catena-Poly[bis­(propane-1,3-diaminium) [[aqua­(sulfato-κO)bis­(sulfato-κ2O,O′)cerate(IV)]-μ-sulfato-κ3O,O′:O′′] dihydrate]

Meer, A.F.; Ahmad, S.; Sharif, S.; Khan, I.U.; Ng, S.W.

doi:10.1107/S1600536811008324

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m413

doi:10.1107/S1600536811008324

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catena-Poly[bis(propane-1,3-diaminium) [[aqua(sulfato-κO)bis(sulfato-κ²O,O′)cerate(IV)]-μ-sulfato-κ³O,O′:O′′] dihydrate]

Ali Farooq Meer,^a Saeed Ahmad,^a Shahzad Sharif,^b Islam Ullah Khan ^b and Seik Weng Ng ^c ^*

^aDepartment of Chemistry, University of Engineering and Technology, Lahore 54890, Pakistan, ^bMaterials Chemistry Laboratory, Department of Chemistry, Government College University, 54000 Lahore, Pakistan, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 11 February 2011; accepted 4 March 2011; online 9 March 2011)

The Ce^IV atom in the title salt, {(H₃NCH₂CH₂CH₂NH₃)₂[Ce(SO₄)₄(H₂O)]·2H₂O}_n, exists in a monocapped square-antiprismatic coordination geometry. The water-coordinated metal atom is bonded to four sulfate ions; one of them is monodentate and two function in a chelating mode. The fourth is also chelating but it uses one of the other two O atoms to bind to an adjacent metal atom, generating a polyanionic chain. The cations are linked to the polyanionic chain as well as to the uncoordinated water molecules, resulting in an O—H⋯O and N—H⋯O hydrogen-bonded three-dimensional network.

Related literature

For (C₂H₁₀N₂)₅[Ce₂(SO₄)₉]^.3H₂O, see: Jabeen et al. (2010 ).

Experimental

Crystal data

(C₃H₁₂N₂)₂[Ce(SO₄)₄(H₂O)]·2H₂O
M_r = 730.70
Monoclinic, P 2₁ /c
a = 8.9459 (1) Å
b = 20.4497 (3) Å
c = 12.8688 (2) Å
β = 99.535 (1)°
V = 2321.71 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.41 mm⁻¹
T = 295 K
0.30 × 0.15 × 0.10 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.531, T_max = 0.794
21238 measured reflections
5296 independent reflections
4663 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.071
S = 1.14
5296 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 1.24 e Å⁻³
Δρ_min = −1.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H1w2⋯O12ⁱ	0.84	2.05	2.854 (4)	162
O2w—H2w1⋯O11ⁱ	0.84	2.24	2.935 (5)	140
O2w—H2w2⋯O15ⁱⁱ	0.84	2.08	2.902 (5)	167
O3w—H3w1⋯O3ⁱ	0.84	1.90	2.729 (5)	169
O3w—H3w2⋯O2w	0.85	1.98	2.802 (5)	163
N1—H11⋯O9ⁱ	0.86	2.04	2.881 (4)	167
N1—H12⋯O3w	0.86	1.95	2.806 (5)	171
N1—H13⋯O13ⁱⁱⁱ	0.86	2.19	3.036 (4)	166
N2—H21⋯O16^iv	0.86	2.09	2.904 (5)	157
N2—H22⋯O16ⁱⁱ	0.86	2.25	2.978 (5)	142
N2—H23⋯O2	0.86	2.49	3.180 (6)	137
N2—H23⋯O5	0.86	2.44	2.989 (4)	122
N3—H31⋯O6^v	0.86	2.04	2.866 (4)	162
N3—H32⋯O4	0.86	2.37	2.882 (6)	119
N3—H32⋯O2w^vi	0.86	2.37	3.085 (6)	141
N3—H33⋯O1	0.86	2.33	3.004 (5)	135
N3—H33⋯O10	0.86	2.43	3.191 (6)	147
N4—H41⋯O6^vii	0.86	2.34	2.986 (4)	132
N4—H41⋯O15^vii	0.86	2.25	2.951 (5)	138
N4—H43⋯O4^viii	0.86	2.00	2.851 (5)	173
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) -x+1, -y, -z+1; (vii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (viii) -x+2, -y, -z+1.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008324/bt5471sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008324/bt5471Isup2.hkl

