Praseodymium(III) sulfate hydroxide, Pr(SO4)(OH)

Wang, X.-J.; Cheng, J.-W.

doi:10.1107/S1600536811000298

inorganic compounds

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Volume 67| Part 2| February 2011| Page i12

doi:10.1107/S1600536811000298

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Praseodymium(III) sulfate hydroxide, Pr(SO₄)(OH)

Xiao-Juan Wang ^a and Jian-Wen Cheng ^a ^*

^aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China
^*Correspondence e-mail: jwcheng@zjnu.cn

(Received 22 December 2010; accepted 5 January 2011; online 15 January 2011)

The title compound, Pr(SO₄)(OH), obtained under hydrothermal conditions, consists of Pr^III ions coordinated by nine O atoms from six sulfate groups and three hydroxide anions. The bridging mode of the O atoms results in the formation of a three-dimensional framework, stabilized by two O—H⋯O hydrogen-bonding interactions.

Related literature

Lanthanide sulfate hydroxides exhibit a variety of architectures, see: Xu et al. (2007 ); Zhang et al. (2004 ). For related structures, see: Yang et al. (2005 ); Ding et al. (2006 ); Zhang et al. (2004); Zhang & Lu (2008 ).

Experimental

Crystal data

Pr(SO₄)(OH)
M_r = 253.98
Monoclinic, P 2₁ /n
a = 4.4891 (18) Å
b = 12.484 (5) Å
c = 6.894 (3) Å
β = 106.310 (7)°
V = 370.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 13.59 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.213, T_max = 0.257
2849 measured reflections
840 independent reflections
813 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.080
S = 1.09
840 reflections
65 parameters
H-atom parameters constrained
Δρ_max = 1.73 e Å⁻³
Δρ_min = −2.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O3ⁱ	0.85	2.20	2.630 (7)	111
O5—H5A⋯O2ⁱⁱ	0.85	2.31	3.082 (7)	152
Symmetry codes: (i) -x, -y+2, -z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); 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 I, global. DOI: 10.1107/S1600536811000298/mg2113sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000298/mg2113Isup2.hkl

checkCIF report

Comment top

Lanthanide sulfate hydroxides exhibit a variety of architectures (Xu et al., 2007; Zhang et al., 2004). We report here the compound Pr(SO₄)(OH), which is isostructural to Ln(SO₄)(OH) (Ln = La, Ce, Eu, Nd) (Zhang et al., 2004; Yang et al., 2005; Ding et al., 2006; Zhang et al., 2008). The Pr^III ion is coordinated in a distorted tricapped trigonal prismatic geometry by the oxygen atoms from six sulfate groups and three hydroxide anions (Fig. 1). All oxygen atoms of the sulfate groups take part in the coordination. The S atom makes four S–O–La linkages through two 2-coordinated oxygen atoms [S–O–La] and two 3-coordinated oxygen atoms [S–(µ₃-O)–La₂]. The oxygen atoms of the hydroxide groups are four-coordinate, [HO—µ₃-La₃], linking three different Pr ions. The bridging mode of the oxygen atoms results in a three-dimensional framework, with the H atom of hydroxide anions forming weak O—H···O hydrogen bonds with two O atoms of sulfate groups (Fig. 2).

Related literature top

Lanthanide sulfate hydroxides exhibit a variety of architectures, see: Xu et al. (2007); Zhang et al. (2004). For related structures, see: Yang et al. (2005); Ding et al. (2006); Zhang et al. (2004, 2008).

Experimental top

A mixture of Pr(NO₃)₃.6H₂O (0.25 mmol, 0.1088 g), MnSO₄.H₂O (0.2 mmol, 0.0338 g), and H₂O (15 mL) was sealed in a 25-mL Teflon-lined stainless steel reactor and heated at 443 K for 72 h, and then cooled to room temperature over 3 days. Light-green prismatic crystals were obtained (yield: 32% based on Pr(NO₃)₃.6H₂O).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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. Coordination of Pr in Pr(SO₄)(OH). Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) x-1/2, -y+3/2, z+1/2; (ii) -x+1, -y+2, -z+1; (iii) x-1, y, z; (iv) -x, -y+2, -z+1; (v) -x+1, -y+2, -z; (vi) -x, -y+2, -z; (vii) x, y, z+1.]
	Fig. 2. Three-dimensional network in Pr(SO₄)(OH).

