Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811000298/mg2113sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536811000298/mg2113Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
A mixture of Pr(NO_{3})_{3}.6H_{2}O (0.25 mmol, 0.1088 g), MnSO_{4}.H_{2}O (0.2 mmol, 0.0338 g), and H_{2}O (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(NO_{3})_{3}.6H_{2}O).
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)].
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).
Pr(SO_{4})(OH) | F(000) = 464 |
M_{r} = 253.98 | D_{x} = 4.550 Mg m^{−}^{3} |
Monoclinic, P2_{1}/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 |
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 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}(F_{o}^{2}) + (0.0348P)^{2} + 1.2539P] where P = (F_{o}^{2} + 2F_{c}^{2})/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+0.001xFc^{2}λ^{3}/sin(2θ)]^{-1/4} |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0303 (17) |
Pr(SO_{4})(OH) | V = 370.8 (3) Å^{3} |
M_{r} = 253.98 | Z = 4 |
Monoclinic, P2_{1}/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)° |
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 |
R[F^{2} > 2σ(F^{2})] = 0.033 | 0 restraints |
wR(F^{2}) = 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 |
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 F^{2} against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^{2}, conventional R-factors R are based on F, with F set to zero for negative F^{2}. The threshold expression of F^{2} > σ(F^{2}) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^{2} are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
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* |
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) |
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. |
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(SO_{4})(OH) |
M_{r} | 253.98 |
Crystal system, space group | Monoclinic, P2_{1}/n |
Temperature (K) | 293 |
a, b, c (Å) | 4.4891 (18), 12.484 (5), 6.894 (3) |
β (°) | 106.310 (7) |
V (Å^{3}) | 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[F^{2} > 2σ(F^{2})], wR(F^{2}), 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).
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O3^{i} | 0.85 | 2.20 | 2.630 (7) | 111 |
O5—H5A···O2^{ii} | 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. |
Lanthanide sulfate hydroxides exhibit a variety of architectures (Xu et al., 2007; Zhang et al., 2004). We report here the compound Pr(SO_{4})(OH), which is isostructural to Ln(SO_{4})(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–(µ_{3}-O)–La_{2}]. The oxygen atoms of the hydroxide groups are four-coordinate, [HO—µ_{3}-La_{3}], 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).