checkCIF report

Comment top

A previous study reports the isolation of pentakis(ethylenediammonium) µ-sulfato-bis[trisulfatocerate(IV) trihydrate, which was synthesized by the reaction of 1,2-diaminoethane with cerium(IV) sulfate (Jabeen et al., 2010). The two independent Ce atoms exist in a nine-coordinate geometry this is best described as a tricapped trigonal prism. Shortening the cationic chain results in the formatoin of a polyanion. The compound obtained with 1,3-diaminopropane in place of 1,2-diamionoethane is 2(H₃NCH₂CH₂CH₂NH₃) [Ce(H₂O)(SO₄)₄]^.2H₂O (Scheme I, Fig. 1). One of the sulfate ions behaving in a bridging mode to link adjacent cerate ions into a chain. The cations are linked to the polyanionic chain as well as to the lattice water molecules to result in a hydrogen-bonded three-dimensional network. The metal atom shows monocapped square-antiprismatic geometry (Fig. 2).

Related literature top

For (C₂H₁₀N₂)₅[Ce₂(SO₄)₉]^.3H₂O, see: Jabeen et al. (2010).

Experimental top

1,3-Diaminopropane (0.148 g, 2 mmol) was placed in a 1 N sulfuric acid solution (5 ml) of cerium(IV) sulfate tetrahydrate (0.202 g, 0.5 mmol). The yellow solution was filtered and then set aside for the growth of crystals.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of a portion of polymeric (H₃NCH₂CH₂CH₂NH₃) [Ce(H₂O)(SO₄)₄]^.2H₂O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Monocapped square-antiprismatic geometry of Ce(IV).

catena-Poly[bis(propane-1,3-diaminium) [[aqua(sulfato-κO)bis(sulfato-κ²O,O')cerate(IV)]- µ-sulfato-κ³O,O':O''] dihydrate] top

Crystal data top

(C₃H₁₂N₂)₂[Ce(SO₄)₄(H₂O)]·2H₂O	F(000) = 1472
M_r = 730.70	D_x = 2.090 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9960 reflections
a = 8.9459 (1) Å	θ = 2.8–28.3°
b = 20.4497 (3) Å	µ = 2.41 mm⁻¹
c = 12.8688 (2) Å	T = 295 K
β = 99.535 (1)°	Prism, yellow
V = 2321.71 (6) Å³	0.30 × 0.15 × 0.10 mm
Z = 4

Data collection top

Bruker Kappa APEXII diffractometer	5296 independent reflections
Radiation source: fine-focus sealed tube	4663 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.531, T_max = 0.794	k = −26→20
21238 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0167P)² + 7.615P] where P = (F_o² + 2F_c²)/3
5296 reflections	(Δ/σ)_max = 0.001
307 parameters	Δρ_max = 1.24 e Å⁻³
0 restraints	Δρ_min = −1.41 e Å⁻³

Crystal data top

(C₃H₁₂N₂)₂[Ce(SO₄)₄(H₂O)]·2H₂O	V = 2321.71 (6) Å³
M_r = 730.70	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.9459 (1) Å	µ = 2.41 mm⁻¹
b = 20.4497 (3) Å	T = 295 K
c = 12.8688 (2) Å	0.30 × 0.15 × 0.10 mm
β = 99.535 (1)°

Data collection top

Bruker Kappa APEXII diffractometer	5296 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4663 reflections with I > 2σ(I)
T_min = 0.531, T_max = 0.794	R_int = 0.024
21238 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 1.14	Δρ_max = 1.24 e Å⁻³
5296 reflections	Δρ_min = −1.41 e Å⁻³
307 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.