Praseodymium(III) sulfate hydroxide top

Crystal data top

Pr(SO₄)(OH)	F(000) = 464
M_r = 253.98	D_x = 4.550 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1066 reflections
a = 4.4891 (18) Å	θ = 3.3–27.4°
b = 12.484 (5) Å	µ = 13.59 mm⁻¹
c = 6.894 (3) Å	T = 293 K
β = 106.310 (7)°	Prism, light green
V = 370.8 (3) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	840 independent reflections
Radiation source: fine-focus sealed tube	813 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ω scans	θ_max = 27.4°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
T_min = 0.213, T_max = 0.257	k = −14→16
2849 measured reflections	l = −8→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0348P)² + 1.2539P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
840 reflections	Δρ_max = 1.73 e Å⁻³
65 parameters	Δρ_min = −2.15 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0303 (17)

Crystal data top

Pr(SO₄)(OH)	V = 370.8 (3) Å³
M_r = 253.98	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.4891 (18) Å	µ = 13.59 mm⁻¹
b = 12.484 (5) Å	T = 293 K
c = 6.894 (3) Å	0.20 × 0.10 × 0.10 mm
β = 106.310 (7)°

Data collection top

Bruker APEXII CCD diffractometer	840 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	813 reflections with I > 2σ(I)
T_min = 0.213, T_max = 0.257	R_int = 0.053
2849 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.09	Δρ_max = 1.73 e Å⁻³
840 reflections	Δρ_min = −2.15 e Å⁻³
65 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
Pr	0.14215 (8)	0.93511 (2)	0.30120 (5)	0.0103 (2)
S	0.4863 (3)	0.85448 (11)	−0.1115 (2)	0.0100 (3)
O1	0.3690 (11)	0.8345 (4)	0.0615 (6)	0.0156 (9)
O2	0.5908 (12)	0.7551 (4)	−0.1798 (7)	0.0189 (10)
O3	0.2507 (11)	0.9045 (4)	−0.2785 (7)	0.0179 (10)
O4	0.7557 (12)	0.9298 (3)	−0.0482 (8)	0.0137 (10)
O5	0.3035 (11)	1.0859 (4)	0.5390 (7)	0.0141 (9)
H5A	0.1434	1.1193	0.5488	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pr	0.0129 (3)	0.0104 (3)	0.0083 (3)	0.00025 (10)	0.00418 (19)	−0.00100 (9)
S	0.0118 (7)	0.0098 (7)	0.0091 (7)	−0.0002 (5)	0.0041 (6)	0.0002 (5)
O1	0.020 (2)	0.020 (2)	0.012 (2)	0.002 (2)	0.0142 (19)	0.0010 (17)
O2	0.027 (2)	0.014 (2)	0.020 (2)	0.001 (2)	0.011 (2)	−0.0016 (17)
O3	0.017 (2)	0.023 (2)	0.015 (2)	0.005 (2)	0.0060 (19)	0.0030 (19)
O4	0.013 (2)	0.013 (2)	0.016 (2)	−0.0039 (15)	0.005 (2)	−0.0022 (14)
O5	0.014 (2)	0.017 (2)	0.012 (2)	0.0037 (18)	0.0044 (18)	−0.0042 (17)

Geometric parameters (Å, º) top

Pr—O2ⁱ	2.393 (5)	S—O1	1.455 (5)
Pr—O5ⁱⁱ	2.436 (5)	S—O3	1.466 (5)
Pr—O5	2.468 (5)	S—O4	1.497 (5)
Pr—O1	2.508 (4)	O2—Pr^viii	2.393 (5)
Pr—O4ⁱⁱⁱ	2.543 (5)	O3—Pr^vi	2.643 (5)
Pr—O5^iv	2.554 (5)	O3—Pr^ix	2.826 (5)
Pr—O4^v	2.558 (5)	O4—Pr^x	2.543 (5)
Pr—O3^vi	2.643 (5)	O4—Pr^v	2.558 (5)
Pr—O3^vii	2.826 (5)	O5—Prⁱⁱ	2.436 (5)
Pr—Pr^iv	3.7056 (12)	O5—Pr^iv	2.554 (5)
Pr—Prⁱⁱ	3.9388 (12)	O5—H5A	0.8500
S—O2	1.450 (5)

