Poly[μ2-hydroxido-μ4-sulfato-neodym­ium(III)]

Zhang, T.; Lu, J.

doi:10.1107/S1600536808021818

inorganic compounds

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Volume 64| Part 8| August 2008| Page i49

doi:10.1107/S1600536808021818

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Poly[μ₂-hydroxido-μ₄-sulfato-neodymium(III)]

Tao Zhang ^a and Jingmei Lu ^a ^*

^aSchool of Life Sciences, Northeast Normal University, Changchun 130024, People's Republic of China
^*Correspondence e-mail: jingmeilu@yahoo.cn

(Received 2 July 2008; accepted 13 July 2008; online 19 July 2008)

The title compound, [Nd(OH)(SO₄)]_n, was obtained hydrothermally from an aqueous solution of neodymium nitrate, 1,2-propanediamine and sulfuric acid. The structure features nonacoordinated neodymium with sulfate and hydroxide anions acting as bridging ligands. The OH group forms a weak O—H⋯O hydrogen bond with an O⋯O distance of 3.224 (5) Å.

Related literature

For related literature, see: Doran et al. (2002 ); Xu, Ding, Zhou & Liu (2006 ); Xu, Ding, Feng et al. (2006 ); Xu et al. (2007 ); Yuan et al. (2004 ); Zhang et al. (2004 ); Ding et al. (2006 ).

Experimental

Crystal data

[Nd(OH)(SO₄)]
M_r = 257.31
Monoclinic, P 2₁ /n
a = 4.4678 (9) Å
b = 12.432 (2) Å
c = 6.8575 (13) Å
β = 106.324 (3)°
V = 365.53 (12) Å³
Z = 4
Mo Kα radiation
μ = 14.66 mm⁻¹
T = 293 (2) K
0.10 × 0.08 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.322, T_max = 0.473 (expected range = 0.282–0.415)
1837 measured reflections
675 independent reflections
669 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.056
S = 1.24
675 reflections
67 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −2.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H1⋯O1ⁱ	0.83 (3)	2.43 (3)	3.224 (5)	160 (6)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021818/br2079sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021818/br2079Isup2.hkl

checkCIF report

Comment top

In the last few years, the synthesis of new three dimensional lanthanide sulfates have received great attention, due to their functional applications in catalysis, ion-exchange, and optical device (Zhang et al.,2004; Yuan et al., 2004; Xu, Ding, Feng et al., 2006; Xu, Ding, Zhou & Liu, 2006; Doran et al., 2002, Xu et al., 2007). In this work, we designed and synthesized the title compound, neodymium(3+) sulfate hydroxide, which features a three–dimensional framework constructed from NdO₉ polyhedra and SO₄ tetrahedra.

Nd(SO₄)(OH) is isostructural with La(SO₄)(OH) (Zhang et al.,2004) and Eu(SO₄)(OH)(Ding et al.,2006), the framework of title compound constructed from NdO₉ polyhedra and SO₄ tetrahedra. As show in Fig. 1, the asymmetric unit contains one Nd³⁺, one SO₄^2– group and one hydroxide group. The Nd³⁺ is coordinated by six bridging sulfate ions, each S atom makes four S–O–Nd linkages by sharing the bridging O atoms. The coordination sphere of Nd is completed by three OH^- groups, which act as briding ligands between three Nd^3+^.

The O-H group is involved hydrogen bonding interactions with O1, O2 and O4, the distances of O—H···O are vary from 2.60 (2) to 2.90 (2) Å.

The Nd —O distances are between of 2.374 (4)– 2.800 (4)Å (Table 1)while the O—Nd—O angles are between 66.02 (13) and 141.55 (12)°. These bond distances and bond angles are in agreement with those found in the reported rare-earth compounds (Zhang et al.,2004; Ding et al.,2006). The bond distances of S—O and angles of O—S—O are unexceptional. Fig. 2 shows the three-dimensional arrangement in the unit cell, displaying the way the different Nd³⁺ are connected by bridging hydroxide and sulfates groups.

