Poly[diethyl­enetriammonium [aquadi-μ2-sulfato-sulfatocerium(III)]]

Zhang, X.-M.; Li, Y.-F.

doi:10.1107/S1600536810016600

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Pages m649-m650

https://doi.org/10.1107/S1600536810016600

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Poly[diethylenetriammonium [aquadi-μ₂-sulfato-sulfatocerium(III)]]

Xiu-Mei Zhang ^a and Ya-Feng Li ^b ^*

^aDepartment of X-ray, First Hospital, Jilin University, Changchun 130021, People's Republic of China, and ^bSchool of Chemical Engineering, Changchun University of Technology, Changchun 130012, People's Republic of China
^*Correspondence e-mail: fly012345@sohu.com

(Received 30 April 2010; accepted 6 May 2010; online 15 May 2010)

A new organically templated open-framework cerium sulfate, {(C₄H₁₆N₃)[Ce(SO₄)₃(H₂O)]}_n, was hydrothermally synthesized. The Ce^III cation is nine-coordinated by nine O atoms, including one water molecule. Two of the SO₄ groups afford one monodentate and bidentate linkages as the bridge to connect adjacent Ce^III cations, while the third SO₄ group attaches the Ce^III cation in a bidentate mode. The crystal structure consists of layers composed of eight-membered-ring networks formed by four CeO₉ polyhedra and four SO₄ tetrahedra. The triply protonated diethylenetriamine cations are located between adjacent layers and connect the layers via hydrogen bonds.

Related literature

For related literature, see: Choudhury et al. (2001 ); Fu et al. (2006 ); Paul et al. (2002 ); Rao et al. (2006 ); Wickleder (2002 ).

Experimental

Crystal data

(C₄H₁₆N₃)[Ce(SO₄)₃(H₂O)]
M_r = 552.51
Monoclinic, P 2₁
a = 6.6774 (13) Å
b = 10.397 (2) Å
c = 11.093 (2) Å
β = 93.77 (3)°
V = 768.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 3.44 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995 ) T_min = 0.480, T_max = 0.561
7575 measured reflections
3485 independent reflections
3443 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.015
wR(F²) = 0.041
S = 1.15
3485 reflections
225 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.71 e Å⁻³
Absolute structure: Flack (1983 )
Flack parameter: −0.009 (8)

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O11ⁱ	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⋯O6ⁱⁱⁱ	0.89	2.05	2.852 (3)	150
N2—H2B⋯O11	0.90	1.92	2.764 (4)	156
N2—H2A⋯O2^iv	0.90	2.16	2.993 (3)	154
N2—H2A⋯O4^iv	0.90	2.30	2.997 (3)	134
N3—H3A⋯O5^v	0.89	2.17	2.808 (3)	128
N3—H3A⋯O3^vi	0.89	2.26	3.059 (4)	150
N3—H3C⋯O12^v	0.89	1.91	2.799 (4)	173
N3—H3B⋯O10^vii	0.89	2.04	2.763 (4)	137
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+2]$ ; (iii) x-1, y, z; (iv) x, y-1, z; (v) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (vi) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (vii) x-1, y-1, z.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810016600/hb5433sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016600/hb5433Isup2.hkl

checkCIF report

Comment top

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 Ce^III cation, three SO₄ groups, one coordination water and one protonated diethylene triamine cation, as shown in Fig.1. The Ce^III 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.

Related literature top

For related literature, see: Choudhury et al. (2001); Fu et al. (2006); Paul et al. (2002); Rao et al. (2006); Wickleder (2002).

Experimental top

(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).

Structure description top

For related literature, see: Choudhury et al. (2001); Fu et al. (2006); Paul et al. (2002); Rao et al. (2006); Wickleder (2002).

Computing details top

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).

Figures top

	Fig. 1. The unit cell of (I), showing the atomic labelling scheme and displacement ellipsoids at the 50% probability level. [Symmetry codes: (i) 1+x, y, z; (ii) 1-x, 0.5+y, -z.]
	Fig. 2. The stick plot of (I), displaying the layer along (101) direction composed by linking the Ce cation with µ₂-S(1)O₄ and µ₂-S(3)O₄. S(1) is shown in yellow, S(2) in green and S(3) in blue.

