)0.0239 (13)0.0004 (9)0.0004 (10)0.0047 (10)
C40.0109 (9)0.0097 (10)0.0069 (9)0.0006 (8)0.0006 (8)0.0003 (8)
C50.0255 (13)0.0094 (10)0.0060 (9)0.0010 (9)0.0011 (9)0.0007 (8)
C60.0241 (18)0.0121 (15)0.0069 (14)0.0035 (13)0.0000.000
Nd10.00657 (10)0.00625 (9)0.00515 (9)0.0000.0000.00042 (5)
O10.0094 (8)0.0097 (8)0.0159 (8)0.0011 (6)0.0001 (7)0.0012 (7)
O20.0170 (8)0.0093 (8)0.0095 (7)0.0009 (6)0.0023 (7)0.0003 (6)
O30.0126 (7)0.0110 (7)0.0077 (8)0.0005 (7)0.0016 (6)0.0013 (6)
O40.0140 (8)0.0108 (8)0.0200 (9)0.0009 (7)0.0052 (7)0.0024 (7)
O50.0308 (13)0.0393 (15)0.065 (2)0.0050 (12)0.0027 (14)0.0174 (15)
O60.046 (3)0.021 (2)0.026 (3)0.0000.0000.0039 (17)
O70.0356 (15)0.0454 (16)0.0452 (17)0.0069 (13)0.0005 (13)0.0047 (14)
O80.0393 (14)0.0489 (16)0.0206 (11)0.0213 (13)0.0084 (10)0.0013 (11)
O90.0380 (15)0.0348 (14)0.0413 (15)0.0003 (12)0.0042 (12)0.0003 (12)
Geometric parameters (Å, º) top
C1—O11.267 (2)Nd1—O4i2.5164 (19)
C1—O1i1.267 (2)Nd1—O1i2.5434 (18)
C1—C21.494 (5)Nd1—O12.5434 (18)
C2—C3i1.392 (3)Nd1—O32.7463 (18)
C2—C31.392 (3)Nd1—O3i2.7463 (18)
C3—C3ii1.384 (5)O4—H4A0.8400
C3—H30.9500O4—H4B0.8400
C4—O21.263 (3)O5—H5A0.8402
C4—O31.269 (3)O5—H5B0.8401
C4—C51.506 (3)O5—H5C0.8401
C5—C61.519 (3)O6—H6A0.8400
C5—H5E0.9900O7—H7A0.8400
C5—H5D0.9900O7—H7B0.8403
C6—C5iii1.519 (3)O7—H7C0.8401
C6—H6C0.9900O7—H7D0.8401
C6—H6B0.9900O8—H8A0.8400
Nd1—O3iv2.4184 (18)O8—H8B0.8400
Nd1—O3v2.4184 (18)O8—H8C0.8400
Nd1—O22.5130 (18)O9—H9A0.8401
Nd1—O2i2.5130 (18)O9—H9B0.8403
Nd1—O42.5164 (19)O9—H9C0.8404
O1—C1—O1i120.7 (3)O4i—Nd1—O1i141.68 (6)
O1—C1—C2119.65 (16)O3iv—Nd1—O1130.76 (6)
O1i—C1—C2119.65 (16)O3v—Nd1—O180.89 (6)
C3i—C2—C3118.9 (3)O2—Nd1—O170.50 (6)
C3i—C2—C1120.56 (17)O2i—Nd1—O176.11 (6)
C3—C2—C1120.55 (17)O4—Nd1—O1141.68 (6)
C3ii—C3—C2120.55 (17)O4i—Nd1—O1132.79 (6)
C3ii—C3—H3119.7O1i—Nd1—O151.30 (8)
C2—C3—H3119.7O3iv—Nd1—O364.15 (7)
O2—C4—O3119.8 (2)O3v—Nd1—O3119.42 (7)
O2—C4—C5120.1 (2)O2—Nd1—O348.97 (5)
O3—C4—C5120.1 (2)O2i—Nd1—O3126.34 (6)
C4—C5—C6114.1 (2)O4—Nd1—O365.06 (6)
C4—C5—H5E108.7O4i—Nd1—O3125.78 (6)
C6—C5—H5E108.7O1i—Nd1—O367.75 (6)
C4—C5—H5D108.7O1—Nd1—O3101.40 (6)
C6—C5—H5D108.7O3iv—Nd1—O3i119.41 (7)
H5E—C5—H5D107.6O3v—Nd1—O3i64.15 (7)
C5iii—C6—C5112.6 (3)O2—Nd1—O3i126.34 (6)
C5iii—C6—H6C109.1O4—Nd1—O3i125.78 (6)
C5—C6—H6C109.1O4i—Nd1—O3i65.06 (6)
C5iii—C6—H6B109.1O1i—Nd1—O3i101.40 (6)
C5—C6—H6B109.1O1—Nd1—O3i67.75 (6)
