Poly[[dodeca­aqua­(μ4-benzene-1,4-dicarboxyl­ato)(μ2-4,4′-bipyridine-κ2N:N′)dicerium(III)] bis­(benzene-1,4-dicarboxyl­ate)]

Kumagai, H.; Sakamoto, Y.; Kawata, S.; Inagaki, S.

doi:10.1107/S1600536812016388

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages m643-m644

doi:10.1107/S1600536812016388

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Poly[[dodecaaqua(μ₄-benzene-1,4-dicarboxylato)(μ₂-4,4′-bipyridine-κ²N:N′)dicerium(III)] bis(benzene-1,4-dicarboxylate)]

Hitoshi Kumagai,^a ^* Yoshiyuki Sakamoto,^a Satoshi Kawata ^b and Shinji Inagaki ^a

^aToyota Central R and D Labs. Inc., Nagakute 41-1, Aichi, Japan, and ^bDepartment of Chemistry, Fukuoka University, Fukuoka 814-0180, Japan
^*Correspondence e-mail: e1254@mosk.tytlabs.co.jp

(Received 29 March 2012; accepted 15 April 2012; online 21 April 2012)

The asymmetric unit of the title compound, {[Ce₂(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)₁₂](C₈H₄O₄)₂}_n, consists of half a Ce^III cation, a quarter of a coordinated benzene-1,4-dicarboxylate (bdc²⁻) dianion, a quarter of a 4,4′-bipyridine (bpy) molecule, three water molecules and a half of an uncoordinated benzene-1,4-dicarboxylate dianion. The Ce^III ion is located on a twofold rotation axis and exhibits a distorted trigonal prism square-face tricapped coordination geometry. The coordinated and uncoordinated bdc²⁻ ions and the bpy molecule lie about special positions of site symmetries 2/m, m and 2/m, respectively. The Ce^III ions are bridged by the bdc²⁻ and bpy ligands, giving a sheet structure parallel to the ac plane. The uncoordinated bdc²⁻ dianion exists between the sheets and links the sheets by intermolecular O—H⋯O hydrogen bonds between the uncoordinated bdc²⁻ and coordinated water molecules. A π–π stacking interaction between the uncoordinated bdc²⁻ dianion and the bpy ligand [centroid–centroid distance = 3.750 (4) Å] is also observed.

Related literature

For coordination polymers, see: Cheetham et al. (1999 ); Furukawa et al. (2010 ). For related host–guest systems, see: Kawata & Kitagawa (2002 ).

Experimental

Crystal data

[Ce₂(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)₁₂](C₈H₄O₄)₂
M_r = 572.48
Orthorhombic, P n n m
a = 6.112 (4) Å
b = 14.278 (8) Å
c = 22.395 (12) Å
V = 1954.3 (18) Å³
Z = 4
Mo Kα radiation
μ = 2.40 mm⁻¹
T = 293 K
0.60 × 0.20 × 0.10 mm

Data collection

Rigaku Mercury70 diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998 ) T_min = 0.511, T_max = 0.787
14945 measured reflections
2246 independent reflections
2163 reflections with F² > 2σ(F²)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.068
S = 1.39
2246 reflections
167 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Selected bond lengths (Å)

Ce1—O1	2.479 (3)
Ce1—O1ⁱ	2.479 (3)
Ce1—O2	2.530 (3)
Ce1—O2ⁱ	2.530 (3)
Ce1—O3	2.551 (3)
Ce1—O3ⁱ	2.551 (3)
Ce1—O4	2.533 (3)
Ce1—O4ⁱ	2.533 (3)
Ce1—N1	2.873 (5)
Symmetry code: (i) -x+2, -y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O5	0.84 (4)	1.93 (4)	2.754 (5)	167 (5)
O2—H3⋯O6ⁱⁱ	0.84 (3)	1.90 (4)	2.725 (5)	166 (4)
O3—H4⋯O5	0.83 (5)	2.02 (5)	2.828 (4)	164 (6)
O3—H5⋯O6ⁱⁱⁱ	0.84 (5)	1.81 (5)	2.650 (4)	175 (6)
O4—H7⋯O5^iv	0.84 (4)	1.91 (4)	2.749 (5)	174 (6)
Symmetry codes: (ii) x+1, y, z; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR2008 (Burla et al., 2007 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: CrystalStructure (Rigaku, 2010 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812016388/is5110sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016388/is5110Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536812016388/is5110Isup4.cdx