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

	x	y	z	U_iso*/U_eq
Ce1	0.682986 (19)	0.252538 (8)	0.326048 (13)	0.01407 (6)
S1	0.58776 (10)	0.08286 (4)	0.35192 (8)	0.02668 (19)
S2	0.57080 (9)	0.24695 (4)	0.08631 (6)	0.01880 (16)
S3	1.02446 (9)	0.22812 (4)	0.34548 (7)	0.02170 (17)
S4	0.66130 (10)	0.39960 (4)	0.35617 (7)	0.02449 (18)
O1	0.6789 (3)	0.14558 (12)	0.3672 (2)	0.0248 (5)
O2	0.4287 (3)	0.10079 (15)	0.3213 (4)	0.0588 (11)
O3	0.6376 (4)	0.04469 (15)	0.2697 (3)	0.0429 (7)
O4	0.6144 (4)	0.04863 (16)	0.4518 (3)	0.0530 (9)
O5	0.6001 (3)	0.19145 (12)	0.16128 (19)	0.0266 (5)
O6	0.6232 (3)	0.30497 (11)	0.15445 (18)	0.0227 (5)
O7	0.4153 (3)	0.25303 (17)	0.0394 (2)	0.0439 (8)
O8	0.6718 (3)	0.24052 (12)	0.00700 (19)	0.0246 (5)
O9	0.9026 (3)	0.23795 (12)	0.24892 (19)	0.0236 (5)
O10	0.9303 (3)	0.23354 (13)	0.4321 (2)	0.0253 (5)
O11	1.0895 (3)	0.16402 (14)	0.3425 (2)	0.0384 (7)
O12	1.1351 (3)	0.27980 (14)	0.3520 (2)	0.0323 (6)
O13	0.8002 (3)	0.35764 (12)	0.3595 (2)	0.0236 (5)
O14	0.5368 (3)	0.35021 (12)	0.3413 (2)	0.0231 (5)
O15	0.6465 (3)	0.44422 (15)	0.2677 (3)	0.0486 (8)
O16	0.6665 (3)	0.43396 (15)	0.4552 (3)	0.0436 (8)
O1w	0.4185 (3)	0.23056 (12)	0.3117 (2)	0.0245 (5)
H1w1	0.4039	0.1903	0.3164	0.037*
H1w2	0.3478	0.2512	0.3315	0.037*
O2w	0.1571 (4)	0.02367 (19)	0.3392 (3)	0.0621 (10)
H2w1	0.1834	0.0622	0.3559	0.093*
H2w2	0.2243	0.0057	0.3107	0.093*
O3w	−0.1048 (4)	0.02558 (18)	0.1859 (3)	0.0572 (9)
H3w1	−0.1861	0.0260	0.2112	0.086*
H3w2	−0.0325	0.0329	0.2360	0.086*
N1	−0.0516 (4)	0.14453 (17)	0.0895 (3)	0.0332 (7)
H11	−0.0698	0.1765	0.1290	0.050*
H12	−0.0780	0.1084	0.1155	0.050*
H13	−0.1022	0.1498	0.0272	0.050*
N2	0.4215 (4)	0.07383 (16)	0.0772 (3)	0.0334 (7)
H21	0.5087	0.0757	0.0575	0.050*
H22	0.4077	0.0352	0.1003	0.050*
H23	0.4179	0.1019	0.1264	0.050*
N3	0.8546 (4)	0.1186 (2)	0.5827 (3)	0.0539 (11)
H31	0.7883	0.1354	0.6161	0.081*
H32	0.8346	0.0778	0.5713	0.081*
H33	0.8522	0.1384	0.5236	0.081*
N4	1.3989 (4)	0.08791 (18)	0.5938 (3)	0.0445 (9)
H41	1.4856	0.0974	0.6304	0.067*
H42	1.3901	0.1068	0.5334	0.067*
H43	1.3920	0.0463	0.5851	0.067*
C1	0.1122 (4)	0.14262 (19)	0.0843 (3)	0.0308 (8)
H1A	0.1699	0.1367	0.1544	0.037*
H1B	0.1430	0.1836	0.0563	0.037*
C2	0.1438 (4)	0.0867 (2)	0.0140 (3)	0.0322 (8)
H2A	0.1307	0.0457	0.0493	0.039*
H2B	0.0703	0.0879	−0.0505	0.039*
C3	0.3013 (4)	0.0886 (2)	−0.0138 (3)	0.0348 (9)
H3A	0.3073	0.0572	−0.0694	0.042*
H3B	0.3193	0.1317	−0.0407	0.042*
C4	1.0041 (5)	0.1253 (2)	0.6454 (4)	0.0438 (11)
H4A	1.0057	0.1038	0.7128	0.053*
H4B	1.0260	0.1713	0.6587	0.053*
C5	1.1240 (5)	0.0961 (2)	0.5913 (4)	0.0379 (9)
H5A	1.1098	0.0491	0.5862	0.045*
H5B	1.1141	0.1134	0.5204	0.045*
