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The title compound, poly[μ-hydroxido-μ-carbonato-neo­dymium], [Nd(CO3)(OH)]n, has a three-dimensional framework structure assembled from NdO10 polyhedra and CO32− groups. The Nd atom is coordinated by eight O atoms from CO32− groups and two OH anions, while the C atom is coordinated by three O atoms. Nd, two O atoms and C are located on mirror planes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703721X/fi2039sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680703721X/fi2039Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](O-C) = 0.005 Å
  • R factor = 0.020
  • wR factor = 0.050
  • Data-to-parameter ratio = 11.2

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.96 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.84 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.75 Ratio
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.843 Tmax scaled 0.364 Tmin scaled 0.292 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Nd1 (2) 2.01 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

Recently, the synthesis of three dimensional frameworks with new topological structures has received great attention, due to their functional applications in catalysis, adsorption, ion-exchange, and radioactive waste remediation. As the building elements of open-frameworks, not only silicon, but germanium and carbon have been choosen to synthesize new open-frameworks (Li et al., 1998; Lin et al., 2003; Plévert et al., 2001; Xu, Fan, Chino et al., 2004; Xu, Fan, Elangovan et al., 2004; Xu, Cheng & You, 2006; Xu, Ding et al.,2006). In the last few years, an important advance in porous materials has been achieved by the study of transition metal carbonates. The diamond-type Na2Zn3(CO3)4·3H2O was reported by Gier et al. (1996), while the face-centered (FC) cubic [Zn6(CO3)12(CH6N3)8Na3[N(CH3)4]·2H2O was synthesized by Abrahams et al. (2004). Compared with other transition metals, the rare-earth elements adopt a large range of coordination numbers. The structure of title compound has been determined by powder diffraction (Dexpert & Caro, 1973). Even a hexagonal high-temperature modification is known (Christensen, 1973). In this work, we synthesized the title compound as single crystals suitable for a structure determination.

The structure features a three-dimensional framework constructed from NdO10 polyhedra and carbonates. As in the previously reported Sm(CO3)(OH), the asymmetric unit of the title compound contains five independent non-H atoms, and all of them belong to the inorganic framework (Fig. 1). The Nd atom is coordinated by ten O atoms from CO32- and OH- anions. The C atom is coordinated by three O atoms with C—O distances ranging from 1.269 (7) to 1.289 (4) Å and angles ranging from 119.4 (5) to 120.2 (2)°. Each C atom makes eight C—O—Nd linkages through bridging O atoms. While each OH- group acts as a µ2-bridging ligang linking two Nd atoms to generate a [Nd—O]n chain. Furthermore, the [Nd—O]n chains are connected by CO32- anions to form a three-dimensional inorganic framework, as shown in Fig. 2. The Nd atom has the typical geometrical parameters, with Nd—O distances in the range 2.346 (4)–2.750 (3) Å. The O—Nd—O angles are between 49.2 (1) and 156.6 (2)°. These bond distances and angles are in agreement with those found in the reported rare-earth compounds (Xu, Ding et al., 2006). The O—H anions are involved in hydrogen bonding with each other; the shortest O···O distance is 3.107 (4) Å and the O—H···O angle is 154 (7)°.

Related literature top

For an earlier structure determination of the title compound from powder data, see: Dexpert & Caro (1973). For a high-temperature modification, see: Christensen (1973). For similar framework materials, see: Li et al. (1998); Lin et al. (2003); Plévert et al. (2001); Xu, Fan, Chino et al. (2004); Xu, Fan, Elangovan et al. (2004); Xu, Cheng & You (2006); Xu, Ding et al. (2006). For related literature, see: Abrahams et al. (2004); Gier et al. (1996).

Experimental top

Purple block-shaped crystals were hydrothermally synthesized from a mixture of Nd(NO3)3 (99%, Shanghai Reagent Company), Cu(NO3)2 (99.5%, Tianjin Bodi Reagent Company), HCO2H (88%, Tianjin Taixing Reagent factory), H2O, tetraethylammoniumhydroxide (10%, Beijing chemical factory), and guanidine nitrate (98%, Shanghai Reagent Company). In a typical synthesis, Nd(NO3)3 (0.3464 g), Cu(NO3)2 (0.0525 g), guanidine nitrate (0.7882 g) were dissolved in the solvent of water (8.0 g) followed by the addition of HCO2H (0.7169 g) and tetraethylammoniumhydroxide (0.7131 g) with constant stirring. Finally, the mixture was kept in a 25 ml Teflon-lined steel autoclave at 180 °C for 7 days. The autoclave was slowly cooled to room temperature, and then the product was filtered, washed with distilled water, and dried at room temperature. Purple block-shaped crystals of title compound were obtained.