O2ⁱ—Pr—O5ⁱⁱ	88.30 (16)	O5—Pr—Pr^iv	43.35 (12)
O2ⁱ—Pr—O5	137.33 (16)	O1—Pr—Pr^iv	173.83 (10)
O5ⁱⁱ—Pr—O5	73.13 (18)	O4ⁱⁱⁱ—Pr—Pr^iv	115.28 (12)
O2ⁱ—Pr—O1	66.58 (17)	O5^iv—Pr—Pr^iv	41.55 (10)
O5ⁱⁱ—Pr—O1	72.04 (15)	O4^v—Pr—Pr^iv	112.38 (11)
O5—Pr—O1	136.21 (16)	O3^vi—Pr—Pr^iv	49.45 (10)
O2ⁱ—Pr—O4ⁱⁱⁱ	88.59 (15)	O3^vii—Pr—Pr^iv	45.31 (10)
O5ⁱⁱ—Pr—O4ⁱⁱⁱ	139.79 (17)	O2ⁱ—Pr—Prⁱⁱ	116.25 (12)
O5—Pr—O4ⁱⁱⁱ	130.10 (14)	O5ⁱⁱ—Pr—Prⁱⁱ	36.83 (11)
O1—Pr—O4ⁱⁱⁱ	70.01 (15)	O5—Pr—Prⁱⁱ	36.29 (11)
O2ⁱ—Pr—O5^iv	77.01 (17)	O1—Pr—Prⁱⁱ	105.16 (11)
O5ⁱⁱ—Pr—O5^iv	128.20 (19)	O4ⁱⁱⁱ—Pr—Prⁱⁱ	151.15 (10)
O5—Pr—O5^iv	84.90 (16)	O5^iv—Pr—Prⁱⁱ	109.08 (11)
O1—Pr—O5^iv	138.17 (15)	O4^v—Pr—Prⁱⁱ	86.32 (11)
O4ⁱⁱⁱ—Pr—O5^iv	89.84 (16)	O3^vi—Pr—Prⁱⁱ	97.46 (11)
O2ⁱ—Pr—O4^v	136.90 (16)	O3^vii—Pr—Prⁱⁱ	57.99 (11)
O5ⁱⁱ—Pr—O4^v	91.33 (16)	Pr^iv—Pr—Prⁱⁱ	71.85 (3)
O5—Pr—O4^v	82.80 (16)	O2—S—O1	110.1 (3)
O1—Pr—O4^v	72.38 (15)	O2—S—O3	109.7 (3)
O4ⁱⁱⁱ—Pr—O4^v	64.96 (17)	O1—S—O3	111.7 (3)
O5^iv—Pr—O4^v	132.35 (15)	O2—S—O4	108.9 (3)
O2ⁱ—Pr—O3^vi	132.98 (17)	O1—S—O4	108.5 (3)
O5ⁱⁱ—Pr—O3^vi	133.47 (15)	O3—S—O4	107.9 (3)
O5—Pr—O3^vi	61.84 (16)	S—O1—Pr	139.7 (3)
O1—Pr—O3^vi	136.71 (14)	S—O2—Pr^viii	155.7 (3)
O4ⁱⁱⁱ—Pr—O3^vi	72.40 (15)	S—O3—Pr^vi	133.7 (3)
O5^iv—Pr—O3^vi	60.84 (15)	S—O3—Pr^ix	137.8 (3)
O4^v—Pr—O3^vi	72.83 (16)	Pr^vi—O3—Pr^ix	85.24 (13)
O2ⁱ—Pr—O3^vii	78.53 (16)	S—O4—Pr^x	125.0 (3)
O5ⁱⁱ—Pr—O3^vii	70.23 (15)	S—O4—Pr^v	120.0 (3)
O5—Pr—O3^vii	59.19 (16)	Pr^x—O4—Pr^v	115.04 (17)
O1—Pr—O3^vii	128.53 (14)	Prⁱⁱ—O5—Pr	106.87 (18)
O4ⁱⁱⁱ—Pr—O3^vii	147.45 (16)	Prⁱⁱ—O5—Pr^iv	128.20 (19)
O5^iv—Pr—O3^vii	58.29 (15)	Pr—O5—Pr^iv	95.10 (16)
O4^v—Pr—O3^vii	140.86 (15)	Prⁱⁱ—O5—H5A	142.8
O3^vi—Pr—O3^vii	94.76 (13)	Pr—O5—H5A	109.3
O2ⁱ—Pr—Pr^iv	109.56 (13)	Pr^iv—O5—H5A	40.0
O5ⁱⁱ—Pr—Pr^iv	103.47 (11)