C6	1.2785 (5)	0.1104 (3)	0.6490 (4)	0.0488 (12)
H6A	1.2885	0.1573	0.6600	0.059*
H6B	1.2907	0.0897	0.7177	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce1	0.01607 (9)	0.01389 (10)	0.01262 (9)	−0.00095 (6)	0.00347 (6)	−0.00052 (6)
S1	0.0263 (4)	0.0165 (4)	0.0378 (5)	−0.0020 (3)	0.0068 (4)	0.0034 (4)
S2	0.0183 (4)	0.0248 (4)	0.0135 (3)	−0.0014 (3)	0.0034 (3)	−0.0013 (3)
S3	0.0178 (4)	0.0231 (4)	0.0246 (4)	0.0031 (3)	0.0048 (3)	−0.0003 (3)
S4	0.0238 (4)	0.0151 (4)	0.0346 (5)	0.0002 (3)	0.0049 (3)	−0.0016 (3)
O1	0.0269 (13)	0.0162 (12)	0.0301 (13)	−0.0039 (10)	0.0017 (10)	0.0035 (10)
O2	0.0221 (14)	0.0242 (16)	0.129 (4)	−0.0024 (12)	0.0085 (17)	−0.0031 (18)
O3	0.0468 (17)	0.0337 (16)	0.0485 (19)	−0.0058 (13)	0.0090 (14)	−0.0141 (14)
O4	0.084 (3)	0.0323 (17)	0.0453 (19)	−0.0127 (16)	0.0176 (18)	0.0116 (14)
O5	0.0414 (15)	0.0198 (12)	0.0197 (12)	−0.0089 (11)	0.0079 (10)	−0.0012 (10)
O6	0.0318 (13)	0.0166 (12)	0.0197 (12)	0.0016 (10)	0.0045 (9)	−0.0005 (9)
O7	0.0197 (13)	0.082 (3)	0.0286 (15)	0.0005 (14)	0.0004 (11)	−0.0020 (15)
O8	0.0264 (12)	0.0317 (14)	0.0173 (12)	0.0022 (10)	0.0085 (10)	0.0005 (10)
O9	0.0202 (11)	0.0301 (14)	0.0204 (12)	0.0001 (10)	0.0031 (9)	−0.0020 (10)
O10	0.0210 (12)	0.0319 (14)	0.0230 (13)	0.0031 (10)	0.0039 (9)	0.0037 (10)
O11	0.0404 (16)	0.0291 (15)	0.0460 (18)	0.0150 (12)	0.0087 (13)	0.0000 (13)
O12	0.0199 (12)	0.0370 (16)	0.0395 (16)	−0.0061 (11)	0.0037 (11)	−0.0016 (12)
O13	0.0197 (11)	0.0184 (12)	0.0326 (14)	−0.0008 (9)	0.0041 (10)	−0.0020 (10)
O14	0.0205 (11)	0.0198 (12)	0.0294 (13)	−0.0002 (9)	0.0049 (10)	−0.0038 (10)
O15	0.0407 (17)	0.0327 (17)	0.069 (2)	0.0003 (13)	0.0012 (15)	0.0261 (16)
O16	0.0383 (16)	0.0337 (16)	0.060 (2)	−0.0041 (13)	0.0110 (14)	−0.0263 (15)
O1w	0.0227 (12)	0.0217 (12)	0.0302 (14)	−0.0015 (10)	0.0076 (10)	−0.0023 (10)
O2w	0.049 (2)	0.054 (2)	0.086 (3)	−0.0027 (17)	0.0191 (19)	0.005 (2)
O3w	0.053 (2)	0.064 (2)	0.056 (2)	−0.0085 (18)	0.0129 (17)	−0.0049 (18)
N1	0.0322 (17)	0.0359 (19)	0.0298 (17)	0.0104 (14)	0.0005 (13)	−0.0055 (14)
N2	0.0296 (16)	0.0261 (17)	0.044 (2)	−0.0017 (13)	0.0034 (14)	−0.0044 (15)
N3	0.037 (2)	0.076 (3)	0.047 (2)	0.022 (2)	0.0011 (17)	−0.008 (2)
N4	0.0301 (18)	0.033 (2)	0.073 (3)	−0.0063 (15)	0.0152 (18)	−0.0067 (18)
C1	0.033 (2)	0.029 (2)	0.030 (2)	0.0023 (16)	0.0053 (15)	−0.0011 (16)
C2	0.0249 (18)	0.035 (2)	0.037 (2)	−0.0001 (16)	0.0035 (15)	−0.0076 (17)
C3	0.033 (2)	0.041 (2)	0.031 (2)	0.0027 (17)	0.0079 (16)	−0.0011 (17)
C4	0.035 (2)	0.046 (3)	0.049 (3)	0.0014 (19)	0.0043 (19)	−0.012 (2)
C5	0.037 (2)	0.035 (2)	0.042 (2)	0.0055 (18)	0.0066 (18)	−0.0005 (18)
C6	0.037 (2)	0.049 (3)	0.062 (3)	−0.007 (2)	0.012 (2)	−0.015 (2)

