Poly[[hexa-aqua-(μ(2)-oxalato-κO,O:O,O)bis(μ(3)-pyridine-2,4-dicarboxyl-ato-κN,O:O:O)dicerium(III)] monohydrate].

In the polymeric title compound, {[Ce(2)(C(7)H(3)NO(4))(2)(C(2)O(4))(H(2)O)(6)]·H(2)O}(n), the Ce(3+) cation is nine-coordinated in a distorted CeNO(8) tricapped trigonal-prismatic geometry, formed by three pyridine-2,4-dicarboxyl-ate anions, one oxalate anion and three water mol-ecules. The mid-point of the oxalate anion is located on an inversion center. The oxalate and pyridine-2,4-dicarboxyl-ate anions bridge the Ce(3+) cations, forming a two-dimensional polymeric complex parallel to (010). Inter-molecular classical O-H⋯O hydrogen bonding and weak C-H⋯O hydrogen bonding are present in the crystal structure and π-π stacking [centroid-centroid distance = 3.558 (2) Å] is observed between parallel pyridine rings of adjacent mol-ecules. The uncoordinated water mol-ecule shows an occupancy of 0.5.

Related literature

For the isotypic La3+ complex, see: Shen & Lush (2011 ▶). For related pyridine-2,4-dicarboxyl­ate complexes, see: Aghabozorg et al. (2011 ▶); Li et al. (2007 ▶); Wang et al. (2009 ▶).

Experimental

Crystal data

[Ce2(C7H3NO4)2(C2O4)(H2O)6]·H2O

M = 824.58

Triclinic,

a = 6.4160 (5) Å

b = 6.6486 (6) Å

c = 13.9920 (12) Å

α = 89.917 (1)°

β = 85.588 (1)°

γ = 73.676 (1)°

V = 570.98 (8) Å3

Z = 1

Mo Kα radiation

μ = 4.04 mm−1

T = 294 K

0.30 × 0.10 × 0.10 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.639, T max = 0.937

6072 measured reflections

2664 independent reflections

2416 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.081

S = 1.10

2664 reflections

177 parameters

H-atom parameters constrained

Δρmax = 2.75 e Å−3

Δρmin = −2.70 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811051956/xu5400sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811051956/xu5400Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ce2(C7H3NO4)2(C2O4)(H2O)6]·H2O	Z = 1
Mr = 824.58	F(000) = 398
Triclinic, P1	Dx = 2.398 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4160 (5) Å	Cell parameters from 4490 reflections
b = 6.6486 (6) Å	θ = 2.5–25.0°
c = 13.9920 (12) Å	µ = 4.04 mm−1
α = 89.917 (1)°	T = 294 K
β = 85.588 (1)°	Columnar, colorless
γ = 73.676 (1)°	0.30 × 0.10 × 0.10 mm
V = 570.98 (8) Å3