Related literature top

For related literature, see: Doran et al. (2002); Xu, Ding Zhou & Liu (2006); Xu, Ding, Feng et al. (2006); Xu et al. (2007); Yuan et al. (2004); Zhang et al. (2004); Ding et al. (2006).

Experimental top

Pink block crystals were synthesized hydrothermally from a mixture of Nd(NO₃)₃.6H₂O, 1,2-propane diamine, H₂SO₄ and water. In a typical synthesis, Nd(NO₃)₃.6H₂O (0.6066 g) was dissolved in a mixture of 1,2-propane diamine (0.2205 g) and water (3.2 ml) followed by the addition of H₂SO₄ (98%) (0.3093 g) with constant stirring. Finally, the mixture was kept in a 25 ml Teflon-lined steel autoclave at 180 °C for 7 days. After the autoclave was slowly cooled to room temperature, Pink block crystals of the title compound were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure for title compound. Displacement ellipsoids at the 50% probability level.
	Fig. 2. The crystal packing in the unit cell of Nd(SO₄)(OH).

Poly[µ₂-hydroxido-µ₄-sulfato-neodymium(III)] top

Crystal data top

[Nd(OH)(SO₄)]	F(000) = 468
M_r = 257.31	D_x = 4.676 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 150 reflections
a = 4.4678 (9) Å	θ = 2.3–22.5°
b = 12.432 (2) Å	µ = 14.66 mm⁻¹
c = 6.8575 (13) Å	T = 293 K
β = 106.324 (3)°	Block, pink
V = 365.53 (12) Å³	0.10 × 0.08 × 0.06 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	675 independent reflections
Radiation source: fine-focus sealed tube	669 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ω scans	θ_max = 25.5°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −3→5
T_min = 0.322, T_max = 0.473	k = −14→15
1837 measured reflections	l = −7→8

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)] = 0.022	Hydrogen site location: difference Fourier map
wR(F²) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.24	w = 1/[σ²(F_o²) + (0.035P)² + 0.7631P] where P = (F_o² + 2F_c²)/3
675 reflections	(Δ/σ)_max = 0.001
67 parameters	Δρ_max = 0.56 e Å⁻³
1 restraint	Δρ_min = −2.28 e Å⁻³

Crystal data top

[Nd(OH)(SO₄)]	V = 365.53 (12) Å³
M_r = 257.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.4678 (9) Å	µ = 14.66 mm⁻¹
b = 12.432 (2) Å	T = 293 K
c = 6.8575 (13) Å	0.10 × 0.08 × 0.06 mm
β = 106.324 (3)°

Data collection top

Bruker APEXII CCD diffractometer	675 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	669 reflections with I > 2σ(I)
T_min = 0.322, T_max = 0.473	R_int = 0.013
1837 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	1 restraint
wR(F²) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.24	Δρ_max = 0.56 e Å⁻³
675 reflections	Δρ_min = −2.28 e Å⁻³
67 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

	x	y	z	U_iso*/U_eq
Nd1	0.14116 (6)	0.93569 (2)	0.80136 (4)	0.00655 (15)
S1	0.4852 (3)	0.85400 (10)	0.38900 (18)	0.0059 (3)
O1	0.3672 (9)	0.8343 (3)	0.5628 (6)	0.0136 (8)
O2	0.2485 (9)	0.9040 (3)	0.2196 (6)	0.0127 (8)
O3	0.7563 (9)	0.9295 (3)	0.4498 (6)	0.0105 (8)
O4	0.5923 (9)	0.7539 (3)	0.3200 (6)	0.0129 (8)
O5	0.3028 (9)	1.0847 (3)	1.0385 (6)	0.0081 (7)
H1	0.295 (14)	1.148 (2)	0.997 (9)	0.010*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Nd1	0.0075 (2)	0.0051 (2)	0.0073 (2)	0.00001 (8)	0.00245 (14)	−0.00073 (8)
S1	0.0073 (6)	0.0040 (6)	0.0068 (6)	0.0003 (4)	0.0026 (5)	−0.0001 (4)
O1	0.0172 (19)	0.0129 (19)	0.0136 (19)	0.0013 (16)	0.0093 (16)	0.0003 (15)
O2	0.0096 (18)	0.0133 (18)	0.0131 (18)	0.0026 (16)	−0.0002 (15)	0.0032 (15)
O3	0.0088 (19)	0.008 (2)	0.015 (2)	−0.0023 (13)	0.0036 (16)	−0.0004 (13)
O4	0.0196 (19)	0.0066 (19)	0.015 (2)	0.0037 (15)	0.0092 (17)	−0.0002 (14)
O5	0.0080 (18)	0.0034 (16)	0.0122 (18)	0.0005 (14)	0.0016 (14)	0.0027 (14)