checkCIF report

Comment top

The design of coordination polymers (CPs), also known as metal-organic frameworks (MOFs), have received considerable attention in recent years due to potential applications for sorption, catalysis, optical, magnetic materials and host-guest interactions (Cheetham et al., 1999; Furukawa et al., 2010; Kawata & Kitagawa, 2002). Here we report synthesis and single-crystal structure of the title compound.

The coordination polymer of the title compound, {[Ce₂(C₈H₄O₄)(C₁₀H₁₀N₂)(H₂O)₁₂](C₈H₄O₄)₂}_n, consists of Ce^III ions, bdc^2- dianions and bpy as bridging ligands, and water molecules. In the crystal, two types of bdc^2- dianions are found. One bdc^2- dianion coordinates to Ce^III ions and acts as a bridging ligand to form a two-dimensional network. The other is an uncoordinated bdc^2- dianion. Uncoordinated bdc^2- dianions are stabilized by intermolecular hydrogen bonds between the uncoordinated bdc^2- and coordinated water molecules and π–π stacking interactions between uncoordinated bdc^2- dianions and bridging ligands to give a three-dimensional network structure.

Related literature top

For coordination polymers, see: Cheetham et al. (1999); Furukawa et al. (2010). For related host–guest systems, see: Kawata & Kitagawa (2002).

Experimental top

An aqueous solution (5 ml) of cerium nitrate hexahydrate (0.81 g) was transferred to a glass tube, then an ethanol-water mixture (5 ml) of tetrabromoerephthalic acid (0.2 g), NaOH (0.08 g) and 4,4'-bpy (0.19 g) was poured into the glass tube without mixing the two solutions. Colorless crystals began to form at ambient temperature in 1 month. One of these crystals was used for X-ray crystallography.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SIR2008 (Burla et al., 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures top

	Fig. 1. View of the title compound with atomic numbering scheme. Hydrogen atoms have been omitted for clarity. [Symmetry codes: (i) -x + 2, -y, z; (iii) x, y, -z + 1; (iv) -x + 2, -y, -z; (vii) x, y, -z.]
	Fig. 2. Packing diagram of the title compound, showing a sheet structure. Hydrogen atoms have been omitted for clarity.
	Fig. 3. Hydrogen bonding interactions for the title compound. Hydrogen atoms and hydrogen bonding interactions are shown as purple color and dashed line, respectively.

Poly[[dodecaaqua(µ₄-benzene-1,4-dicarboxylato)(µ₂-4,4'-bipyridine- κ²N:N')dicerium(III)] bis(benzene-1,4-dicarboxylate)] top

Crystal data top

[Ce₂(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)₁₂](C₈H₄O₄)₂	F(000) = 1140.00
M_r = 572.48	D_x = 1.946 Mg m⁻³
Orthorhombic, Pnnm	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2 2n	Cell parameters from 3992 reflections
a = 6.112 (4) Å	θ = 3.1–27.5°
b = 14.278 (8) Å	µ = 2.40 mm⁻¹
c = 22.395 (12) Å	T = 293 K
V = 1954.3 (18) Å³	Platelet, colorless
Z = 4	0.60 × 0.20 × 0.10 mm

Data collection top

Rigaku Mercury70 diffractometer	2163 reflections with F² > 2σ(F²)
Detector resolution: 7.314 pixels mm^-1	R_int = 0.029
ω scans	θ_max = 27.5°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −7→7
T_min = 0.511, T_max = 0.787	k = −18→18
14945 measured reflections	l = −29→29
2246 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.39	w = 1/[σ²(F_o²) + (0.P)² + 7.6254P] where P = (F_o² + 2F_c²)/3
2246 reflections	(Δ/σ)_max < 0.001
167 parameters	Δρ_max = 0.49 e Å⁻³
6 restraints	Δρ_min = −0.42 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