Geometric parameters (Å, º) top

Ce1—O1	2.252 (2)	N1—C1	1.479 (5)
Ce1—O8ⁱ	2.352 (2)	N1—H11	0.8600
Ce1—O9	2.362 (2)	N1—H12	0.8600
Ce1—O1w	2.385 (2)	N1—H13	0.8600
Ce1—O13	2.399 (2)	N2—C3	1.484 (5)
Ce1—O14	2.413 (2)	N2—H21	0.8600
Ce1—O10	2.431 (2)	N2—H22	0.8600
Ce1—O6	2.433 (2)	N2—H23	0.8600
Ce1—O5	2.467 (2)	N3—C4	1.450 (6)
S1—O3	1.444 (3)	N3—H31	0.8600
S1—O4	1.448 (3)	N3—H32	0.8600
S1—O2	1.459 (3)	N3—H33	0.8600
S1—O1	1.515 (2)	N4—C6	1.460 (6)
S2—O7	1.427 (3)	N4—H41	0.8600
S2—O8	1.477 (2)	N4—H42	0.8600
S2—O5	1.485 (3)	N4—H43	0.8600
S2—O6	1.503 (2)	C1—C2	1.514 (5)
S3—O11	1.437 (3)	C1—H1A	0.9700
S3—O12	1.441 (3)	C1—H1B	0.9700
S3—O10	1.508 (3)	C2—C3	1.510 (5)
S3—O9	1.524 (3)	C2—H2A	0.9700
S4—O15	1.448 (3)	C2—H2B	0.9700
S4—O16	1.449 (3)	C3—H3A	0.9700
S4—O14	1.492 (2)	C3—H3B	0.9700
S4—O13	1.505 (2)	C4—C5	1.496 (6)
O8—Ce1ⁱⁱ	2.352 (2)	C4—H4A	0.9700
O1w—H1w1	0.8368	C4—H4B	0.9700
O1w—H1w2	0.8351	C5—C6	1.486 (6)
O2w—H2w1	0.8401	C5—H5A	0.9700
O2w—H2w2	0.8390	C5—H5B	0.9700
O3w—H3w1	0.8444	C6—H6A	0.9700
O3w—H3w2	0.8478	C6—H6B	0.9700