O2—S—O1—Pr	179.4 (4)	O1—S—O4—Pr^x	33.7 (4)
O3—S—O1—Pr	−58.5 (5)	O3—S—O4—Pr^x	154.9 (3)
O4—S—O1—Pr	60.3 (5)	O2—S—O4—Pr^v	93.2 (3)
O2ⁱ—Pr—O1—S	167.8 (5)	O1—S—O4—Pr^v	−147.0 (3)
O5ⁱⁱ—Pr—O1—S	−96.1 (4)	O3—S—O4—Pr^v	−25.8 (4)
O5—Pr—O1—S	−57.3 (5)	O2ⁱ—Pr—O5—Prⁱⁱ	68.0 (3)
O4ⁱⁱⁱ—Pr—O1—S	70.4 (4)	O5ⁱⁱ—Pr—O5—Prⁱⁱ	0.0
O5^iv—Pr—O1—S	136.1 (4)	O1—Pr—O5—Prⁱⁱ	−38.5 (3)
O4^v—Pr—O1—S	1.3 (4)	O4ⁱⁱⁱ—Pr—O5—Prⁱⁱ	−141.99 (18)
O3^vi—Pr—O1—S	39.2 (5)	O5^iv—Pr—O5—Prⁱⁱ	132.5 (2)
O3^vii—Pr—O1—S	−140.6 (4)	O4^v—Pr—O5—Prⁱⁱ	−93.60 (19)
Pr^iv—Pr—O1—S	−140.0 (7)	O3^vi—Pr—O5—Prⁱⁱ	−167.9 (2)
Prⁱⁱ—Pr—O1—S	−79.7 (4)	O3^vii—Pr—O5—Prⁱⁱ	76.67 (19)
O1—S—O2—Pr^viii	13.5 (8)	Pr^iv—Pr—O5—Prⁱⁱ	132.5 (2)
O3—S—O2—Pr^viii	−109.8 (7)	O2ⁱ—Pr—O5—Pr^iv	−64.5 (3)
O4—S—O2—Pr^viii	132.3 (7)	O5ⁱⁱ—Pr—O5—Pr^iv	−132.5 (2)
O2—S—O3—Pr^vi	168.4 (4)	O1—Pr—O5—Pr^iv	−171.07 (15)
O1—S—O3—Pr^vi	46.0 (5)	O4ⁱⁱⁱ—Pr—O5—Pr^iv	85.5 (2)
O4—S—O3—Pr^vi	−73.1 (4)	O5^iv—Pr—O5—Pr^iv	0.0
O2—S—O3—Pr^ix	−39.4 (5)	O4^v—Pr—O5—Pr^iv	133.87 (16)
O1—S—O3—Pr^ix	−161.8 (4)	O3^vi—Pr—O5—Pr^iv	59.53 (16)
O4—S—O3—Pr^ix	79.1 (5)	O3^vii—Pr—O5—Pr^iv	−55.86 (15)
O2—S—O4—Pr^x	−86.1 (4)	Prⁱⁱ—Pr—O5—Pr^iv	−132.5 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O3^vi	0.85	2.20	2.630 (7)	111
O5—H5A···O2^xi	0.85	2.31	3.082 (7)	152

Symmetry codes: (vi) −x, −y+2, −z; (xi) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	Pr(SO₄)(OH)
M_r	253.98
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	4.4891 (18), 12.484 (5), 6.894 (3)
β (°)	106.310 (7)
V (Å³)	370.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	13.59
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.213, 0.257
No. of measured, independent and observed [I > 2σ(I)] reflections	2849, 840, 813
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.080, 1.09
No. of reflections	840
No. of parameters	65
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.73, −2.15

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), 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—H5A···O3ⁱ	0.85	2.20	2.630 (7)	111
O5—H5A···O2ⁱⁱ	0.85	2.31	3.082 (7)	152

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

References

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