[Ce₂(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)₁₂](C₈H₄O₄)₂	V = 1954.3 (18) Å³
M_r = 572.48	Z = 4
Orthorhombic, Pnnm	Mo Kα radiation
a = 6.112 (4) Å	µ = 2.40 mm⁻¹
b = 14.278 (8) Å	T = 293 K
c = 22.395 (12) Å	0.60 × 0.20 × 0.10 mm

Data collection top

Rigaku Mercury70 diffractometer	2246 independent reflections
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	2163 reflections with F² > 2σ(F²)
T_min = 0.511, T_max = 0.787	R_int = 0.029
14945 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	6 restraints
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.39	Δρ_max = 0.49 e Å⁻³
2246 reflections	Δρ_min = −0.42 e Å⁻³
167 parameters

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (σt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (σt).

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

	x	y	z	U_iso*/U_eq
Ce1	1.0000	0.0000	0.286968 (11)	0.01450 (9)
O1	0.6621 (5)	0.03486 (19)	0.34397 (11)	0.0229 (6)
O2	1.0784 (5)	0.1316 (2)	0.35957 (13)	0.0257 (6)
O3	0.8063 (5)	0.14579 (19)	0.24774 (12)	0.0234 (6)
O4	0.6817 (5)	−0.0885 (2)	0.24157 (13)	0.0259 (6)
O5	0.7801 (5)	0.2740 (2)	0.34373 (11)	0.0276 (7)
O6	0.4224 (6)	0.2508 (3)	0.34529 (12)	0.0331 (8)
N1	1.0000	0.0000	0.15870 (19)	0.0230 (10)
C1	0.5000	0.0000	0.4378 (2)	0.0152 (9)
C2	0.6884 (6)	0.0245 (3)	0.46904 (14)	0.0171 (8)
C3	0.5000	0.0000	0.37044 (19)	0.0152 (9)
C4	0.8241 (7)	0.0259 (3)	0.12810 (16)	0.0252 (9)
C5	0.8174 (7)	0.0271 (3)	0.06620 (16)	0.0244 (9)
C6	1.0000	0.0000	0.0334 (2)	0.0187 (10)
C7	0.6065 (7)	0.2588 (3)	0.43811 (15)	0.0182 (7)
C8	0.7943 (7)	0.2825 (3)	0.46897 (16)	0.0209 (8)
C9	0.4180 (7)	0.2347 (3)	0.46905 (15)	0.0218 (8)
C10	0.6024 (7)	0.2610 (3)	0.37083 (16)	0.0214 (8)
H1	0.8145	0.0410	0.4483	0.0206*
H2	0.983 (7)	0.174 (3)	0.361 (3)	0.041 (15)*
H3	1.197 (5)	0.160 (3)	0.353 (2)	0.030 (14)*
H4	0.778 (11)	0.188 (4)	0.272 (2)	0.07 (2)*
H5	0.848 (10)	0.176 (4)	0.2178 (18)	0.062 (19)*
H6	0.555 (5)	−0.094 (5)	0.255 (3)	0.059 (19)*
H7	0.684 (10)	−0.130 (3)	0.2149 (18)	0.053 (17)*
H8	0.6998	0.0439	0.1491	0.0303*
H9	0.6908	0.0461	0.0466	0.0293*
H10	0.9207	0.2984	0.4482	0.0251*
H11	0.2917	0.2186	0.4483	0.0262*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce1	0.01572 (15)	0.01786 (15)	0.00993 (13)	−0.00118 (11)	0.0000	0.0000
O1	0.0214 (14)	0.0323 (15)	0.0151 (12)	−0.0021 (12)	0.0063 (11)	−0.0001 (11)
O2	0.0233 (15)	0.0241 (15)	0.0296 (15)	0.0009 (13)	−0.0026 (13)	−0.0080 (12)
O3	0.0324 (17)	0.0219 (14)	0.0160 (13)	0.0043 (13)	0.0037 (12)	0.0031 (11)
O4	0.0189 (15)	0.0319 (16)	0.0269 (15)	−0.0084 (13)	0.0037 (12)	−0.0094 (12)
O5	0.0305 (17)	0.0330 (16)	0.0191 (13)	0.0052 (14)	0.0063 (12)	0.0056 (11)
O6	0.0366 (18)	0.0413 (18)	0.0215 (14)	−0.0084 (15)	−0.0094 (13)	0.0093 (13)
N1	0.024 (3)	0.022 (3)	0.023 (2)	−0.004 (3)	0.0000	0.0000
C1	0.017 (3)	0.017 (3)	0.011 (2)	0.001 (3)	0.0000	0.0000
C2	0.0144 (18)	0.0205 (19)	0.0165 (17)	−0.0018 (14)	0.0031 (14)	0.0010 (13)
C3	0.020 (3)	0.014 (3)	0.012 (2)	0.002 (3)	0.0000	0.0000
C4	0.023 (2)	0.033 (3)	0.0206 (18)	0.0004 (17)	0.0021 (15)	−0.0021 (15)
C5	0.023 (2)	0.031 (3)	0.0193 (18)	0.0004 (17)	−0.0021 (15)	−0.0005 (15)
C6	0.025 (3)	0.015 (3)	0.016 (3)	−0.009 (3)	0.0000	0.0000
C7	0.0205 (19)	0.0173 (18)	0.0167 (16)	0.0034 (15)	0.0002 (14)	0.0015 (13)
C8	0.017 (2)	0.0222 (19)	0.0233 (19)	−0.0012 (16)	0.0033 (15)	0.0021 (15)
C9	0.0181 (19)	0.027 (2)	0.0199 (18)	0.0009 (16)	−0.0045 (15)	0.0000 (15)
C10	0.029 (2)	0.0168 (18)	0.0184 (17)	0.0037 (16)	−0.0012 (15)	0.0026 (14)