Bruker SMART 1000 CCD area-detector diffractometer	2664 independent reflections
Radiation source: fine-focus sealed tube	2416 reflections with I > 2σ(I)
graphite	Rint = 0.030
Detector resolution: 9 pixels mm-1	θmax = 27.8°, θmin = 1.5°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −8→8
Tmin = 0.639, Tmax = 0.937	l = −18→18
6072 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)] = 0.028	H-atom parameters constrained
wR(F2) = 0.081	w = 1/[σ2(Fo2) + (0.0523P)2 + 0.4154P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max = 0.019
2664 reflections	Δρmax = 2.75 e Å−3
177 parameters	Δρmin = −2.70 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0071 (15)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	Occ. (<1)
Ce	0.36484 (3)	0.33000 (3)	0.80343 (1)	0.0198 (1)
O1	0.7620 (6)	0.3463 (6)	0.2798 (2)	0.0356 (11)
O2	1.0901 (6)	0.2177 (7)	0.3373 (3)	0.0438 (13)
O3	1.0817 (5)	0.2746 (6)	0.7009 (2)	0.0350 (10)
O4	0.7595 (5)	0.3214 (7)	0.7822 (2)	0.0380 (13)
O5	0.5054 (7)	0.2476 (5)	0.9655 (2)	0.0408 (13)
O6	0.5773 (6)	0.3678 (5)	1.1047 (2)	0.0360 (10)
O7	0.0036 (8)	0.5134 (8)	0.8992 (4)	0.0729 (14)
O8	0.5654 (6)	−0.0533 (6)	0.7844 (3)	0.0419 (11)
O9	0.1789 (8)	0.0870 (8)	0.8994 (4)	0.0729 (14)
N1	0.5723 (5)	0.2600 (6)	0.6274 (2)	0.0208 (9)
C1	0.7770 (7)	0.2748 (6)	0.6150 (3)	0.0218 (11)
C2	0.5683 (7)	0.2406 (7)	0.4556 (3)	0.0248 (11)
C3	0.7772 (7)	0.2622 (7)	0.4439 (3)	0.0227 (11)
C4	0.8836 (7)	0.2747 (7)	0.5250 (3)	0.0251 (11)
C5	0.4745 (7)	0.2392 (7)	0.5484 (3)	0.0256 (12)
C6	0.8875 (8)	0.2745 (7)	0.3451 (3)	0.0275 (12)
C7	0.8828 (7)	0.2921 (7)	0.7052 (3)	0.0246 (11)
C8	0.5247 (7)	0.3884 (6)	1.0201 (3)	0.0237 (11)
O10	−0.1094 (13)	−0.0862 (13)	0.9223 (7)	0.050 (3)	0.500
H2A	0.49300	0.22740	0.40290	0.039 (15)*
H4A	1.02630	0.28290	0.51910	0.0300*
H5A	0.33490	0.22280	0.55600	0.0300*
H7A	−0.07800	0.47060	0.86320	0.0800*
H7B	−0.02500	0.63680	0.88280	0.0800*
H8A	0.53670	−0.16200	0.81820	0.0800*
H8B	0.65420	−0.09500	0.73490	0.0800*
H9A	0.24360	−0.06740	0.89420	0.0800*
H9B	0.06500	0.09050	0.87300	0.0800*
H10A	−0.21970	0.00790	0.90760	0.0800*	0.500
H10B	−0.12520	−0.12960	0.98560	0.0800*	0.500

	U11	U22	U33	U12	U13	U23
Ce	0.0191 (2)	0.0294 (2)	0.0134 (1)	−0.0113 (1)	−0.0006 (1)	0.0005 (1)
O1	0.0380 (19)	0.044 (2)	0.0238 (16)	−0.0092 (16)	−0.0055 (14)	0.0092 (14)
O2	0.0270 (18)	0.064 (3)	0.0303 (19)	0.0011 (17)	0.0068 (15)	0.0078 (17)
O3	0.0199 (15)	0.061 (2)	0.0274 (17)	−0.0163 (15)	−0.0040 (13)	−0.0028 (15)
O4	0.0268 (17)	0.075 (3)	0.0185 (15)	−0.0250 (17)	−0.0004 (13)	−0.0012 (16)
O5	0.074 (3)	0.0266 (17)	0.0225 (16)	−0.0142 (17)	−0.0080 (17)	−0.0003 (13)
O6	0.058 (2)	0.0306 (17)	0.0222 (16)	−0.0141 (16)	−0.0143 (15)	0.0071 (13)
O7	0.055 (2)	0.061 (2)	0.088 (3)	−0.0018 (16)	0.0304 (19)	0.0251 (19)
O8	0.048 (2)	0.0333 (19)	0.041 (2)	−0.0115 (16)	0.0176 (17)	−0.0007 (15)
O9	0.055 (2)	0.061 (2)	0.088 (3)	−0.0018 (16)	0.0304 (19)	0.0251 (19)
N1	0.0174 (16)	0.0268 (17)	0.0193 (16)	−0.0077 (13)	−0.0030 (13)	0.0001 (13)
C1	0.0197 (19)	0.024 (2)	0.022 (2)	−0.0068 (16)	−0.0017 (15)	0.0017 (15)
C2	0.028 (2)	0.030 (2)	0.0179 (19)	−0.0099 (17)	−0.0049 (16)	−0.0011 (16)
C3	0.024 (2)	0.025 (2)	0.0162 (18)	−0.0024 (16)	−0.0005 (15)	0.0042 (15)
C4	0.0172 (19)	0.035 (2)	0.022 (2)	−0.0057 (17)	−0.0003 (16)	0.0045 (17)
C5	0.022 (2)	0.031 (2)	0.026 (2)	−0.0110 (17)	−0.0029 (16)	0.0014 (17)
C6	0.033 (2)	0.029 (2)	0.017 (2)	−0.0045 (18)	0.0037 (17)	−0.0004 (16)
C7	0.0196 (19)	0.033 (2)	0.025 (2)	−0.0129 (17)	−0.0041 (16)	0.0032 (17)
C8	0.028 (2)	0.023 (2)	0.0189 (19)	−0.0052 (16)	−0.0027 (16)	0.0009 (15)
O10	0.037 (4)	0.042 (4)	0.072 (6)	−0.010 (3)	−0.013 (4)	0.009 (4)