H6C—C6—H6B107.8O3—Nd1—O3i168.48 (8)
O3iv—Nd1—O3v148.16 (9)Nd1iv—O3—Nd1115.85 (7)
O3iv—Nd1—O2113.11 (6)Nd1—O4—H4A125.7
O3v—Nd1—O277.42 (6)Nd1—O4—H4B116.7
O3iv—Nd1—O2i77.42 (6)H4A—O4—H4B107.0
O3v—Nd1—O2i113.11 (6)H5A—O5—H5B115.5
O2—Nd1—O2i142.88 (9)H5A—O5—H5C114.1
O3iv—Nd1—O477.69 (6)H5B—O5—H5C81.7
O3v—Nd1—O476.57 (6)H7A—O7—H7B100.3
O2—Nd1—O474.57 (6)H7A—O7—H7C130.0
O2i—Nd1—O4141.53 (6)H7B—O7—H7C117.7
O3iv—Nd1—O4i76.57 (6)H7A—O7—H7D96.1
O3v—Nd1—O4i77.69 (6)H7B—O7—H7D113.4
O2—Nd1—O4i141.53 (6)H7C—O7—H7D97.0
O2i—Nd1—O4i74.57 (6)H8A—O8—H8B132.3
O4—Nd1—O4i71.43 (9)H8A—O8—H8C104.3
O3iv—Nd1—O1i80.89 (6)H8B—O8—H8C117.8
O3v—Nd1—O1i130.76 (6)H9A—O9—H9B109.7
O2—Nd1—O1i76.11 (6)H9A—O9—H9C100.2
O2i—Nd1—O1i70.50 (6)H9B—O9—H9C94.2
O4—Nd1—O1i132.79 (6)
O1—C1—C2—C3i176.61 (18)O1i—Nd1—O2—C475.74 (15)
O1i—C1—C2—C3i3.39 (18)O1—Nd1—O2—C4129.18 (16)
O1—C1—C2—C33.39 (18)O3—Nd1—O2—C43.30 (14)
O1i—C1—C2—C3176.61 (18)O3i—Nd1—O2—C4169.80 (14)
C3i—C2—C3—C3ii0.0O2—C4—O3—Nd1iv176.6 (2)
C1—C2—C3—C3ii180.0C5—C4—O3—Nd1iv3.4 (5)
O2—C4—C5—C631.4 (4)O2—C4—O3—Nd15.6 (2)
O3—C4—C5—C6148.7 (3)C5—C4—O3—Nd1174.4 (2)
C4—C5—C6—C5iii176.4 (2)O3iv—Nd1—O3—C4175.62 (19)
O1i—C1—O1—Nd10.0O3v—Nd1—O3—C431.47 (12)
C2—C1—O1—Nd1180.0O2—Nd1—O3—C43.22 (13)
O3iv—Nd1—O1—C116.60 (14)O2i—Nd1—O3—C4135.45 (14)
O3v—Nd1—O1—C1167.34 (11)O4—Nd1—O3—C487.68 (15)
O2—Nd1—O1—C187.55 (10)O4i—Nd1—O3—C4127.48 (14)
O2i—Nd1—O1—C175.97 (10)O1i—Nd1—O3—C493.91 (15)
O4—Nd1—O1—C1112.95 (11)O1—Nd1—O3—C454.41 (15)
O4i—Nd1—O1—C1128.93 (9)O3i—Nd1—O3—C473.58 (14)
O1i—Nd1—O1—C10.0C1—Nd1—O3—C473.57 (14)
O3—Nd1—O1—C148.98 (11)O3iv—Nd1—O3—Nd1iv0.0
O3i—Nd1—O1—C1126.96 (11)O3v—Nd1—O3—Nd1iv144.14 (10)
O3—C4—O2—Nd16.2 (3)O2—Nd1—O3—Nd1iv178.84 (12)
C5—C4—O2—Nd1173.78 (19)O2i—Nd1—O3—Nd1iv48.93 (11)
O3iv—Nd1—O2—C42.17 (17)O4—Nd1—O3—Nd1iv87.94 (9)
O3v—Nd1—O2—C4146.16 (16)O4i—Nd1—O3—Nd1iv48.13 (11)
O2i—Nd1—O2—C4102.03 (15)O1i—Nd1—O3—Nd1iv90.47 (8)
O4—Nd1—O2—C466.84 (15)O1—Nd1—O3—Nd1iv129.97 (8)
O4i—Nd1—O2—C495.37 (17)O3i—Nd1—O3—Nd1iv110.80 (7)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y, z; (iii) x, y, z+1/2; (iv) x+1/2, y+1/2, z+1; (v) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O50.841.912.750 (3)176
O4—H4B···O1vi0.841.932.762 (3)168
O5—H5A···O90.841.922.751 (4)168
O5—H5B···O60.841.922.764 (3)178
O5—H5C···O70.841.912.720 (5)161
O6—H6A···O50.841.972.764 (3)156
O7—H7A···O80.841.902.699 (4)158
