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Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810016600/hb5433sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810016600/hb5433Isup2.hkl |
CCDC reference: 781204
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(C-C) = 0.005 Å
- R factor = 0.015
- wR factor = 0.041
- Data-to-parameter ratio = 15.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 -- O3 .. 8.34 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 -- O6 .. 9.04 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 -- O8_a .. 7.16 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 -- O2_c .. 8.02 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 -- O9_c .. 8.45 su PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 2 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 3 PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings Differ ? PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 11
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.48 From the CIF: _reflns_number_total 3485 Count of symmetry unique reflns 1862 Completeness (_total/calc) 187.16% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1623 Fraction of Friedel pairs measured 0.872 Are heavy atom types Z>Si present yes PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 4 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 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 0 ALERT type 5 Informative message, check
(I) was synthesized under hydrothermal condition. In a typically route, Ce(NO3)3.6H2O (0.30 g, 0.7 mmol) was dissolved in 5 ml deionized water under stirring, and then H2SO4 (95%, 0.25 ml, 4.55 mmol) and DETA (0.22 ml, 2.8 mmol) were dropwisely added to a clear solution with pH=3.0. After continuously stirred for 3 h, the solution with the molar ratio of Ce(NO3)3.6H2O : 6.5H2SO4 : 2.8DETA : 397H2O was transferred into 23 ml autoclave and heated at 438 K for 5 days. After naturally cooling to room temperature, colorless block soluble product was collected by filtration as a single phase. The atomic ratio of Ce : S determined by EDX was 1 : 3, in consistence with the results of structural determination of (I).
Water H atoms were located in a difference Fourier map and were refined with O—H = 0.82 (2) Å, H···H = 1.37 (2) Å and Uiso(H) = 1.2Ueq(O). The remaining H-atoms were placed in calculated positions (C—H = 0.89 Å, N—H = 0.89-0.90 Å) and were included in the refinement in the riding-model approximation, with U(H) = 1.2Ueq(C, N).
The hydrous and anhydrous lanthanide sulfates have been intensively studied due to use of the separation of rare earth elements (Wickleder, 2002). Since the pioneering works of Rao et al. (Choudhury, et al., 2001; Paul, et al., 2002; Rao, et al., 2006) on the preparation of organically templated open-framework metal sulfates, a remarkable plenty of organically templated open-framework rare-earth sulfates have been describled also. The example of organically templated cerium sulfate is few reported except for (C4H12N2)4.[Ce8(SO4)16(H2O)8] and (C2H10N2)2.[Ce2(SO4)5(H2O)2] (Fu, et al., 2006). In this work, a new layer cerium sulfate, {(C4H16N3)[Ce(SO4)3(H2O)]}n, is obtained.
The asymmetric unit of (I) comprises of one CeIII cation, three SO4 groups, one coordination water and one protonated diethylene triamine cation, as shown in Fig.1. The CeIII cation is 9-coordinated by nine oxygen including one water molecule with the bond distances from 2.468 (2) Å to 2.588 (27) Å and the angles of O—Ce—O between 54.18 (10)° and 149.13 (10)°. Three SO4 can be divided into two modes: S(1) and S(3) consist of three S—O—Ce linkages and links adjacent Ce atoms through one bidentate and one monodentate; S(2) makes two S—O—Ce linkages as a ligand of one Ce atom through bidentate. The bond angles of S—O—Ce of bidentate coordination range from 99.23 (10)° to 101.8 (1)°, and the S—O—Ce of monodentate coordination is at 141.81 (9)° and 144.17 (13)°.
As shown in Fig.2, the layer of (I) is accomplished by connect the Ce cations by µ2-S(1)O4 and µ2-S(3)O4 as the bridge along (100) and (010) direction, respectively. The S(2)O4 do not take part in the formation of layer and coordinates to Ce cation by the bidentate mode. The protonated H3DETA interacts with the layer by the H-bond of N—H···O.