Geometric parameters (Å, º) top

Ce1—O1	2.479 (3)	C5—C6	1.391 (5)
Ce1—O1ⁱ	2.479 (3)	C6—C6^iv	1.496 (7)
Ce1—O2	2.530 (3)	C7—C8	1.382 (6)
Ce1—O2ⁱ	2.530 (3)	C7—C9	1.388 (6)
Ce1—O3	2.551 (3)	C7—C10	1.507 (5)
Ce1—O3ⁱ	2.551 (3)	C8—C8ⁱⁱⁱ	1.390 (6)
Ce1—O4	2.533 (3)	C9—C9ⁱⁱⁱ	1.386 (5)
Ce1—O4ⁱ	2.533 (3)	O2—H2	0.84 (4)
Ce1—N1	2.873 (5)	O2—H3	0.84 (4)
O1—C3	1.257 (4)	O3—H4	0.83 (5)
O5—C10	1.258 (5)	O3—H5	0.84 (5)
O6—C10	1.248 (5)	O4—H6	0.84 (4)
N1—C4	1.327 (5)	O4—H7	0.84 (4)
N1—C4ⁱ	1.327 (5)	C2—H1	0.930
C1—C2	1.392 (5)	C4—H8	0.930
C1—C2ⁱⁱ	1.392 (5)	C5—H9	0.930
C1—C3	1.509 (7)	C8—H10	0.930
C2—C2ⁱⁱⁱ	1.387 (5)	C9—H11	0.930
C4—C5	1.387 (6)

C5···C7^v	3.532 (6)	C6···C8^vi	3.589 (4)
C5···C9^v	3.544 (6)	C7···C2	3.453 (6)
C6···C7^v	3.562 (4)	C7···C5^vii	3.532 (6)
C6···C7^vi	3.562 (4)	C7···C6^vii	3.562 (4)
C6···C8^v	3.589 (4)	C8···C6^vii	3.589 (4)