Ce—N1	2.684 (3)	O8—H8B	0.8600
Ce—O1i	2.409 (4)	O9—H9B	0.8400
Ce—O3ii	2.505 (3)	O9—H9A	0.9900
Ce—O4	2.511 (3)	O10—H10A	0.8400
Ce—O5	2.508 (3)	O10—H10B	0.9400
Ce—O6iii	2.515 (3)	N1—C5	1.338 (5)
Ce—O7	2.568 (5)	N1—C1	1.343 (6)
Ce—O8	2.515 (4)	C1—C4	1.386 (6)
Ce—O9	2.582 (5)	C1—C7	1.498 (6)
O1—C6	1.268 (6)	C2—C3	1.385 (7)
O2—C6	1.244 (7)	C2—C5	1.390 (6)
O3—C7	1.245 (6)	C3—C6	1.517 (6)
O4—C7	1.268 (5)	C3—C4	1.383 (6)
O5—C8	1.248 (5)	C8—C8iii	1.543 (5)
O6—C8	1.253 (5)	C2—H2A	0.9300
O7—H7B	0.8300	C4—H4A	0.9300
O7—H7A	0.8600	C5—H5A	0.9300
O8—H8A	0.9200
O4—Ce—O5	74.74 (12)	Ce—O5—C8	121.3 (3)
O4—Ce—O7	142.54 (15)	Ceiii—O6—C8	120.9 (3)
O4—Ce—O8	75.62 (14)	Ce—O7—H7B	105.00
O4—Ce—O9	130.01 (15)	H7A—O7—H7B	99.00
O4—Ce—N1	61.02 (10)	Ce—O7—H7A	96.00
O3ii—Ce—O4	137.32 (10)	Ce—O8—H8A	127.00
O1i—Ce—O4	94.76 (13)	H8A—O8—H8B	113.00
O4—Ce—O6iii	70.50 (13)	Ce—O8—H8B	119.00
O5—Ce—O7	84.31 (15)	Ce—O9—H9A	120.00
O5—Ce—O8	78.05 (12)	H9A—O9—H9B	96.00
O5—Ce—O9	67.22 (15)	Ce—O9—H9B	107.00
O5—Ce—N1	130.72 (12)	H10A—O10—H10B	112.00
O3ii—Ce—O5	141.57 (12)	Ce—N1—C5	123.6 (3)
O1i—Ce—O5	132.71 (11)	Ce—N1—C1	118.7 (2)
O5—Ce—O6iii	64.05 (10)	C1—N1—C5	117.1 (3)
O7—Ce—O8	130.23 (15)	N1—C1—C4	122.5 (4)
O7—Ce—O9	64.30 (16)	N1—C1—C7	115.4 (4)
O7—Ce—N1	144.66 (14)	C4—C1—C7	122.1 (4)
O3ii—Ce—O7	76.31 (14)	C3—C2—C5	118.1 (4)
O1i—Ce—O7	76.97 (15)	C2—C3—C6	121.4 (4)
O6iii—Ce—O7	72.47 (15)	C4—C3—C6	120.3 (4)
O8—Ce—O9	65.94 (15)	C2—C3—C4	118.3 (4)
O8—Ce—N1	71.24 (12)	C1—C4—C3	119.8 (4)
O3ii—Ce—O8	89.53 (13)	N1—C5—C2	124.1 (4)
O1i—Ce—O8	144.86 (12)	O1—C6—O2	127.1 (4)
O6iii—Ce—O8	134.19 (12)	O2—C6—C3	116.8 (4)
O9—Ce—N1	127.54 (14)	O1—C6—C3	116.0 (4)
O3ii—Ce—O9	74.47 (14)	O4—C7—C1	116.2 (4)
O1i—Ce—O9	134.92 (15)	O3—C7—C1	119.4 (4)
O6iii—Ce—O9	116.36 (14)	O3—C7—O4	124.4 (4)
O3ii—Ce—N1	76.35 (10)	O5—C8—O6	126.7 (4)
O1i—Ce—N1	74.55 (11)	O5—C8—C8iii	116.7 (4)
O6iii—Ce—N1	114.97 (11)	O6—C8—C8iii	116.6 (4)
O1i—Ce—O3ii	74.72 (12)	C5—C2—H2A	121.00
O3ii—Ce—O6iii	136.22 (12)	C3—C2—H2A	121.00
O1i—Ce—O6iii	68.95 (11)	C1—C4—H4A	120.00
Cei—O1—C6	138.2 (3)	C3—C4—H4A	120.00
Ceiv—O3—C7	140.1 (3)	N1—C5—H5A	118.00
Ce—O4—C7	127.9 (3)	C2—C5—H5A	118.00
O5—Ce—O4—C7	158.0 (4)	N1—Ce—O1i—C6i	73.5 (5)
O7—Ce—O4—C7	−143.7 (4)	O4—Ce—O6iii—C8iii	−87.9 (4)
O8—Ce—O4—C7	76.7 (4)	O5—Ce—O6iii—C8iii	−5.9 (3)