For related literature, see: Choudhury et al. (2001); Fu et al. (2006); Paul et al. (2002); Rao et al. (2006); Wickleder (2002).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(C4H16N3)[Ce(SO4)3(H2O)] | F(000) = 546 |
Mr = 552.51 | Dx = 2.388 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1000 reflections |
a = 6.6774 (13) Å | θ = 3.1–24.8° |
b = 10.397 (2) Å | µ = 3.44 mm−1 |
c = 11.093 (2) Å | T = 293 K |
β = 93.77 (3)° | Block, colorless |
V = 768.5 (3) Å3 | 0.25 × 0.22 × 0.19 mm |
Z = 2 |
Rigaku R-AXIS RAPID diffractometer | 3485 independent reflections |
Radiation source: fine-focus sealed tube | 3443 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −7→8 |
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995) | k = −13→13 |
Tmin = 0.480, Tmax = 0.561 | l = −14→14 |
7575 measured reflections |
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)] = 0.015 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.041 | w = 1/[σ2(Fo2) + (0.005P)2 + 0.1027P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max = 0.001 |
3485 reflections | Δρmax = 0.56 e Å−3 |
225 parameters | Δρmin = −0.71 e Å−3 |
4 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.009 (8) |
(C4H16N3)[Ce(SO4)3(H2O)] | V = 768.5 (3) Å3 |
Mr = 552.51 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.6774 (13) Å | µ = 3.44 mm−1 |
b = 10.397 (2) Å | T = 293 K |
c = 11.093 (2) Å | 0.25 × 0.22 × 0.19 mm |
β = 93.77 (3)° |
Rigaku R-AXIS RAPID diffractometer | 3485 independent reflections |
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995) | 3443 reflections with I > 2σ(I) |
Tmin = 0.480, Tmax = 0.561 | Rint = 0.017 |
7575 measured reflections |
R[F2 > 2σ(F2)] = 0.015 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.041 | Δρmax = 0.56 e Å−3 |
S = 1.15 | Δρmin = −0.71 e Å−3 |
3485 reflections | Absolute structure: Flack (1983) |
225 parameters | Absolute structure parameter: −0.009 (8) |
4 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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. |
x | y | z | Uiso*/Ueq | ||
Ce1 | 0.468643 (16) | 0.636197 (16) | 0.819119 (10) | 0.00928 (4) | |
S1 | 1.00549 (10) | 0.68984 (7) | 0.75724 (6) | 0.01204 (13) | |
S2 | 0.57509 (11) | 0.41208 (7) | 0.63748 (6) | 0.01388 (14) | |
S3 | 0.57345 (10) | 0.97128 (6) | 0.93682 (6) | 0.01258 (13) | |
O1 | 0.5483 (3) | 0.8315 (2) | 0.9420 (2) | 0.0190 (4) | |
O2 | 0.3896 (3) | 1.0370 (2) | 0.97444 (19) | 0.0198 (4) | |
O3 | 0.5087 (3) | 0.5445 (2) | 0.60536 (19) | 0.0199 (4) | |
O4 | 0.6164 (4) | 1.0119 (2) | 0.81523 (19) | 0.0249 (5) | |
O5 | 1.1298 (3) | 0.5804 (2) | 0.71992 (18) | 0.0181 (4) | |
O6 | 0.5651 (3) | 0.40504 (19) | 0.77192 (18) | 0.0172 (4) | |
O7 | 0.8387 (2) | 0.6423 (3) | 0.82503 (16) | 0.0198 (4) | |
O8 | 1.1447 (3) | 0.7667 (2) | 0.83878 (18) | 0.0160 (4) | |