Refinement top

The highest peak in the difference map is 1.17 e/Å3, and 0.85 (2) Å from Nd1, while the minimum peak is 0.77 (2) Å from Nd1. The H atom was located from the Fourier map.

Structure description top

Recently, the synthesis of three dimensional frameworks with new topological structures has received great attention, due to their functional applications in catalysis, adsorption, ion-exchange, and radioactive waste remediation. As the building elements of open-frameworks, not only silicon, but germanium and carbon have been choosen to synthesize new open-frameworks (Li et al., 1998; Lin et al., 2003; Plévert et al., 2001; Xu, Fan, Chino et al., 2004; Xu, Fan, Elangovan et al., 2004; Xu, Cheng & You, 2006; Xu, Ding et al.,2006). In the last few years, an important advance in porous materials has been achieved by the study of transition metal carbonates. The diamond-type Na2Zn3(CO3)4·3H2O was reported by Gier et al. (1996), while the face-centered (FC) cubic [Zn6(CO3)12(CH6N3)8Na3[N(CH3)4]·2H2O was synthesized by Abrahams et al. (2004). Compared with other transition metals, the rare-earth elements adopt a large range of coordination numbers. The structure of title compound has been determined by powder diffraction (Dexpert & Caro, 1973). Even a hexagonal high-temperature modification is known (Christensen, 1973). In this work, we synthesized the title compound as single crystals suitable for a structure determination.

The structure features a three-dimensional framework constructed from NdO10 polyhedra and carbonates. As in the previously reported Sm(CO3)(OH), the asymmetric unit of the title compound contains five independent non-H atoms, and all of them belong to the inorganic framework (Fig. 1). The Nd atom is coordinated by ten O atoms from CO32- and OH- anions. The C atom is coordinated by three O atoms with C—O distances ranging from 1.269 (7) to 1.289 (4) Å and angles ranging from 119.4 (5) to 120.2 (2)°. Each C atom makes eight C—O—Nd linkages through bridging O atoms. While each OH- group acts as a µ2-bridging ligang linking two Nd atoms to generate a [Nd—O]n chain. Furthermore, the [Nd—O]n chains are connected by CO32- anions to form a three-dimensional inorganic framework, as shown in Fig. 2. The Nd atom has the typical geometrical parameters, with Nd—O distances in the range 2.346 (4)–2.750 (3) Å. The O—Nd—O angles are between 49.2 (1) and 156.6 (2)°. These bond distances and angles are in agreement with those found in the reported rare-earth compounds (Xu, Ding et al., 2006). The O—H anions are involved in hydrogen bonding with each other; the shortest O···O distance is 3.107 (4) Å and the O—H···O angle is 154 (7)°.