Poly[diethylenetriammonium [aquadi-µ₂-sulfato-sulfatocerium(III)]] top

Crystal data top

(C₄H₁₆N₃)[Ce(SO₄)₃(H₂O)]	F(000) = 546
M_r = 552.51	D_x = 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

Data collection top

Rigaku R-AXIS RAPID diffractometer	3485 independent reflections
Radiation source: fine-focus sealed tube	3443 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −7→8
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	k = −13→13
T_min = 0.480, T_max = 0.561	l = −14→14
7575 measured reflections

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)] = 0.015	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.041	w = 1/[σ²(F_o²) + (0.005P)² + 0.1027P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max = 0.001
3485 reflections	Δρ_max = 0.56 e Å⁻³
225 parameters	Δρ_min = −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)

Crystal data top

(C₄H₁₆N₃)[Ce(SO₄)₃(H₂O)]	V = 768.5 (3) Å³
M_r = 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)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3485 independent reflections
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	3443 reflections with I > 2σ(I)
T_min = 0.480, T_max = 0.561	R_int = 0.017
7575 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.015	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.041	Δρ_max = 0.56 e Å⁻³
S = 1.15	Δρ_min = −0.71 e Å⁻³
3485 reflections	Absolute structure: Flack (1983)
225 parameters	Absolute structure parameter: −0.009 (8)
4 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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—Ce1^iv	130.80 (10)
O7—Ce1—O9ⁱⁱ	124.15 (7)	O4—S3—Ce1^iv	130.80 (10)
O1W—Ce1—O9ⁱⁱ	148.88 (7)	O1—S3—Ce1^iv	118.49 (10)
O1—Ce1—O9ⁱⁱ	98.55 (7)	O9—S3—Ce1^iv	51.63 (9)
O5ⁱ—Ce1—O9ⁱⁱ	71.27 (7)	O2—S3—Ce1^iv	53.35 (8)
O6—Ce1—O9ⁱⁱ	79.38 (7)	S3—O1—Ce1	144.17 (13)
O8ⁱ—Ce1—O9ⁱⁱ	74.23 (7)	S3—O2—Ce1^iv	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—Ce1^iv	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—Ce1^iv	−126.59 (11)
O1W—Ce1—S2—O12	78.04 (14)	O4—S3—O2—Ce1^iv	−126.59 (11)
O1—Ce1—S2—O12	9.97 (17)	O1—S3—O2—Ce1^iv	111.08 (11)
O5ⁱ—Ce1—S2—O12	163.83 (14)	O9—S3—O2—Ce1^iv	−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)	Ce1^iv—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)
Ce1^iv—S3—O1—Ce1	158.70 (17)	O4—S3—O9—Ce1^iv	125.76 (12)
O7—Ce1—O1—S3	93.1 (2)	O4—S3—O9—Ce1^iv	125.76 (12)
O1W—Ce1—O1—S3	5.1 (2)	O1—S3—O9—Ce1^iv	−111.24 (12)
O5ⁱ—Ce1—O1—S3	−70.6 (3)	O2—S3—O9—Ce1^iv	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.

Hydrogen-bond geometry (Å, º) top

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···O11^v	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···O2^vi	0.90	2.16	2.993 (3)	154
N2—H2A···O4^vi	0.90	2.30	2.997 (3)	134
N3—H3A···O5^vii	0.89	2.17	2.808 (3)	128
N3—H3A···O3^viii	0.89	2.26	3.059 (4)	150
N3—H3C···O12^vii	0.89	1.91	2.799 (4)	173
N3—H3B···O10^ix	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)]
M_r	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)
T_min, T_max	0.480, 0.561
No. of measured, independent and observed [I > 2σ(I)] reflections	7575, 3485, 3443
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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···O2^iv	0.90	2.16	2.993 (3)	154.2
N2—H2A···O4^iv	0.90	2.30	2.997 (3)	133.8
N3—H3A···O5^v	0.89	2.17	2.808 (3)	127.7
N3—H3A···O3^vi	0.89	2.26	3.059 (4)	149.5
N3—H3C···O12^v	0.89	1.91	2.799 (4)	173.2
N3—H3B···O10^vii	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.

Acknowledgements

This project was sponsored by the Scientific Research Foundation for Returned Overseas Chinese Scholars, Chinese Education Ministry (grant No. 20071108) and the Scientific Research Foundation for the Returned Overseas Team, Chinese Education Ministry.

References

Brandenburg, K. (2000). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Choudhury, A., Krishnamoorthy, J. & Rao, C. N. R. (2001). Chem. Commun. pp. 2610–2611. Web of Science CSD CrossRef Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fu, Y., Xu, Z. & Ren, J. (2006). J. Mol. Struct. 788, 190–193. Web of Science CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Paul, G., Choudhury, A. & Rao, C. N. R. (2002). J. Chem. Soc. Dalton Trans. pp. 3859–3867. Web of Science CSD CrossRef Google Scholar
Rao, C. N. R., Behera, J. N. & Dan, M. (2006). Chem. Soc. Rev. 35, 375–387. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wickleder, M. S. (2002). Chem. Rev. 102, 2011–2087. Web of Science CrossRef PubMed CAS Google Scholar