O9 | 0.7341 (3) | 1.01219 (19) | 1.02740 (19) | 0.0178 (4) | |
O10 | 0.9302 (3) | 0.7643 (2) | 0.6533 (2) | 0.0264 (5) | |
O11 | 0.4326 (3) | 0.3179 (2) | 0.5804 (2) | 0.0242 (5) | |
O12 | 0.7762 (3) | 0.3875 (2) | 0.6036 (2) | 0.0276 (5) | |
O1W | 0.4833 (4) | 0.8105 (2) | 0.66809 (19) | 0.0199 (4) | |
H1F | 0.529 (5) | 0.879 (2) | 0.696 (3) | 0.024* | |
H1G | 0.520 (5) | 0.799 (3) | 0.600 (2) | 0.024* | |
N1 | −0.0899 (4) | 0.3572 (3) | 0.9309 (2) | 0.0214 (5) | |
H1A | −0.1665 | 0.3382 | 0.9912 | 0.026* | |
H1B | −0.1653 | 0.3921 | 0.8703 | 0.026* | |
H1C | 0.0049 | 0.4127 | 0.9567 | 0.026* | |
N2 | 0.2464 (4) | 0.1635 (2) | 0.7422 (2) | 0.0204 (6) | |
H2A | 0.3274 | 0.1334 | 0.8039 | 0.025* | |
H2B | 0.3257 | 0.1928 | 0.6856 | 0.025* | |
N3 | −0.0952 (4) | −0.0122 (3) | 0.5183 (2) | 0.0245 (6) | |
H3A | −0.1851 | 0.0142 | 0.4609 | 0.029* | |
H3B | −0.1518 | −0.0693 | 0.5653 | 0.029* | |
H3C | 0.0079 | −0.0486 | 0.4845 | 0.029* | |
C1 | 0.0052 (5) | 0.2382 (3) | 0.8884 (3) | 0.0223 (6) | |
H1D | −0.0969 | 0.1769 | 0.8604 | 0.027* | |
H1E | 0.0873 | 0.1992 | 0.9540 | 0.027* | |
C2 | 0.1330 (5) | 0.2739 (3) | 0.7870 (3) | 0.0182 (6) | |
H2C | 0.0477 | 0.3090 | 0.7208 | 0.022* | |
H2D | 0.2268 | 0.3405 | 0.8147 | 0.022* | |
C3 | 0.1272 (5) | 0.0532 (3) | 0.6894 (3) | 0.0234 (7) | |
H3D | 0.0579 | 0.0108 | 0.7524 | 0.028* | |
H3E | 0.2169 | −0.0087 | 0.6558 | 0.028* | |
C4 | −0.0234 (5) | 0.0989 (3) | 0.5919 (3) | 0.0279 (8) | |
H4A | −0.1355 | 0.1398 | 0.6280 | 0.034* | |
H4B | 0.0383 | 0.1615 | 0.5412 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ce1 | 0.00800 (7) | 0.00962 (6) | 0.01010 (6) | −0.00022 (6) | −0.00020 (5) | −0.00028 (7) |
S1 | 0.0082 (3) | 0.0151 (3) | 0.0127 (3) | −0.0003 (2) | −0.0003 (3) | 0.0010 (2) |
S2 | 0.0137 (3) | 0.0150 (3) | 0.0128 (3) | 0.0005 (3) | −0.0002 (3) | −0.0029 (2) |
S3 | 0.0141 (3) | 0.0122 (3) | 0.0113 (3) | −0.0004 (2) | −0.0007 (3) | −0.0016 (2) |
O1 | 0.0245 (11) | 0.0130 (10) | 0.0190 (10) | −0.0016 (8) | −0.0016 (9) | −0.0026 (8) |
O2 | 0.0165 (10) | 0.0207 (10) | 0.0216 (10) | 0.0066 (8) | −0.0027 (9) | −0.0042 (8) |
O3 | 0.0222 (11) | 0.0194 (10) | 0.0178 (10) | 0.0059 (8) | −0.0012 (9) | 0.0004 (8) |
O4 | 0.0369 (13) | 0.0251 (12) | 0.0131 (10) | −0.0070 (10) | 0.0043 (10) | 0.0000 (8) |
O5 | 0.0118 (9) | 0.0214 (10) | 0.0208 (10) | 0.0010 (8) | −0.0019 (9) | −0.0082 (8) |
O6 | 0.0212 (10) | 0.0181 (10) | 0.0118 (9) | −0.0005 (8) | −0.0022 (9) | 0.0000 (8) |
O7 | 0.0102 (7) | 0.0279 (10) | 0.0216 (8) | −0.0029 (11) | 0.0029 (7) | 0.0037 (12) |
O8 | 0.0133 (9) | 0.0177 (10) | 0.0171 (9) | −0.0015 (7) | 0.0012 (8) | −0.0040 (8) |
O9 | 0.0142 (9) | 0.0185 (10) | 0.0202 (10) | −0.0012 (8) | −0.0033 (9) | −0.0053 (8) |
O10 | 0.0243 (11) | 0.0317 (13) | 0.0220 (11) | 0.0019 (10) | −0.0074 (10) | 0.0097 (9) |