O1—Ce1—O1ⁱ	118.00 (9)	C2—C1—C2ⁱⁱ	119.7 (4)
O1—Ce1—O2	71.20 (10)	C2—C1—C3	120.2 (2)
O1—Ce1—O2ⁱ	70.15 (10)	C2ⁱⁱ—C1—C3	120.2 (2)
O1—Ce1—O3	68.08 (10)	C1—C2—C2ⁱⁱⁱ	120.2 (4)
O1—Ce1—O3ⁱ	136.72 (9)	O1—C3—O1ⁱⁱ	123.7 (4)
O1—Ce1—O4	70.53 (10)	O1—C3—C1	118.1 (2)
O1—Ce1—O4ⁱ	138.31 (10)	O1ⁱⁱ—C3—C1	118.1 (2)
O1—Ce1—N1	121.00 (7)	N1—C4—C5	122.9 (4)
O1ⁱ—Ce1—O2	70.15 (10)	C4—C5—C6	120.1 (4)
O1ⁱ—Ce1—O2ⁱ	71.20 (10)	C5—C6—C5ⁱ	116.2 (4)
O1ⁱ—Ce1—O3	136.72 (9)	C5—C6—C6^iv	121.9 (3)
O1ⁱ—Ce1—O3ⁱ	68.08 (10)	C5ⁱ—C6—C6^iv	121.9 (3)
O1ⁱ—Ce1—O4	138.31 (10)	C8—C7—C9	120.0 (4)
O1ⁱ—Ce1—O4ⁱ	70.53 (10)	C8—C7—C10	120.6 (4)
O1ⁱ—Ce1—N1	121.00 (7)	C9—C7—C10	119.4 (4)
O2—Ce1—O2ⁱ	100.03 (11)	C7—C8—C8ⁱⁱⁱ	120.0 (4)
O2—Ce1—O3	72.74 (10)	C7—C9—C9ⁱⁱⁱ	120.0 (4)
O2—Ce1—O3ⁱ	137.67 (10)	O5—C10—O6	123.9 (4)
O2—Ce1—O4	140.68 (10)	O5—C10—C7	118.1 (4)
O2—Ce1—O4ⁱ	75.06 (10)	O6—C10—C7	118.1 (4)
O2—Ce1—N1	129.99 (7)	Ce1—O2—H2	115 (3)
O2ⁱ—Ce1—O3	137.67 (10)	Ce1—O2—H3	114 (3)
O2ⁱ—Ce1—O3ⁱ	72.74 (10)	H2—O2—H3	104 (4)
O2ⁱ—Ce1—O4	75.06 (10)	Ce1—O3—H4	117 (4)
O2ⁱ—Ce1—O4ⁱ	140.68 (10)	Ce1—O3—H5	124 (4)
O2ⁱ—Ce1—N1	129.99 (7)	H4—O3—H5	102 (5)
O3—Ce1—O3ⁱ	139.71 (9)	Ce1—O4—H6	128 (4)
O3—Ce1—O4	84.96 (10)	Ce1—O4—H7	128 (4)
O3—Ce1—O4ⁱ	79.12 (10)	H6—O4—H7	102 (6)
O3—Ce1—N1	69.85 (7)	C1—C2—H1	119.897
O3ⁱ—Ce1—O4	79.12 (10)	C2ⁱⁱⁱ—C2—H1	119.930
O3ⁱ—Ce1—O4ⁱ	84.96 (10)	N1—C4—H8	118.556
O3ⁱ—Ce1—N1	69.85 (7)	C5—C4—H8	118.540
O4—Ce1—O4ⁱ	132.66 (10)	C4—C5—H9	119.957
O4—Ce1—N1	66.33 (7)	C6—C5—H9	119.991
O4ⁱ—Ce1—N1	66.33 (7)	C7—C8—H10	119.995
Ce1—O1—C3	145.08 (19)	C8ⁱⁱⁱ—C8—H10	119.992
Ce1—N1—C4	121.1 (3)	C7—C9—H11	120.023
Ce1—N1—C4ⁱ	121.1 (3)	C9ⁱⁱⁱ—C9—H11	120.026
C4—N1—C4ⁱ	117.8 (4)