O1—Ce1—O8ⁱ	79.66 (9)	S4—O14—Ce1	99.66 (12)
O1—Ce1—O9	91.34 (9)	Ce1—O1w—H1w1	110.1
O8ⁱ—Ce1—O9	126.76 (9)	Ce1—O1w—H1w2	132.2
O1—Ce1—O1w	77.33 (9)	H1w1—O1w—H1w2	109.9
O8ⁱ—Ce1—O1w	83.33 (9)	H2w1—O2w—H2w2	109.4
O9—Ce1—O1w	145.79 (8)	H3w1—O3w—H3w2	107.6
O1—Ce1—O13	148.37 (9)	C1—N1—H11	109.5
O8ⁱ—Ce1—O13	81.78 (9)	C1—N1—H12	109.5
O9—Ce1—O13	79.59 (8)	H11—N1—H12	109.5
O1w—Ce1—O13	125.54 (8)	C1—N1—H13	109.5
O1—Ce1—O14	138.98 (8)	H11—N1—H13	109.5
O8ⁱ—Ce1—O14	75.94 (9)	H12—N1—H13	109.5
O9—Ce1—O14	129.67 (8)	C3—N2—H21	109.5
O1w—Ce1—O14	67.56 (8)	C3—N2—H22	109.5
O13—Ce1—O14	58.03 (8)	H21—N2—H22	109.5
O1—Ce1—O10	76.20 (9)	C3—N2—H23	109.5
O8ⁱ—Ce1—O10	68.77 (8)	H21—N2—H23	109.5
O9—Ce1—O10	58.17 (8)	H22—N2—H23	109.5
O1w—Ce1—O10	144.34 (9)	C4—N3—H31	109.5
O13—Ce1—O10	73.27 (8)	C4—N3—H32	109.5
O14—Ce1—O10	122.81 (8)	H31—N3—H32	109.5
O1—Ce1—O6	129.18 (9)	C4—N3—H33	109.5
O8ⁱ—Ce1—O6	146.41 (8)	H31—N3—H33	109.5
O9—Ce1—O6	75.37 (8)	H32—N3—H33	109.5
O1w—Ce1—O6	86.94 (8)	C6—N4—H41	109.5
O13—Ce1—O6	78.00 (8)	C6—N4—H42	109.5
O14—Ce1—O6	70.63 (8)	H41—N4—H42	109.5
O10—Ce1—O6	128.51 (8)	C6—N4—H43	109.5
O1—Ce1—O5	72.31 (9)	H41—N4—H43	109.5
O8ⁱ—Ce1—O5	145.65 (8)	H42—N4—H43	109.5
O9—Ce1—O5	74.19 (8)	N1—C1—C2	109.4 (3)
O1w—Ce1—O5	71.61 (9)	N1—C1—H1A	109.8
O13—Ce1—O5	131.94 (8)	C2—C1—H1A	109.8
O14—Ce1—O5	113.52 (9)	N1—C1—H1B	109.8
O10—Ce1—O5	121.19 (9)	C2—C1—H1B	109.8
O6—Ce1—O5	56.88 (8)	H1A—C1—H1B	108.2
O3—S1—O4	111.3 (2)	C3—C2—C1	113.3 (3)
O3—S1—O2	110.1 (2)	C3—C2—H2A	108.9
O4—S1—O2	111.7 (2)	C1—C2—H2A	108.9
O3—S1—O1	109.16 (17)	C3—C2—H2B	108.9
O4—S1—O1	106.74 (18)	C1—C2—H2B	108.9
O2—S1—O1	107.59 (16)	H2A—C2—H2B	107.7
O7—S2—O8	112.34 (16)	N2—C3—C2	113.0 (3)
O7—S2—O5	113.34 (18)	N2—C3—H3A	109.0
O8—S2—O5	108.60 (15)	C2—C3—H3A	109.0
O7—S2—O6	111.47 (17)	N2—C3—H3B	109.0
O8—S2—O6	107.82 (14)	C2—C3—H3B	109.0
O5—S2—O6	102.71 (14)	H3A—C3—H3B	107.8
O11—S3—O12	113.18 (17)	N3—C4—C5	111.7 (4)
O11—S3—O10	111.37 (17)	N3—C4—H4A	109.3
O12—S3—O10	111.43 (16)	C5—C4—H4A	109.3
O11—S3—O9	109.67 (17)	N3—C4—H4B	109.3
O12—S3—O9	110.01 (16)	C5—C4—H4B	109.3
O10—S3—O9	100.44 (14)	H4A—C4—H4B	107.9
O15—S4—O16	111.8 (2)	C6—C5—C4	111.5 (4)
O15—S4—O14	110.90 (17)	C6—C5—H5A	109.3
O16—S4—O14	110.85 (16)	C4—C5—H5A	109.3
O15—S4—O13	110.46 (17)	C6—C5—H5B	109.3
O16—S4—O13	110.17 (17)	C4—C5—H5B	109.3
O14—S4—O13	102.30 (14)	H5A—C5—H5B	108.0
S1—O1—Ce1	145.18 (15)	N4—C6—C5	113.2 (4)
S2—O5—Ce1	99.61 (12)	N4—C6—H6A	108.9
S2—O6—Ce1	100.49 (12)	C5—C6—H6A	108.9
S2—O8—Ce1ⁱⁱ	144.13 (15)	N4—C6—H6B	108.9
S3—O9—Ce1	101.91 (12)	C5—C6—H6B	108.9
S3—O10—Ce1	99.48 (12)	H6A—C6—H6B	107.7
S4—O13—Ce1	99.86 (12)