O11 | 0.0277 (12) | 0.0270 (12) | 0.0176 (10) | −0.0095 (10) | −0.0012 (10) | −0.0062 (9) |
O12 | 0.0199 (10) | 0.0321 (13) | 0.0317 (12) | 0.0067 (9) | 0.0077 (10) | −0.0061 (10) |
O1W | 0.0268 (11) | 0.0179 (11) | 0.0153 (10) | −0.0013 (10) | 0.0034 (9) | 0.0011 (8) |
N1 | 0.0179 (13) | 0.0301 (15) | 0.0164 (11) | −0.0004 (10) | 0.0017 (11) | 0.0016 (10) |
N2 | 0.0166 (11) | 0.0171 (16) | 0.0268 (12) | 0.0019 (9) | −0.0046 (11) | −0.0027 (9) |
N3 | 0.0334 (15) | 0.0221 (14) | 0.0174 (12) | −0.0037 (11) | −0.0025 (12) | 0.0021 (10) |
C1 | 0.0245 (16) | 0.0212 (15) | 0.0213 (14) | −0.0046 (12) | 0.0027 (13) | 0.0043 (11) |
C2 | 0.0202 (14) | 0.0151 (14) | 0.0193 (13) | −0.0008 (11) | 0.0025 (12) | −0.0001 (11) |
C3 | 0.0255 (16) | 0.0140 (14) | 0.0300 (16) | 0.0022 (11) | −0.0046 (14) | −0.0006 (12) |
C4 | 0.0401 (19) | 0.0169 (15) | 0.0250 (15) | 0.0030 (12) | −0.0111 (16) | −0.0025 (11) |
Ce1—O7 | 2.4685 (17) | N1—C1 | 1.481 (4) |
Ce1—O1W | 2.474 (2) | N1—H1A | 0.8900 |
Ce1—O1 | 2.484 (2) | N1—H1B | 0.8900 |
Ce1—O5i | 2.518 (2) | N1—H1C | 0.8900 |
Ce1—O6 | 2.551 (2) | N2—C2 | 1.479 (4) |
Ce1—O8i | 2.575 (2) | N2—C3 | 1.493 (4) |
Ce1—O3 | 2.586 (2) | N2—H2A | 0.9000 |
Ce1—O9ii | 2.588 (2) | N2—H2B | 0.9000 |
Ce1—O2ii | 2.631 (2) | N3—C4 | 1.476 (4) |
S1—O10 | 1.451 (2) | N3—H3A | 0.8900 |
S1—O7 | 1.470 (2) | N3—H3B | 0.8900 |
S1—O5 | 1.483 (2) | N3—H3C | 0.8900 |
S1—O8 | 1.487 (2) | C1—C2 | 1.502 (4) |
S2—O12 | 1.441 (2) | C1—H1D | 0.9700 |
S2—O11 | 1.478 (2) | C1—H1E | 0.9700 |
S2—O3 | 1.482 (2) | C2—H2C | 0.9700 |
S2—O6 | 1.499 (2) | C2—H2D | 0.9700 |
S3—O4 | 1.460 (2) | C3—C4 | 1.504 (4) |
S3—O1 | 1.465 (2) | C3—H3D | 0.9700 |
S3—O9 | 1.483 (2) | C3—H3E | 0.9700 |
S3—O2 | 1.488 (2) | C4—H4A | 0.9700 |
O1W—H1F | 0.828 (18) | C4—H4B | 0.9700 |
O1W—H1G | 0.813 (18) | ||
O7—Ce1—O1W | 85.13 (8) | O11—S2—O3 | 109.76 (14) |
O7—Ce1—O1 | 77.68 (8) | O11—S2—O3 | 109.76 (14) |
O1W—Ce1—O1 | 75.90 (8) | O12—S2—O6 | 110.75 (13) |
O7—Ce1—O5i | 152.47 (7) | O11—S2—O6 | 108.94 (13) |
O1W—Ce1—O5i | 86.97 (8) | O11—S2—O6 | 108.94 (13) |
O1—Ce1—O5i | 125.59 (7) | O3—S2—O6 | 104.62 (12) |
O7—Ce1—O6 | 76.34 (8) | O12—S2—Ce1 | 122.98 (10) |
O1W—Ce1—O6 | 121.95 (7) | O11—S2—Ce1 | 126.18 (10) |
O1—Ce1—O6 | 146.61 (7) | O11—S2—Ce1 | 126.18 (10) |
O5i—Ce1—O6 | 85.70 (7) | O3—S2—Ce1 | 53.00 (8) |
O7—Ce1—O8i | 146.03 (8) | O6—S2—Ce1 | 51.77 (8) |
O1W—Ce1—O8i | 75.06 (7) | O4—S3—O1 | 110.70 (14) |
O1—Ce1—O8i | 70.94 (7) | O4—S3—O1 | 110.70 (14) |
O5i—Ce1—O8i | 54.73 (6) | O4—S3—O9 | 111.45 (13) |
O6—Ce1—O8i | 137.61 (6) | O4—S3—O9 | 111.45 (13) |
O7—Ce1—O3 | 82.53 (7) | O1—S3—O9 | 109.74 (12) |
O1W—Ce1—O3 | 68.78 (7) | O4—S3—O2 | 109.99 (14) |
O1—Ce1—O3 | 140.66 (7) | O4—S3—O2 | 109.99 (14) |
O5i—Ce1—O3 | 70.03 (7) | O1—S3—O2 | 110.21 (14) |
O6—Ce1—O3 | 54.67 (6) | O9—S3—O2 | 104.58 (12) |