O7—H7B···O50.841.912.720 (5)163
O7—H7C···O7vii0.841.932.756 (6)167
O7—H7D···O7iii0.841.932.760 (6)171
O8—H8A···O70.841.892.699 (4)162
O8—H8B···O2vi0.841.922.741 (3)167
O8—H8C···O8iii0.841.902.734 (5)174
O9—H9A···O8viii0.841.922.727 (4)162
O9—H9B···O9vii0.841.922.749 (6)169
O9—H9C···O9iii0.842.012.846 (6)177
Symmetry codes: (iii) x, y, z+1/2; (vi) x+1/2, y1/2, z; (vii) x+1, y, z; (viii) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Nd2(C5H6O4)2(C8H4O4)(H2O)4]·17H2O
Mr1091.12
Crystal system, space groupOrthorhombic, Cmcm
Temperature (K)100
a, b, c (Å)24.0265 (16), 8.7253 (6), 19.4746 (13)
V3)4082.6 (5)
Z4
Radiation typeMo Kα
µ (mm1)2.62
Crystal size (mm)0.31 × 0.29 × 0.10
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(APEX2; Bruker, 2009)
Tmin, Tmax0.622, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
36277, 3403, 2941
Rint0.026
(sin θ/λ)max1)0.734
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.083, 1.05
No. of reflections3403
No. of parameters125
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0401P)2 + 34.0861P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)2.45, 0.84

Computer programs: APEX2 (Bruker, 2009), SHELXTL (Sheldrick, 2008), CrystalMaker for Mac (Palmer, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O50.841.912.750 (3)176.2
O4—H4B···O1i0.841.932.762 (3)168.1
O5—H5A···O90.841.922.751 (4)168.2
O5—H5B···O60.841.922.764 (3)177.6
O5—H5C···O70.841.912.720 (5)160.8
O6—H6A···O50.841.972.764 (3)156.2
O7—H7A···O80.841.902.699 (4)158.3
O7—H7B···O50.841.912.720 (5)163.0
O7—H7C···O7ii0.841.932.756 (6)167.2
O7—H7D···O7iii0.841.932.760 (6)170.6
O8—H8A···O70.841.892.699 (4)161.6
O8—H8B···O2i0.841.922.741 (3)167.0
O8—H8C···O8iii0.841.902.734 (5)174.0
O9—H9A···O8iv0.841.922.727 (4)162.1
O9—H9B···O9ii0.841.922.749 (6)168.7
O9—H9C···O9iii0.842.012.846 (6)176.8
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x+1, y, z; (iii) x, y, z+1/2; (iv) x, y+1, z.
Independent Nd—O bond distances (Å) in the NdO10 polyhedron of (I) top
BondBond distanceDescription
Nd1—O32.4184 (18)Carboxylate groups from glutarate units (µ2)
Nd1—O22.5130 (18)Carboxylate groups from glutarate units (µ1)
Nd1—O42.5164 (19)Coordinating H2O
Nd1—O12.5434 (18)Carboxylate groups from terephthalate units
Nd1—O32.7463 (18)Carboxylate groups from glutarate units (µ2)
 

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