For an earlier structure determination of the title compound from powder data, see: Dexpert & Caro (1973). For a high-temperature modification, see: Christensen (1973). For similar framework materials, see: Li et al. (1998); Lin et al. (2003); Plévert et al. (2001); Xu, Fan, Chino et al. (2004); Xu, Fan, Elangovan et al. (2004); Xu, Cheng & You (2006); Xu, Ding et al. (2006). For related literature, see: Abrahams et al. (2004); Gier et al. (1996).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The coordination of Nd in the title compound. Displacement ellipsoids at the 70% probability level. [Symmetry codes: (i) 1/2 + x, y, -3/2 - z; (ii) x, y + 1, z; (iii) 1/2 + x, 1/2 - y, 3/2 - z; (iv) 1/2, 1/2 + y, 1/2 + z; (v) 1/2 - x, -y, 1/2 + z; (vi) x, 1/2 - y, z; (vii) 1/2 + x, -1/2 - y, 3/2 - z; (viii) 1/2 + x, 1 + y, 3/2 - z); (ix) 1/2 + x, y, 3/2 - z; (x) x, -1/2 - y, z.
[Figure 2] Fig. 2. Threedimensional open framework with 6-membered ring channels viewed along b axis.
poly[µ-hydroxido-µ-carbonato-neodymium] top
Crystal data top
[Nd(CO3)(OH)]F(000) = 396
Mr = 221.26Dx = 4.823 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 1700 reflections
a = 7.231 (5) Åθ = 3.7–27.0°
b = 4.964 (4) ŵ = 16.86 mm1
c = 8.489 (6) ÅT = 293 K
V = 304.7 (4) Å3Block, pink
Z = 40.08 × 0.08 × 0.06 mm
Data collection top
Bruker APEXII CCD
diffractometer
424 independent reflections
Radiation source: fine-focus sealed tube399 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω scansθmax = 28.7°, θmin = 3.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 39
Tmin = 0.346, Tmax = 0.431k = 66
1730 measured reflectionsl = 1011
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020Only H-atom coordinates refined
wR(F2) = 0.050 w = 1/[σ2(Fo2) + (0.0319P)2 + 0.2734P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.015
424 reflectionsΔρmax = 1.17 e Å3
38 parametersΔρmin = 1.09 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 1997b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.040 (2)
Crystal data top
[Nd(CO3)(OH)]V = 304.7 (4) Å3
Mr = 221.26Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 7.231 (5) ŵ = 16.86 mm1
b = 4.964 (4) ÅT = 293 K
c = 8.489 (6) Å0.08 × 0.08 × 0.06 mm
Data collection top
Bruker APEXII CCD
diffractometer
424 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
399 reflections with I > 2σ(I)
Tmin = 0.346, Tmax = 0.431Rint = 0.027
1730 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0201 restraint
wR(F2) = 0.050Only H-atom coordinates refined
S = 1.07Δρmax = 1.17 e Å3
424 reflectionsΔρmin = 1.09 e Å3
38 parameters
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*/UeqOcc. (<1)
Nd10.35584 (4)0.25000.83332 (3)0.00774 (18)
O10.1525 (3)0.0258 (6)0.6121 (4)0.0095 (6)
O20.0386 (6)0.25000.8949 (5)0.0144 (9)
H10.000 (14)0.154 (15)0.970 (7)0.017*0.50
O30.2941 (7)0.25000.8032 (5)0.0141 (9)
C10.1960 (9)0.25000.6793 (6)0.0074 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Nd10.0073 (2)0.0066 (2)0.0093 (2)0.0000.00035 (9)0.000
O10.0106 (14)0.0075 (15)0.0103 (14)0.0010 (10)0.0005 (10)0.0007 (13)
O20.010 (2)0.024 (2)0.0089 (19)0.0000.0002 (16)0.000
O30.021 (2)0.008 (2)0.0140 (19)0.0000.0064 (18)0.000
C10.007 (3)0.006 (3)0.009 (3)0.0000.0028 (19)0.000
Geometric parameters (Å, º) top
Nd1—O2i2.346 (4)Nd1—C13.034 (4)
Nd1—O22.353 (4)O1—C11.289 (4)
Nd1—O32.535 (2)O1—Nd1vii2.587 (3)
Nd1—O3ii2.535 (2)O1—Nd1viii2.616 (4)
Nd1—O1iii2.587 (3)O2—Nd1vii2.346 (4)
Nd1—O1i2.587 (3)O2—H10.84 (2)
Nd1—O1iv2.616 (4)O3—C11.269 (7)
Nd1—O1v2.616 (4)O3—Nd1ix2.535 (2)
Nd1—O12.750 (3)C1—O1x1.289 (4)
Nd1—O1vi2.750 (3)C1—Nd1viii2.961 (6)
Nd1—C1v2.961 (6)C1—Nd1ix3.034 (4)
O2i—Nd1—O2137.14 (12)O3—Nd1—C1v94.45 (10)
O2i—Nd1—O390.92 (11)O3ii—Nd1—C1v94.45 (10)
O2—Nd1—O381.41 (12)O1iii—Nd1—C1v85.83 (13)
O2i—Nd1—O3ii90.92 (11)O1i—Nd1—C1v85.83 (13)
O2—Nd1—O3ii81.41 (12)O1iv—Nd1—C1v25.80 (8)
O3—Nd1—O3ii156.6 (2)O1v—Nd1—C1v25.80 (8)
O2i—Nd1—O1iii71.38 (12)O1—Nd1—C1v127.56 (12)
O2—Nd1—O1iii140.24 (10)O1vi—Nd1—C1v127.56 (12)
O3—Nd1—O1iii133.04 (13)O2i—Nd1—C181.87 (12)
O3ii—Nd1—O1iii69.26 (14)O2—Nd1—C174.00 (13)
O2i—Nd1—O1i71.38 (11)O3—Nd1—C124.29 (13)
O2—Nd1—O1i140.24 (10)O3ii—Nd1—C1133.66 (14)
O3—Nd1—O1i69.26 (14)O1iii—Nd1—C1145.70 (13)
O3ii—Nd1—O1i133.04 (13)O1i—Nd1—C187.72 (14)
O1iii—Nd1—O1i63.92 (14)O1iv—Nd1—C1136.82 (12)
O2i—Nd1—O1iv139.50 (10)O1v—Nd1—C191.91 (12)
O2—Nd1—O1iv77.08 (11)O1—Nd1—C125.14 (11)
O3—Nd1—O1iv120.24 (12)O1vi—Nd1—C184.79 (12)
O3ii—Nd1—O1iv70.77 (12)C1v—Nd1—C1112.29 (9)
O1iii—Nd1—O1iv68.40 (10)C1—O1—Nd1vii125.5 (3)
O1i—Nd1—O1iv94.72 (7)C1—O1—Nd1viii92.2 (3)
O2i—Nd1—O1v139.50 (10)Nd1vii—O1—Nd1viii111.60 (10)
O2—Nd1—O1v77.08 (11)C1—O1—Nd189.9 (3)
O3—Nd1—O1v70.77 (12)Nd1vii—O1—Nd193.30 (11)
O3ii—Nd1—O1v120.24 (12)Nd1viii—O1—Nd1147.34 (11)
O1iii—Nd1—O1v94.72 (7)Nd1vii—O2—Nd1111.45 (17)
O1i—Nd1—O1v68.40 (10)Nd1vii—O2—H1116 (7)
O1iv—Nd1—O1v50.35 (15)Nd1—O2—H1119 (7)
O2i—Nd1—O174.76 (12)C1—O3—Nd1100.49 (10)
O2—Nd1—O168.32 (11)C1—O3—Nd1ix100.49 (10)
O3—Nd1—O149.42 (12)Nd1—O3—Nd1ix156.6 (2)
O3ii—Nd1—O1108.93 (12)O3—C1—O1x120.2 (3)
O1iii—Nd1—O1146.02 (6)O3—C1—O1120.2 (3)
O1i—Nd1—O1107.59 (12)O1x—C1—O1119.4 (5)
O1iv—Nd1—O1144.81 (6)O3—C1—Nd1viii153.3 (4)
O1v—Nd1—O1113.18 (5)O1x—C1—Nd1viii62.0 (2)
O2i—Nd1—O1vi74.76 (12)O1—C1—Nd1viii62.0 (2)
O2—Nd1—O1vi68.32 (11)O3—C1—Nd155.22 (10)
O3—Nd1—O1vi108.93 (12)O1x—C1—Nd1171.7 (4)
O3ii—Nd1—O1vi49.42 (12)O1—C1—Nd165.0 (2)
O1iii—Nd1—O1vi107.59 (12)Nd1viii—C1—Nd1118.41 (10)
O1i—Nd1—O1vi146.02 (6)O3—C1—Nd1ix55.22 (10)
O1iv—Nd1—O1vi113.18 (5)O1x—C1—Nd1ix65.0 (2)
O1v—Nd1—O1vi144.81 (6)O1—C1—Nd1ix171.7 (4)
O1—Nd1—O1vi59.71 (14)Nd1viii—C1—Nd1ix118.41 (10)
O2i—Nd1—C1v152.98 (16)Nd1—C1—Nd1ix109.76 (19)
O2—Nd1—C1v69.88 (16)
Symmetry codes: (i) x+1/2, y, z+3/2; (ii) x, y+1, z; (iii) x+1/2, y+1/2, z+3/2; (iv) x+1/2, y+1/2, z+1/2; (v) x+1/2, y, z+1/2; (vi) x, y+1/2, z; (vii) x1/2, y, z+3/2; (viii) x+1/2, y, z1/2; (ix) x, y1, z; (x) x, y1/2, z.