O8i—Ce1—O3 | 114.22 (7) | O4—S3—Ce1iv | 130.80 (10) |
O7—Ce1—O9ii | 124.15 (7) | O4—S3—Ce1iv | 130.80 (10) |
O1W—Ce1—O9ii | 148.88 (7) | O1—S3—Ce1iv | 118.49 (10) |
O1—Ce1—O9ii | 98.55 (7) | O9—S3—Ce1iv | 51.63 (9) |
O5i—Ce1—O9ii | 71.27 (7) | O2—S3—Ce1iv | 53.35 (8) |
O6—Ce1—O9ii | 79.38 (7) | S3—O1—Ce1 | 144.17 (13) |
O8i—Ce1—O9ii | 74.23 (7) | S3—O2—Ce1iv | 99.66 (10) |
O3—Ce1—O9ii | 120.64 (7) | S2—O3—Ce1 | 99.75 (10) |
O7—Ce1—O2ii | 71.62 (7) | S1—O5—Ce1iii | 101.82 (10) |
O1W—Ce1—O2ii | 148.08 (7) | S2—O6—Ce1 | 100.75 (10) |
O1—Ce1—O2ii | 77.94 (7) | S1—O7—Ce1 | 141.80 (12) |
O5i—Ce1—O2ii | 123.49 (7) | S1—O8—Ce1iii | 99.21 (10) |
O6—Ce1—O2ii | 74.22 (7) | S3—O9—Ce1iv | 101.66 (10) |
O8i—Ce1—O2ii | 112.91 (7) | Ce1—O1W—H1F | 114 (3) |
O3—Ce1—O2ii | 126.92 (7) | Ce1—O1W—H1G | 123 (3) |
O9ii—Ce1—O2ii | 53.54 (6) | H1F—O1W—H1G | 110 (3) |
O7—Ce1—S1i | 163.95 (6) | C1—N1—H1A | 109.5 |
O1W—Ce1—S1i | 78.82 (6) | C1—N1—H1B | 109.5 |
O1—Ce1—S1i | 98.37 (5) | H1A—N1—H1B | 109.5 |
O5i—Ce1—S1i | 27.23 (5) | C1—N1—H1C | 109.5 |
O6—Ce1—S1i | 112.13 (5) | H1A—N1—H1C | 109.5 |
O8i—Ce1—S1i | 27.55 (4) | H1B—N1—H1C | 109.5 |
O3—Ce1—S1i | 91.41 (6) | C2—N2—C3 | 117.1 (2) |
O9ii—Ce1—S1i | 71.66 (5) | C2—N2—H2A | 108.0 |
O2ii—Ce1—S1i | 123.17 (5) | C3—N2—H2A | 108.0 |
O7—Ce1—S2 | 76.78 (6) | C2—N2—H2B | 108.0 |
O1W—Ce1—S2 | 94.98 (6) | C3—N2—H2B | 108.0 |
O1—Ce1—S2 | 153.51 (6) | H2A—N2—H2B | 107.3 |
O5i—Ce1—S2 | 77.70 (5) | C4—N3—H3A | 109.5 |
O6—Ce1—S2 | 27.48 (4) | C4—N3—H3B | 109.5 |
O8i—Ce1—S2 | 131.42 (5) | H3A—N3—H3B | 109.5 |
O3—Ce1—S2 | 27.25 (5) | C4—N3—H3C | 109.5 |
O9ii—Ce1—S2 | 101.51 (5) | H3A—N3—H3C | 109.5 |
O2ii—Ce1—S2 | 100.43 (5) | H3B—N3—H3C | 109.5 |
S1i—Ce1—S2 | 104.25 (3) | N1—C1—C2 | 108.0 (2) |
O7—Ce1—S3ii | 97.66 (6) | N1—C1—H1D | 110.1 |
O1W—Ce1—S3ii | 164.83 (5) | C2—C1—H1D | 110.1 |
O1—Ce1—S3ii | 90.07 (5) | N1—C1—H1E | 110.1 |
O5i—Ce1—S3ii | 96.83 (6) | C2—C1—H1E | 110.1 |
O6—Ce1—S3ii | 73.10 (5) | H1D—C1—H1E | 108.4 |
O8i—Ce1—S3ii | 95.10 (5) | N2—C2—C1 | 112.9 (2) |
O3—Ce1—S3ii | 126.32 (5) | N2—C2—H2C | 109.0 |
O9ii—Ce1—S3ii | 26.70 (4) | C1—C2—H2C | 109.0 |
O2ii—Ce1—S3ii | 26.99 (4) | N2—C2—H2D | 109.0 |
S1i—Ce1—S3ii | 97.89 (3) | C1—C2—H2D | 109.0 |
S2—Ce1—S3ii | 100.18 (2) | H2C—C2—H2D | 107.8 |
O10—S1—O7 | 110.58 (13) | N2—C3—C4 | 110.7 (2) |
O10—S1—O5 | 111.01 (14) | N2—C3—H3D | 109.5 |
O7—S1—O5 | 109.98 (15) | C4—C3—H3D | 109.5 |
O10—S1—O8 | 111.51 (13) | N2—C3—H3E | 109.5 |
O7—S1—O8 | 109.51 (12) | C4—C3—H3E | 109.5 |
O5—S1—O8 | 104.08 (11) | H3D—C3—H3E | 108.1 |
O10—S1—Ce1iii | 123.20 (11) | N3—C4—C3 | 109.2 (3) |
O7—S1—Ce1iii | 126.20 (9) | N3—C4—H4A | 109.8 |
O5—S1—Ce1iii | 50.96 (8) | C3—C4—H4A | 109.8 |
O8—S1—Ce1iii | 53.24 (8) | N3—C4—H4B | 109.8 |
O12—S2—O11 | 110.80 (15) | C3—C4—H4B | 109.8 |
O12—S2—O11 | 110.80 (15) | H4A—C4—H4B | 108.3 |