O9—Ce—O4—C7	116.9 (4)	O7—Ce—O6iii—C8iii	86.3 (4)
N1—Ce—O4—C7	0.5 (4)	O8—Ce—O6iii—C8iii	−43.3 (4)
O3ii—Ce—O4—C7	3.6 (5)	O9—Ce—O6iii—C8iii	37.9 (4)
O1i—Ce—O4—C7	−68.9 (4)	N1—Ce—O6iii—C8iii	−130.9 (3)
O6iii—Ce—O4—C7	−134.6 (4)	Cei—O1—C6—O2	−76.7 (7)
O4—Ce—O5—C8	80.8 (4)	Cei—O1—C6—C3	101.7 (5)
O7—Ce—O5—C8	−67.9 (4)	Ceiv—O3—C7—O4	−12.4 (8)
O8—Ce—O5—C8	158.9 (4)	Ceiv—O3—C7—C1	168.6 (3)
O9—Ce—O5—C8	−132.4 (4)	Ce—O4—C7—O3	−174.5 (3)
N1—Ce—O5—C8	106.9 (4)	Ce—O4—C7—C1	4.5 (6)
O3ii—Ce—O5—C8	−127.4 (4)	Ce—O5—C8—O6	174.3 (4)
O1i—Ce—O5—C8	−1.5 (5)	Ce—O5—C8—C8iii	−4.7 (6)
O6iii—Ce—O5—C8	5.4 (4)	Ceiii—O6—C8—O5	175.0 (4)
O4—Ce—N1—C1	−6.1 (3)	Ceiii—O6—C8—C8iii	−6.0 (5)
O4—Ce—N1—C5	−176.6 (4)	Ce—N1—C1—C4	−169.4 (3)
O5—Ce—N1—C1	−35.2 (4)	Ce—N1—C1—C7	10.5 (5)
O5—Ce—N1—C5	154.3 (3)	C5—N1—C1—C4	1.7 (6)
O7—Ce—N1—C1	135.9 (3)	C5—N1—C1—C7	−178.4 (4)
O7—Ce—N1—C5	−34.6 (5)	Ce—N1—C5—C2	168.0 (3)
O8—Ce—N1—C1	−89.7 (3)	C1—N1—C5—C2	−2.7 (7)
O8—Ce—N1—C5	99.8 (4)	N1—C1—C4—C3	1.0 (6)
O9—Ce—N1—C1	−126.2 (3)	C7—C1—C4—C3	−178.8 (4)
O9—Ce—N1—C5	63.3 (4)	N1—C1—C7—O3	169.2 (4)
O3ii—Ce—N1—C1	176.1 (3)	N1—C1—C7—O4	−9.8 (6)
O3ii—Ce—N1—C5	5.6 (3)	C4—C1—C7—O3	−11.0 (6)
O1i—Ce—N1—C1	98.5 (3)	C4—C1—C7—O4	170.0 (4)
O1i—Ce—N1—C5	−72.0 (3)	C5—C2—C3—C4	2.0 (6)
O6iii—Ce—N1—C1	41.2 (3)	C5—C2—C3—C6	−177.4 (4)
O6iii—Ce—N1—C5	−129.3 (3)	C3—C2—C5—N1	0.9 (7)
O4—Ce—O3ii—C7ii	−172.6 (4)	C2—C3—C4—C1	−2.8 (7)
O5—Ce—O3ii—C7ii	49.5 (6)	C6—C3—C4—C1	176.5 (4)
O7—Ce—O3ii—C7ii	−12.4 (5)	C2—C3—C6—O1	27.1 (6)
O8—Ce—O3ii—C7ii	119.4 (5)	C2—C3—C6—O2	−154.4 (5)
O9—Ce—O3ii—C7ii	54.3 (5)	C4—C3—C6—O1	−152.3 (4)
N1—Ce—O3ii—C7ii	−169.8 (5)	C4—C3—C6—O2	26.3 (6)
O4—Ce—O1i—C6i	131.6 (5)	O5—C8—C8iii—O5iii	−180.0 (5)
O5—Ce—O1i—C6i	−154.8 (4)	O5—C8—C8iii—O6iii	−0.9 (6)
O7—Ce—O1i—C6i	−85.4 (5)	O6—C8—C8iii—O5iii	0.9 (6)
O8—Ce—O1i—C6i	60.0 (6)	O6—C8—C8iii—O6iii	180.0 (4)
O9—Ce—O1i—C6i	−54.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O4ii	0.86	2.03	2.879 (6)	171.00
O7—H7B···O10v	0.83	1.84	2.569 (10)	146.00
O8—H8A···O6vi	0.92	2.00	2.910 (5)	170.00
O8—H8B···O2vii	0.86	1.84	2.655 (6)	159.00
O9—H9A···O6vi	0.99	2.01	2.987 (6)	169.00
O9—H9B···O10	0.84	1.93	2.440 (10)	118.00
O10—H10A···O5ii	0.84	2.12	2.844 (9)	143.00
O10—H10A···O8ii	0.84	2.39	2.913 (10)	121.00
O10—H10B···O9viii	0.94	1.63	2.501 (11)	153.00
C5—H5A···O3ii	0.93	2.46	3.131 (5)	129.