Experimental details

Crystal data
Chemical formula[Nd(CO3)(OH)]
Mr221.26
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)293
a, b, c (Å)7.231 (5), 4.964 (4), 8.489 (6)
V3)304.7 (4)
Z4
Radiation typeMo Kα
µ (mm1)16.86
Crystal size (mm)0.08 × 0.08 × 0.06
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.346, 0.431
No. of measured, independent and
observed [I > 2σ(I)] reflections
1730, 424, 399
Rint0.027
(sin θ/λ)max1)0.676
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.050, 1.07
No. of reflections424
No. of parameters38
No. of restraints1
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)1.17, 1.09

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 1997a), SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997b), SHELXTL.

Selected bond lengths (Å) top
Nd1—O2i2.346 (4)Nd1—O1i2.587 (3)
Nd1—O22.353 (4)Nd1—O1iv2.616 (4)
Nd1—O32.535 (2)Nd1—O1v2.616 (4)
Nd1—O3ii2.535 (2)Nd1—O12.750 (3)
Nd1—O1iii2.587 (3)Nd1—O1vi2.750 (3)
Symmetry codes: (i) x+1/2, y, z+3/2; (ii) x, y+1, z; (iii) x+1/2, y+1/2, z+3/2; (iv) x+1/2, y+1/2, z+1/2; (v) x+1/2, y, z+1/2; (vi) x, y+1/2, z.
 

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