O12—S2—O3 | 111.77 (14) | ||
O7—Ce1—S2—O12 | −5.76 (14) | O4—S3—O2—Ce1iv | −126.59 (11) |
O1W—Ce1—S2—O12 | 78.04 (14) | O4—S3—O2—Ce1iv | −126.59 (11) |
O1—Ce1—S2—O12 | 9.97 (17) | O1—S3—O2—Ce1iv | 111.08 (11) |
O5i—Ce1—S2—O12 | 163.83 (14) | O9—S3—O2—Ce1iv | −6.81 (12) |
O6—Ce1—S2—O12 | −91.51 (16) | O12—S2—O3—Ce1 | −115.66 (13) |
O8i—Ce1—S2—O12 | 152.48 (14) | O11—S2—O3—Ce1 | 120.98 (12) |
O3—Ce1—S2—O12 | 93.70 (17) | O11—S2—O3—Ce1 | 120.98 (12) |
O9ii—Ce1—S2—O12 | −128.49 (13) | O6—S2—O3—Ce1 | 4.23 (12) |
O2ii—Ce1—S2—O12 | −73.88 (13) | O7—Ce1—O3—S2 | 75.58 (12) |
S1i—Ce1—S2—O12 | 157.75 (12) | O1W—Ce1—O3—S2 | 163.23 (14) |
S3ii—Ce1—S2—O12 | −101.32 (13) | O1—Ce1—O3—S2 | 135.61 (11) |
O7—Ce1—S2—O11 | 172.06 (13) | O5i—Ce1—O3—S2 | −102.14 (12) |
O1W—Ce1—S2—O11 | −104.14 (14) | O6—Ce1—O3—S2 | −2.95 (8) |
O1—Ce1—S2—O11 | −172.22 (17) | O8i—Ce1—O3—S2 | −135.32 (10) |
O5i—Ce1—S2—O11 | −18.35 (13) | O9ii—Ce1—O3—S2 | −49.90 (13) |
O6—Ce1—S2—O11 | 86.31 (16) | O2ii—Ce1—O3—S2 | 15.33 (15) |
O8i—Ce1—S2—O11 | −29.70 (14) | S1i—Ce1—O3—S2 | −119.34 (10) |
O3—Ce1—S2—O11 | −88.48 (17) | S3ii—Ce1—O3—S2 | −18.47 (13) |
O9ii—Ce1—S2—O11 | 49.33 (13) | O1—S3—O4—O4 | 0.0 (7) |
O2ii—Ce1—S2—O11 | 103.93 (13) | O9—S3—O4—O4 | 0.0 (7) |
S1i—Ce1—S2—O11 | −24.43 (12) | O2—S3—O4—O4 | 0.0 (7) |
S3ii—Ce1—S2—O11 | 76.49 (12) | Ce1iv—S3—O4—O4 | 0.0 (8) |
O7—Ce1—S2—O11 | 172.06 (13) | O10—S1—O5—Ce1iii | 116.35 (13) |
O1W—Ce1—S2—O11 | −104.14 (14) | O7—S1—O5—Ce1iii | −120.96 (10) |
O1—Ce1—S2—O11 | −172.22 (17) | O8—S1—O5—Ce1iii | −3.73 (13) |
O5i—Ce1—S2—O11 | −18.35 (13) | O12—S2—O6—Ce1 | 116.27 (13) |
O6—Ce1—S2—O11 | 86.31 (16) | O11—S2—O6—Ce1 | −121.62 (12) |
O8i—Ce1—S2—O11 | −29.70 (14) | O11—S2—O6—Ce1 | −121.62 (12) |
O3—Ce1—S2—O11 | −88.48 (17) | O3—S2—O6—Ce1 | −4.30 (12) |
O9ii—Ce1—S2—O11 | 49.33 (13) | O7—Ce1—O6—S2 | −87.55 (11) |
O2ii—Ce1—S2—O11 | 103.93 (13) | O1W—Ce1—O6—S2 | −12.30 (13) |
S1i—Ce1—S2—O11 | −24.43 (12) | O1—Ce1—O6—S2 | −127.41 (12) |
S3ii—Ce1—S2—O11 | 76.49 (12) | O5i—Ce1—O6—S2 | 71.42 (11) |
O7—Ce1—S2—O3 | −99.46 (13) | O8i—Ce1—O6—S2 | 91.15 (13) |
O1W—Ce1—S2—O3 | −15.66 (13) | O3—Ce1—O6—S2 | 2.92 (8) |
O1—Ce1—S2—O3 | −83.74 (16) | O9ii—Ce1—O6—S2 | 143.15 (11) |
O5i—Ce1—S2—O3 | 70.13 (13) | O2ii—Ce1—O6—S2 | −161.97 (11) |
O6—Ce1—S2—O3 | 174.79 (15) | S1i—Ce1—O6—S2 | 78.11 (10) |
O8i—Ce1—S2—O3 | 58.78 (13) | S3ii—Ce1—O6—S2 | 169.90 (10) |
O9ii—Ce1—S2—O3 | 137.81 (12) | O10—S1—O7—Ce1 | 3.9 (3) |
O2ii—Ce1—S2—O3 | −167.59 (12) | O5—S1—O7—Ce1 | −119.0 (2) |
S1i—Ce1—S2—O3 | 64.05 (11) | O8—S1—O7—Ce1 | 127.2 (2) |
S3ii—Ce1—S2—O3 | 164.97 (11) | Ce1iii—S1—O7—Ce1 | −174.67 (17) |
O7—Ce1—S2—O6 | 85.75 (12) | O1W—Ce1—O7—S1 | −16.4 (3) |
O1W—Ce1—S2—O6 | 169.55 (12) | O1—Ce1—O7—S1 | −93.0 (3) |
O1—Ce1—S2—O6 | 101.48 (15) | O5i—Ce1—O7—S1 | 57.5 (4) |