O3—S1—O1—Ce1	96.8 (3)	O13—Ce1—O9—S3	76.58 (13)
O4—S1—O1—Ce1	−142.7 (3)	O14—Ce1—O9—S3	108.19 (13)
O2—S1—O1—Ce1	−22.7 (4)	O10—Ce1—O9—S3	−0.09 (11)
O8ⁱ—Ce1—O1—S1	112.7 (3)	O6—Ce1—O9—S3	156.76 (14)
O9—Ce1—O1—S1	−120.1 (3)	O5—Ce1—O9—S3	−144.11 (14)
O1w—Ce1—O1—S1	27.3 (3)	O11—S3—O10—Ce1	−116.21 (16)
O13—Ce1—O1—S1	167.8 (2)	O12—S3—O10—Ce1	116.37 (15)
O14—Ce1—O1—S1	58.6 (3)	O9—S3—O10—Ce1	−0.13 (15)
O10—Ce1—O1—S1	−176.8 (3)	O1—Ce1—O10—S3	100.51 (14)
O6—Ce1—O1—S1	−48.0 (3)	O8ⁱ—Ce1—O10—S3	−175.39 (15)
O5—Ce1—O1—S1	−47.2 (3)	O9—Ce1—O10—S3	0.09 (11)
O7—S2—O5—Ce1	−115.29 (16)	O1w—Ce1—O10—S3	143.65 (13)
O8—S2—O5—Ce1	119.11 (13)	O13—Ce1—O10—S3	−87.88 (13)
O6—S2—O5—Ce1	5.10 (15)	O14—Ce1—O10—S3	−119.49 (13)
O1—Ce1—O5—S2	177.08 (15)	O6—Ce1—O10—S3	−28.99 (18)
O8ⁱ—Ce1—O5—S2	140.24 (13)	O5—Ce1—O10—S3	41.46 (16)
O9—Ce1—O5—S2	−86.27 (13)	O15—S4—O13—Ce1	−114.54 (17)
O1w—Ce1—O5—S2	94.93 (14)	O16—S4—O13—Ce1	121.47 (16)
O13—Ce1—O5—S2	−26.73 (18)	O14—S4—O13—Ce1	3.56 (15)
O14—Ce1—O5—S2	40.62 (15)	O1—Ce1—O13—S4	−135.59 (15)
O10—Ce1—O5—S2	−121.98 (13)	O8ⁱ—Ce1—O13—S4	−81.04 (13)
O6—Ce1—O5—S2	−3.67 (11)	O9—Ce1—O13—S4	149.06 (14)
O7—S2—O6—Ce1	116.49 (16)	O1w—Ce1—O13—S4	−5.37 (17)
O8—S2—O6—Ce1	−119.76 (13)	O14—Ce1—O13—S4	−2.54 (11)
O5—S2—O6—Ce1	−5.19 (15)	O10—Ce1—O13—S4	−151.25 (14)
O1—Ce1—O6—S2	4.56 (17)	O6—Ce1—O13—S4	71.98 (13)
O8ⁱ—Ce1—O6—S2	−139.44 (13)	O5—Ce1—O13—S4	91.57 (15)
O9—Ce1—O6—S2	84.09 (12)	O15—S4—O14—Ce1	114.25 (18)
O1w—Ce1—O6—S2	−66.35 (12)	O16—S4—O14—Ce1	−120.97 (16)
O13—Ce1—O6—S2	166.31 (13)	O13—S4—O14—Ce1	−3.54 (15)
O14—Ce1—O6—S2	−133.63 (14)	O1—Ce1—O14—S4	146.82 (12)
O10—Ce1—O6—S2	109.35 (13)	O8ⁱ—Ce1—O14—S4	91.56 (13)
O5—Ce1—O6—S2	3.63 (11)	O9—Ce1—O14—S4	−34.86 (17)
O7—S2—O8—Ce1ⁱⁱ	9.8 (3)	O1w—Ce1—O14—S4	−179.93 (15)
O5—S2—O8—Ce1ⁱⁱ	136.0 (2)	O13—Ce1—O14—S4	2.56 (11)
O6—S2—O8—Ce1ⁱⁱ	−113.4 (3)	O10—Ce1—O14—S4	38.84 (16)
O11—S3—O9—Ce1	117.48 (15)	O6—Ce1—O14—S4	−85.13 (13)
O12—S3—O9—Ce1	−117.42 (15)	O5—Ce1—O14—S4	−123.43 (12)
O10—S3—O9—Ce1	0.13 (15)	N1—C1—C2—C3	168.6 (3)
O1—Ce1—O9—S3	−72.92 (13)	C1—C2—C3—N2	70.0 (5)
O8ⁱ—Ce1—O9—S3	5.16 (17)	N3—C4—C5—C6	172.7 (4)
O1w—Ce1—O9—S3	−142.07 (13)	C4—C5—C6—N4	−174.8 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w2···O12ⁱⁱⁱ	0.84	2.05	2.854 (4)	162
O2w—H2w1···O11ⁱⁱⁱ	0.84	2.24	2.935 (5)	140
O2w—H2w2···O15^iv	0.84	2.08	2.902 (5)	167
O3w—H3w1···O3ⁱⁱⁱ	0.84	1.90	2.729 (5)	169
O3w—H3w2···O2w	0.85	1.98	2.802 (5)	163
N1—H11···O9ⁱⁱⁱ	0.86	2.04	2.881 (4)	167
N1—H12···O3w	0.86	1.95	2.806 (5)	171
N1—H13···O13^v	0.86	2.19	3.036 (4)	166
N2—H21···O16ⁱⁱ	0.86	2.09	2.904 (5)	157
N2—H22···O16^iv	0.86	2.25	2.978 (5)	142
N2—H23···O2	0.86	2.49	3.180 (6)	137
N2—H23···O5	0.86	2.44	2.989 (4)	122
N3—H31···O6ⁱ	0.86	2.04	2.866 (4)	162
N3—H32···O4	0.86	2.37	2.882 (6)	119
N3—H32···O2w^vi	0.86	2.37	3.085 (6)	141
N3—H33···O1	0.86	2.33	3.004 (5)	135
N3—H33···O10	0.86	2.43	3.191 (6)	147
N4—H41···O6^vii	0.86	2.34	2.986 (4)	132
N4—H41···O15^vii	0.86	2.25	2.951 (5)	138
N4—H43···O4^viii	0.86	2.00	2.851 (5)	173