O1—Ce1—O1ⁱ—C3^viii	−84.2 (3)	O4ⁱ—Ce1—N1—C4ⁱ	51.94 (8)
O1ⁱ—Ce1—O1—C3	−84.2 (3)	Ce1—O1—C3—O1ⁱⁱ	−75.3 (4)
O2—Ce1—O1—C3	−138.3 (3)	Ce1—O1—C3—C1	104.7 (4)
O2ⁱ—Ce1—O1—C3	−29.7 (3)	Ce1—N1—C4—C5	179.8 (2)
O3—Ce1—O1—C3	143.3 (4)	Ce1—N1—C4ⁱ—C5ⁱ	179.8 (2)
O3ⁱ—Ce1—O1—C3	2.8 (4)	C4—N1—C4ⁱ—C5ⁱ	−0.2 (5)
O4—Ce1—O1—C3	50.9 (3)	C4ⁱ—N1—C4—C5	−0.2 (5)
O4ⁱ—Ce1—O1—C3	−175.9 (3)	C2—C1—C2ⁱⁱ—C2^ix	0.0 (4)
O1—Ce1—N1—C4	5.40 (8)	C2ⁱⁱ—C1—C2—C2ⁱⁱⁱ	0.0 (4)
O1—Ce1—N1—C4ⁱ	−174.60 (8)	C2—C1—C3—O1	−9.77 (16)
N1—Ce1—O1—C3	95.8 (3)	C2—C1—C3—O1ⁱⁱ	170.23 (16)
O2—Ce1—O1ⁱ—C3^viii	−29.7 (3)	C2ⁱⁱ—C1—C3—O1	170.23 (16)
O2ⁱ—Ce1—O1ⁱ—C3^viii	−138.3 (3)	C2ⁱⁱ—C1—C3—O1ⁱⁱ	−9.77 (16)
O3—Ce1—O1ⁱ—C3^viii	2.8 (4)	C1—C2—C2ⁱⁱⁱ—C1^ix	0.0 (5)
O3ⁱ—Ce1—O1ⁱ—C3^viii	143.3 (4)	N1—C4—C5—C6	0.4 (6)
O4—Ce1—O1ⁱ—C3^viii	−175.9 (3)	C4—C5—C6—C5ⁱ	−0.2 (4)
O4ⁱ—Ce1—O1ⁱ—C3^viii	50.9 (3)	C4—C5—C6—C6^iv	179.8 (3)
O1ⁱ—Ce1—N1—C4	−174.60 (8)	C5—C6—C6^iv—C5^iv	180.00 (19)
O1ⁱ—Ce1—N1—C4ⁱ	5.40 (8)	C5—C6—C6^iv—C5^x	0.00 (19)
N1—Ce1—O1ⁱ—C3^viii	95.8 (3)	C5ⁱ—C6—C6^iv—C5^iv	0.00 (19)
O2—Ce1—N1—C4	−85.35 (10)	C8—C7—C9—C9ⁱⁱⁱ	0.2 (6)
O2—Ce1—N1—C4ⁱ	94.65 (10)	C9—C7—C8—C8ⁱⁱⁱ	−0.2 (6)
O2ⁱ—Ce1—N1—C4	94.65 (10)	C8—C7—C10—O5	8.2 (6)
O2ⁱ—Ce1—N1—C4ⁱ	−85.35 (10)	C8—C7—C10—O6	−170.9 (4)
O3—Ce1—N1—C4	−41.42 (8)	C10—C7—C8—C8ⁱⁱⁱ	178.4 (3)
O3—Ce1—N1—C4ⁱ	138.58 (8)	C9—C7—C10—O5	−173.2 (4)
O3ⁱ—Ce1—N1—C4	138.58 (8)	C9—C7—C10—O6	7.6 (5)
O3ⁱ—Ce1—N1—C4ⁱ	−41.42 (8)	C10—C7—C9—C9ⁱⁱⁱ	−178.4 (3)
O4—Ce1—N1—C4	51.94 (8)	C7—C8—C8ⁱⁱⁱ—C7ⁱⁱⁱ	0.0 (6)
O4—Ce1—N1—C4ⁱ	−128.06 (8)	C7—C9—C9ⁱⁱⁱ—C7ⁱⁱⁱ	0.0 (6)
O4ⁱ—Ce1—N1—C4	−128.06 (8)