O5i—Ce1—S2—O6 | −104.66 (12) | O6—Ce1—O7—S1 | 108.2 (3) |
O8i—Ce1—S2—O6 | −116.01 (12) | O8i—Ce1—O7—S1 | −70.3 (3) |
O3—Ce1—S2—O6 | −174.79 (15) | O3—Ce1—O7—S1 | 52.8 (3) |
O9ii—Ce1—S2—O6 | −36.98 (11) | O9ii—Ce1—O7—S1 | 175.0 (2) |
O2ii—Ce1—S2—O6 | 17.63 (11) | O2ii—Ce1—O7—S1 | −174.2 (3) |
S1i—Ce1—S2—O6 | −110.74 (10) | S1i—Ce1—O7—S1 | −15.7 (5) |
S3ii—Ce1—S2—O6 | −9.81 (10) | S2—Ce1—O7—S1 | 79.9 (3) |
O4—S3—O1—Ce1 | −21.6 (3) | S3ii—Ce1—O7—S1 | 178.6 (3) |
O4—S3—O1—Ce1 | −21.6 (3) | O10—S1—O8—Ce1iii | −116.13 (12) |
O9—S3—O1—Ce1 | −145.0 (2) | O7—S1—O8—Ce1iii | 121.17 (12) |
O2—S3—O1—Ce1 | 100.3 (2) | O5—S1—O8—Ce1iii | 3.62 (12) |
Ce1iv—S3—O1—Ce1 | 158.70 (17) | O4—S3—O9—Ce1iv | 125.76 (12) |
O7—Ce1—O1—S3 | 93.1 (2) | O4—S3—O9—Ce1iv | 125.76 (12) |
O1W—Ce1—O1—S3 | 5.1 (2) | O1—S3—O9—Ce1iv | −111.24 (12) |
O5i—Ce1—O1—S3 | −70.6 (3) | O2—S3—O9—Ce1iv | 6.96 (13) |
O6—Ce1—O1—S3 | 132.7 (2) | O12—S2—O11—O11 | 0.0 (2) |
O8i—Ce1—O1—S3 | −73.7 (2) | O3—S2—O11—O11 | 0.0 (2) |
O3—Ce1—O1—S3 | 31.6 (3) | O6—S2—O11—O11 | 0.00 (19) |
O9ii—Ce1—O1—S3 | −143.6 (2) | Ce1—S2—O11—O11 | 0.00 (19) |
O2ii—Ce1—O1—S3 | 166.7 (2) | C3—N2—C2—C1 | 61.8 (3) |
S1i—Ce1—O1—S3 | −71.1 (2) | N1—C1—C2—N2 | 176.3 (2) |
S2—Ce1—O1—S3 | 77.5 (3) | C2—N2—C3—C4 | 53.3 (4) |
S3ii—Ce1—O1—S3 | −169.0 (2) | N2—C3—C4—N3 | 163.5 (3) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y−1/2, −z+2; (iii) x+1, y, z; (iv) −x+1, y+1/2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1F···O4 | 0.83 (2) | 1.98 (2) | 2.766 (3) | 159 (4) |
O1W—H1G···O11v | 0.81 (2) | 2.06 (2) | 2.850 (3) | 164 (4) |
N1—H1A···O8ii | 0.89 | 2.02 | 2.769 (3) | 141 |
N1—H1C···O9ii | 0.89 | 2.02 | 2.883 (3) | 162 |
N1—H1B···O6i | 0.89 | 2.05 | 2.852 (3) | 150 |
N2—H2B···O11 | 0.90 | 1.92 | 2.764 (4) | 156 |
N2—H2A···O2vi | 0.90 | 2.16 | 2.993 (3) | 154 |
N2—H2A···O4vi | 0.90 | 2.30 | 2.997 (3) | 134 |
N3—H3A···O5vii | 0.89 | 2.17 | 2.808 (3) | 128 |
N3—H3A···O3viii | 0.89 | 2.26 | 3.059 (4) | 150 |
N3—H3C···O12vii | 0.89 | 1.91 | 2.799 (4) | 173 |
N3—H3B···O10ix | 0.89 | 2.04 | 2.763 (4) | 137 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y−1/2, −z+2; (v) −x+1, y+1/2, −z+1; (vi) x, y−1, z; (vii) −x+1, y−1/2, −z+1; (viii) −x, y−1/2, −z+1; (ix) x−1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | (C4H16N3)[Ce(SO4)3(H2O)] |
Mr | 552.51 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 6.6774 (13), 10.397 (2), 11.093 (2) |
β (°) | 93.77 (3) |
V (Å3) | 768.5 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.44 |
Crystal size (mm) | 0.25 × 0.22 × 0.19 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Empirical (using intensity measurements) (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.480, 0.561 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7575, 3485, 3443 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.015, 0.041, 1.15 |