Geometric parameters (Å, º) top

Nd1—O4ⁱ	2.374 (4)	S1—O1	1.453 (4)
Nd1—O5ⁱⁱ	2.431 (4)	S1—O4	1.459 (4)
Nd1—O5	2.437 (4)	S1—O2	1.470 (4)
Nd1—O1	2.492 (4)	S1—O3	1.496 (4)
Nd1—O3ⁱⁱⁱ	2.535 (4)	O2—Nd1^vi	2.624 (4)
Nd1—O5^iv	2.536 (4)	O2—Nd1^viii	2.800 (4)
Nd1—O3^v	2.538 (4)	O3—Nd1ⁱⁱⁱ	2.535 (4)
Nd1—O2^vi	2.624 (4)	O3—Nd1^ix	2.538 (4)
Nd1—O2^vii	2.800 (4)	O4—Nd1^x	2.374 (4)
Nd1—Nd1^iv	3.6744 (7)	O5—Nd1ⁱⁱ	2.431 (4)
Nd1—Nd1ⁱⁱ	3.9178 (7)	O5—Nd1^iv	2.536 (4)

O4ⁱ—Nd1—O5ⁱⁱ	88.26 (13)	O4ⁱ—Nd1—Nd1^iv	109.65 (10)
O4ⁱ—Nd1—O5	137.19 (13)	O5ⁱⁱ—Nd1—Nd1^iv	103.34 (9)
O5ⁱⁱ—Nd1—O5	72.81 (14)	O5—Nd1—Nd1^iv	43.41 (9)
O4ⁱ—Nd1—O1	66.02 (13)	O1—Nd1—Nd1^iv	173.45 (9)
O5ⁱⁱ—Nd1—O1	72.10 (13)	O3ⁱⁱⁱ—Nd1—Nd1^iv	112.42 (8)
O5—Nd1—O1	136.35 (13)	O5^iv—Nd1—Nd1^iv	41.33 (8)
O4ⁱ—Nd1—O3ⁱⁱⁱ	136.85 (12)	O3^v—Nd1—Nd1^iv	115.79 (9)
O5ⁱⁱ—Nd1—O3ⁱⁱⁱ	91.10 (13)	O2^vi—Nd1—Nd1^iv	49.41 (8)
O5—Nd1—O3ⁱⁱⁱ	82.80 (13)	O2^vii—Nd1—Nd1^iv	45.37 (8)
O1—Nd1—O3ⁱⁱⁱ	72.80 (12)	O4ⁱ—Nd1—Nd1ⁱⁱ	115.94 (9)
O4ⁱ—Nd1—O5^iv	77.43 (13)	O5ⁱⁱ—Nd1—Nd1ⁱⁱ	36.45 (9)
O5ⁱⁱ—Nd1—O5^iv	128.19 (16)	O5—Nd1—Nd1ⁱⁱ	36.35 (9)
O5—Nd1—O5^iv	84.74 (13)	O1—Nd1—Nd1ⁱⁱ	105.03 (9)
O1—Nd1—O5^iv	138.09 (13)	O3ⁱⁱⁱ—Nd1—Nd1ⁱⁱ	86.21 (9)
O3ⁱⁱⁱ—Nd1—O5^iv	132.32 (12)	O5^iv—Nd1—Nd1ⁱⁱ	109.06 (9)
O4ⁱ—Nd1—O3^v	88.46 (12)	O3^v—Nd1—Nd1ⁱⁱ	151.19 (8)
O5ⁱⁱ—Nd1—O3^v	139.42 (13)	O2^vi—Nd1—Nd1ⁱⁱ	97.41 (9)
O5—Nd1—O3^v	130.63 (11)	O2^vii—Nd1—Nd1ⁱⁱ	58.27 (8)
O1—Nd1—O3^v	69.68 (13)	Nd1^iv—Nd1—Nd1ⁱⁱ	72.017 (16)
O3ⁱⁱⁱ—Nd1—O3^v	65.06 (14)	O1—S1—O4	110.5 (2)
O5^iv—Nd1—O3^v	90.27 (13)	O1—S1—O2	111.9 (2)
O4ⁱ—Nd1—O2^vi	133.45 (13)	O4—S1—O2	109.4 (2)
O5ⁱⁱ—Nd1—O2^vi	133.02 (12)	O1—S1—O3	109.2 (2)
O5—Nd1—O2^vi	61.74 (12)	O4—S1—O3	108.2 (2)
O1—Nd1—O2^vi	137.14 (12)	O2—S1—O3	107.5 (2)
O3ⁱⁱⁱ—Nd1—O2^vi	72.81 (13)	S1—O1—Nd1	139.5 (2)