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

Experimental details

Crystal data
Chemical formula	(C₃H₁₂N₂)₂[Ce(SO₄)₄(H₂O)]·2H₂O
M_r	730.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	8.9459 (1), 20.4497 (3), 12.8688 (2)
β (°)	99.535 (1)
V (Å³)	2321.71 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.41
Crystal size (mm)	0.30 × 0.15 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.531, 0.794
No. of measured, independent and observed [I > 2σ(I)] reflections	21238, 5296, 4663
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.071, 1.14
No. of reflections	5296
No. of parameters	307
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.24, −1.41

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w2···O12ⁱ	0.84	2.05	2.854 (4)	162
O2w—H2w1···O11ⁱ	0.84	2.24	2.935 (5)	140
O2w—H2w2···O15ⁱⁱ	0.84	2.08	2.902 (5)	167
O3w—H3w1···O3ⁱ	0.84	1.90	2.729 (5)	169
O3w—H3w2···O2w	0.85	1.98	2.802 (5)	163
N1—H11···O9ⁱ	0.86	2.04	2.881 (4)	167
N1—H12···O3w	0.86	1.95	2.806 (5)	171
N1—H13···O13ⁱⁱⁱ	0.86	2.19	3.036 (4)	166
N2—H21···O16^iv	0.86	2.09	2.904 (5)	157
N2—H22···O16ⁱⁱ	0.86	2.25	2.978 (5)	142
N2—H23···O2	0.86	2.49	3.180 (6)	137
N2—H23···O5	0.86	2.44	2.989 (4)	122
N3—H31···O6^v	0.86	2.04	2.866 (4)	162
N3—H32···O4	0.86	2.37	2.882 (6)	119
N3—H32···O2w^vi	0.86	2.37	3.085 (6)	141
N3—H33···O1	0.86	2.33	3.004 (5)	135
N3—H33···O10	0.86	2.43	3.191 (6)	147
N4—H41···O6^vii	0.86	2.34	2.986 (4)	132
N4—H41···O15^vii	0.86	2.25	2.951 (5)	138
N4—H43···O4^viii	0.86	2.00	2.851 (5)	173

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

Acknowledgements

We thank the Higher Education Commission of Pakistan, GC University and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
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Jabeen, N., Ahmad, S., Meer, A. F., Khan, I. U. & Ng, S. W. (2010). Acta Cryst. E66, m797–m798. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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