No. of reflections | 3485 |
No. of parameters | 225 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.56, −0.71 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.009 (8) |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1F···O4 | 0.828 (18) | 1.975 (18) | 2.766 (3) | 159 (4) |
O1W—H1G···O11i | 0.813 (18) | 2.06 (2) | 2.850 (3) | 164 (4) |
N1—H1A···O8ii | 0.89 | 2.02 | 2.769 (3) | 140.5 |
N1—H1C···O9ii | 0.89 | 2.02 | 2.883 (3) | 161.7 |
N1—H1B···O6iii | 0.89 | 2.05 | 2.852 (3) | 149.7 |
N2—H2B···O11 | 0.90 | 1.92 | 2.764 (4) | 156.0 |
N2—H2A···O2iv | 0.90 | 2.16 | 2.993 (3) | 154.2 |
N2—H2A···O4iv | 0.90 | 2.30 | 2.997 (3) | 133.8 |
N3—H3A···O5v | 0.89 | 2.17 | 2.808 (3) | 127.7 |
N3—H3A···O3vi | 0.89 | 2.26 | 3.059 (4) | 149.5 |
N3—H3C···O12v | 0.89 | 1.91 | 2.799 (4) | 173.2 |
N3—H3B···O10vii | 0.89 | 2.04 | 2.763 (4) | 137.2 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+2; (iii) x−1, y, z; (iv) x, y−1, z; (v) −x+1, y−1/2, −z+1; (vi) −x, y−1/2, −z+1; (vii) x−1, y−1, z. |
The hydrous and anhydrous lanthanide sulfates have been intensively studied due to use of the separation of rare earth elements (Wickleder, 2002). Since the pioneering works of Rao et al. (Choudhury, et al., 2001; Paul, et al., 2002; Rao, et al., 2006) on the preparation of organically templated open-framework metal sulfates, a remarkable plenty of organically templated open-framework rare-earth sulfates have been describled also. The example of organically templated cerium sulfate is few reported except for (C4H12N2)4.[Ce8(SO4)16(H2O)8] and (C2H10N2)2.[Ce2(SO4)5(H2O)2] (Fu, et al., 2006). In this work, a new layer cerium sulfate, {(C4H16N3)[Ce(SO4)3(H2O)]}n, is obtained.
The asymmetric unit of (I) comprises of one CeIII cation, three SO4 groups, one coordination water and one protonated diethylene triamine cation, as shown in Fig.1. The CeIII cation is 9-coordinated by nine oxygen including one water molecule with the bond distances from 2.468 (2) Å to 2.588 (27) Å and the angles of O—Ce—O between 54.18 (10)° and 149.13 (10)°. Three SO4 can be divided into two modes: S(1) and S(3) consist of three S—O—Ce linkages and links adjacent Ce atoms through one bidentate and one monodentate; S(2) makes two S—O—Ce linkages as a ligand of one Ce atom through bidentate. The bond angles of S—O—Ce of bidentate coordination range from 99.23 (10)° to 101.8 (1)°, and the S—O—Ce of monodentate coordination is at 141.81 (9)° and 144.17 (13)°.
As shown in Fig.2, the layer of (I) is accomplished by connect the Ce cations by µ2-S(1)O4 and µ2-S(3)O4 as the bridge along (100) and (010) direction, respectively. The S(2)O4 do not take part in the formation of layer and coordinates to Ce cation by the bidentate mode. The protonated H3DETA interacts with the layer by the H-bond of N—H···O.