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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](S-O) = 0.005 Å
• R factor = 0.033
• wR factor = 0.080
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT973_ALERT_2_B Large Calcd. Positive Residual Density on     Pr       1.76 eA-3

Alert level C
PLAT213_ALERT_2_C Atom O1              has ADP max/min Ratio .....       3.90 oblat
PLAT303_ALERT_2_C Full Occupancy H-Atom  H5A    with # Connections          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3
PLAT774_ALERT_1_C Suspect X-Y Bond in CIF:   PR     --  PR      ..       3.71 Ang.
PLAT774_ALERT_1_C Suspect X-Y Bond in CIF:   PR     --  PR      ..       3.94 Ang.

Alert level G
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         12
            PR  -PR  -O1  -S    -140.00  0.70   3.576   1.555   1.555   1.555
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... #         75
              PR   -O5   -H5A     3.576   1.555   1.555             40.00 Deg.
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Pr      .......       4.23

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

The oxygen-bound H-atoms were located in the difference Fourier map and refined with the O—H distance restrained to 0.85 Å [U_iso(H) = 1.2U_eq(O)].

Computing details

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

	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

Crystal data

Pr(SO4)(OH)	F(000) = 464
Mr = 253.98	Dx = 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) Å^3	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection

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

Refinement

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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Pr—O2^i	2.393 (5)	S—O1	1.455 (5)
Pr—O5^ii	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—O4^iii	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—Pr^ii	2.436 (5)
Pr—Pr^iv	3.7056 (12)	O5—Pr^iv	2.554 (5)
Pr—Pr^ii	3.9388 (12)	O5—H5A	0.8500
S—O2	1.450 (5)
O2^i—Pr—O5^ii	88.30 (16)	O5—Pr—Pr^iv	43.35 (12)
O2^i—Pr—O5	137.33 (16)	O1—Pr—Pr^iv	173.83 (10)
O5^ii—Pr—O5	73.13 (18)	O4^iii—Pr—Pr^iv	115.28 (12)
O2^i—Pr—O1	66.58 (17)	O5^iv—Pr—Pr^iv	41.55 (10)
O5^ii—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)
O2^i—Pr—O4^iii	88.59 (15)	O3^vii—Pr—Pr^iv	45.31 (10)
O5^ii—Pr—O4^iii	139.79 (17)	O2^i—Pr—Pr^ii	116.25 (12)
O5—Pr—O4^iii	130.10 (14)	O5^ii—Pr—Pr^ii	36.83 (11)
O1—Pr—O4^iii	70.01 (15)	O5—Pr—Pr^ii	36.29 (11)
O2^i—Pr—O5^iv	77.01 (17)	O1—Pr—Pr^ii	105.16 (11)
O5^ii—Pr—O5^iv	128.20 (19)	O4^iii—Pr—Pr^ii	151.15 (10)
O5—Pr—O5^iv	84.90 (16)	O5^iv—Pr—Pr^ii	109.08 (11)
O1—Pr—O5^iv	138.17 (15)	O4^v—Pr—Pr^ii	86.32 (11)
O4^iii—Pr—O5^iv	89.84 (16)	O3^vi—Pr—Pr^ii	97.46 (11)
O2^i—Pr—O4^v	136.90 (16)	O3^vii—Pr—Pr^ii	57.99 (11)
O5^ii—Pr—O4^v	91.33 (16)	Pr^iv—Pr—Pr^ii	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)
O4^iii—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)
O2^i—Pr—O3^vi	132.98 (17)	O1—S—O4	108.5 (3)
O5^ii—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)
O4^iii—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)
O2^i—Pr—O3^vii	78.53 (16)	S—O4—Pr^x	125.0 (3)
O5^ii—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)	Pr^ii—O5—Pr	106.87 (18)
O4^iii—Pr—O3^vii	147.45 (16)	Pr^ii—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)	Pr^ii—O5—H5A	142.8
O3^vi—Pr—O3^vii	94.76 (13)	Pr—O5—H5A	109.3
O2^i—Pr—Pr^iv	109.56 (13)	Pr^iv—O5—H5A	40.0
O5^ii—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)
O2^i—Pr—O1—S	167.8 (5)	O1—S—O4—Pr^v	−147.0 (3)
O5^ii—Pr—O1—S	−96.1 (4)	O3—S—O4—Pr^v	−25.8 (4)
O5—Pr—O1—S	−57.3 (5)	O2^i—Pr—O5—Pr^ii	68.0 (3)
O4^iii—Pr—O1—S	70.4 (4)	O5^ii—Pr—O5—Pr^ii	0.0
O5^iv—Pr—O1—S	136.1 (4)	O1—Pr—O5—Pr^ii	−38.5 (3)
O4^v—Pr—O1—S	1.3 (4)	O4^iii—Pr—O5—Pr^ii	−141.99 (18)
O3^vi—Pr—O1—S	39.2 (5)	O5^iv—Pr—O5—Pr^ii	132.5 (2)
O3^vii—Pr—O1—S	−140.6 (4)	O4^v—Pr—O5—Pr^ii	−93.60 (19)
Pr^iv—Pr—O1—S	−140.0 (7)	O3^vi—Pr—O5—Pr^ii	−167.9 (2)
Pr^ii—Pr—O1—S	−79.7 (4)	O3^vii—Pr—O5—Pr^ii	76.67 (19)
O1—S—O2—Pr^viii	13.5 (8)	Pr^iv—Pr—O5—Pr^ii	132.5 (2)
O3—S—O2—Pr^viii	−109.8 (7)	O2^i—Pr—O5—Pr^iv	−64.5 (3)
O4—S—O2—Pr^viii	132.3 (7)	O5^ii—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)	O4^iii—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)	Pr^ii—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)

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.