Table 1

Selected bond lengths (Å)

Ce—N1	2.684 (3)
Ce—O1i	2.409 (4)
Ce—O3ii	2.505 (3)
Ce—O4	2.511 (3)
Ce—O5	2.508 (3)
Ce—O6iii	2.515 (3)
Ce—O7	2.568 (5)
Ce—O8	2.515 (4)
Ce—O9	2.582 (5)

Symmetry codes: (i) ; (ii) ; (iii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O4ii	0.86	2.03	2.879 (6)	171
O7—H7B⋯O10iv	0.83	1.84	2.569 (10)	146
O8—H8A⋯O6v	0.92	2.00	2.910 (5)	170
O8—H8B⋯O2vi	0.86	1.84	2.655 (6)	159
O9—H9A⋯O6v	0.99	2.01	2.987 (6)	169
O9—H9B⋯O10	0.84	1.93	2.440 (10)	118
O10—H10A⋯O5ii	0.84	2.12	2.844 (9)	143
O10—H10A⋯O8ii	0.84	2.39	2.913 (10)	121
O10—H10B⋯O9vii	0.94	1.63	2.501 (11)	153
C5—H5A⋯O3ii	0.93	2.46	3.131 (5)	129

Symmetry codes: (ii) ; (iv) ; (v) ; (vi) ; (vii) .