Symmetry codes: (i) −x+2, −y, z; (ii) −x+1, −y, z; (iii) x, y, −z+1; (iv) −x+2, −y, −z; (v) x+1/2, −y+1/2, −z+1/2; (vi) −x+3/2, y−1/2, −z+1/2; (vii) x−1/2, −y+1/2, −z+1/2; (viii) x+1, y, z; (ix) −x+1, −y, −z+1; (x) x, y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O5	0.84 (4)	1.93 (4)	2.754 (5)	167 (5)
O2—H3···O6^viii	0.84 (3)	1.90 (4)	2.725 (5)	166 (4)
O3—H4···O5	0.83 (5)	2.02 (5)	2.828 (4)	164 (6)
O3—H5···O6^v	0.84 (5)	1.81 (5)	2.650 (4)	175 (6)
O4—H7···O5^vi	0.84 (4)	1.91 (4)	2.749 (5)	174 (6)

Symmetry codes: (v) x+1/2, −y+1/2, −z+1/2; (vi) −x+3/2, y−1/2, −z+1/2; (viii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Ce₂(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)₁₂](C₈H₄O₄)₂
M_r	572.48
Crystal system, space group	Orthorhombic, Pnnm
Temperature (K)	293
a, b, c (Å)	6.112 (4), 14.278 (8), 22.395 (12)
V (Å³)	1954.3 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.40
Crystal size (mm)	0.60 × 0.20 × 0.10

Data collection
Diffractometer	Rigaku Mercury70 diffractometer
Absorption correction	Multi-scan (REQAB; Rigaku, 1998)
T_min, T_max	0.511, 0.787
No. of measured, independent and observed [F² > 2σ(F²)] reflections	14945, 2246, 2163
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.068, 1.39
No. of reflections	2246
No. of parameters	167
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.42

Computer programs: CrystalClear (Rigaku/MSC, 2005), SIR2008 (Burla et al., 2007), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku, 2010).

Selected bond lengths (Å) top

Ce1—O1	2.479 (3)	Ce1—O3ⁱ	2.551 (3)
Ce1—O1ⁱ	2.479 (3)	Ce1—O4	2.533 (3)
Ce1—O2	2.530 (3)	Ce1—O4ⁱ	2.533 (3)
Ce1—O2ⁱ	2.530 (3)	Ce1—N1	2.873 (5)
Ce1—O3	2.551 (3)

Symmetry code: (i) −x+2, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O5	0.84 (4)	1.93 (4)	2.754 (5)	167 (5)
O2—H3···O6ⁱⁱ	0.84 (3)	1.90 (4)	2.725 (5)	166 (4)
O3—H4···O5	0.83 (5)	2.02 (5)	2.828 (4)	164 (6)
O3—H5···O6ⁱⁱⁱ	0.84 (5)	1.81 (5)	2.650 (4)	175 (6)
O4—H7···O5^iv	0.84 (4)	1.91 (4)	2.749 (5)	174 (6)

Symmetry codes: (ii) x+1, y, z; (iii) x+1/2, −y+1/2, −z+1/2; (iv) −x+3/2, y−1/2, −z+1/2.

References

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G., Siliqi, D. & Spagna, R. (2007). J. Appl. Cryst. 40, 609–613. Web of Science CrossRef CAS IUCr Journals Google Scholar
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