O5^iv—Nd1—O2^vi	60.80 (12)	S1—O2—Nd1^vi	133.1 (2)
O3^v—Nd1—O2^vi	73.07 (12)	S1—O2—Nd1^viii	138.3 (2)
O4ⁱ—Nd1—O2^vii	78.28 (12)	Nd1^vi—O2—Nd1^viii	85.22 (11)
O5ⁱⁱ—Nd1—O2^vii	70.32 (12)	S1—O3—Nd1ⁱⁱⁱ	120.8 (2)
O5—Nd1—O2^vii	59.36 (12)	S1—O3—Nd1^ix	124.3 (2)
O1—Nd1—O2^vii	128.08 (12)	Nd1ⁱⁱⁱ—O3—Nd1^ix	114.94 (14)
O3ⁱⁱⁱ—Nd1—O2^vii	141.03 (12)	S1—O4—Nd1^x	155.2 (3)
O5^iv—Nd1—O2^vii	58.11 (12)	Nd1ⁱⁱ—O5—Nd1	107.19 (14)
O3^v—Nd1—O2^vii	147.55 (12)	Nd1ⁱⁱ—O5—Nd1^iv	128.19 (16)
O2^vi—Nd1—O2^vii	94.78 (11)	Nd1—O5—Nd1^iv	95.26 (12)

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+2, −z+2; (iii) −x+1, −y+2, −z+1; (iv) −x, −y+2, −z+2; (v) x−1, y, z; (vi) −x, −y+2, −z+1; (vii) x, y, z+1; (viii) x, y, z−1; (ix) x+1, y, z; (x) x+1/2, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O1^xi	0.83 (3)	2.43 (3)	3.224 (5)	160 (6)

Symmetry code: (xi) −x+1/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Nd(OH)(SO₄)]
M_r	257.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	4.4678 (9), 12.432 (2), 6.8575 (13)
β (°)	106.324 (3)
V (Å³)	365.53 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	14.66
Crystal size (mm)	0.10 × 0.08 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.322, 0.473
No. of measured, independent and observed [I > 2σ(I)] reflections	1837, 675, 669
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.056, 1.24
No. of reflections	675
No. of parameters	67
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.56, −2.28

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O1ⁱ	0.83 (3)	2.43 (3)	3.224 (5)	160 (6)

Symmetry code: (i) −x+1/2, y+1/2, −z+3/2.

Acknowledgements

The authors thank Dr Zhang for help with the structural analysis.

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