Poly[tetra-aqua-(5-hy-droxy-pyridin-1-ium-3-carboxyl-ato-κO (3))tris-(μ-oxalato-κ(4) O (1),O (2):O (1'),O (2'))dieuropium(III)].

In the title compound, [Eu2(C6H5NO3)2(C2O4)3(H2O)4] n , the Eu(III) atom is bonded to one O atom from a monodentate 5-hy-droxy-pyridin-1-ium-3-carboxyl-ate ligand, six O atoms from three oxalate ligands and two water mol-ecules, exhibiting a highly distorted tricapped trigonal geometry. Three independent oxalate ligands, each lying on an inversion center, bridge the Eu(III) atoms, forming a brickwall-like layer parallel to (001), which is stabilized by intra-layer O-H⋯O hydrogen bonds. The layers are further linked through inter-layer O-H⋯O and N-H⋯O hydrogen bonds and π-π inter-actions between the pyridine rings [centroid-centroid distance = 3.5741 (14) Å] into a three-dimensional supra-molecular network.

Related literature

For background to metal complexes of pyridine-carb­oxy­lic derivatives, see: Black et al. (2009 ▶); Cañadillas-Delgado et al. (2010 ▶); Hu et al. (2007 ▶); Sun et al. (2010 ▶); Wen et al. (2007 ▶); Xu et al. (2008 ▶). For structures and properties of coordination polymers derived from 5-hy­droxy­nicotinic acid, see: Bunzli (2010 ▶); Decadt et al. (2012 ▶); Gai et al. (2012 ▶); Ramya et al. (2012 ▶); Yang et al. (2011 ▶); Zhang et al. (2012 ▶).

Experimental

Crystal data

[Eu2(C6H5NO3)2(C2O4)3(H2O)4]

M = 918.26

Triclinic,

a = 7.5912 (2) Å

b = 8.0973 (3) Å

c = 10.6706 (3) Å

α = 103.493 (3)°

β = 98.589 (3)°

γ = 92.240 (3)°

V = 628.78 (3) Å3

Z = 1

Mo Kα radiation

μ = 5.05 mm−1

T = 153 K

0.24 × 0.17 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.377, T max = 0.688

12455 measured reflections

3135 independent reflections

2965 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.038

S = 1.09

3135 reflections

221 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.55 e Å−3

Δρmin = −0.54 e Å−3

Data collection: APEX2 (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: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813011057/hy2623sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011057/hy2623Isup2.hkl

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

[Eu2(C6H5NO3)2(C2O4)3(H2O)4]	Z = 1
Mr = 918.26	F(000) = 442
Triclinic, P1	Dx = 2.425 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5912 (2) Å	Cell parameters from 3135 reflections
b = 8.0973 (3) Å	θ = 2.6–29.4°
c = 10.6706 (3) Å	µ = 5.05 mm−1
α = 103.493 (3)°	T = 153 K
β = 98.589 (3)°	Block, colorless
γ = 92.240 (3)°	0.24 × 0.17 × 0.08 mm
V = 628.78 (3) Å3

Bruker APEXII CCD diffractometer	3135 independent reflections
Radiation source: fine-focus sealed tube	2965 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
φ and ω scans	θmax = 29.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.377, Tmax = 0.688	k = −11→10
12455 measured reflections	l = −13→14

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)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.038	w = 1/[σ2(Fo2) + (0.0087P)2 + 0.3669P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.002
3135 reflections	Δρmax = 0.55 e Å−3
221 parameters	Δρmin = −0.54 e Å−3
0 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0094 (4)

Experimental. IR (cm-1, KBr): 3495(s), 3380(s), 3103(m), 3076(w), 3047(w), 2929(w), 2461(m), 2146(m), 1968(w), 1893(w), 1695(s), 1655(s), 1621(s), 1602(s), 1575(s), 1379(s), 1320(s), 1256(m), 1147(w), 1114(w), 1010(w), 935(w), 880(m), 806(s), 784(s), 667(m), 620(w), 565(w), 531(w), 484(m).

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.

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
C1	0.7687 (3)	0.8846 (3)	0.9610 (2)	0.0095 (5)
C2	0.7420 (3)	0.7295 (3)	1.0146 (2)	0.0094 (5)
C3	0.7733 (3)	0.5691 (3)	0.9454 (2)	0.0116 (5)
H3	0.8082	0.5552	0.8639	0.014*
C4	0.7525 (4)	0.4283 (3)	0.9978 (2)	0.0127 (5)
C5	0.7046 (4)	0.4541 (3)	1.1205 (2)	0.0132 (5)
H5	0.6934	0.3631	1.1590	0.016*
C6	0.6887 (3)	0.7479 (3)	1.1353 (2)	0.0110 (5)
H6	0.6631	0.8540	1.1818	0.013*
C7	0.5536 (3)	1.0035 (3)	0.4431 (2)	0.0099 (5)
C8	1.0255 (3)	0.5479 (3)	0.4489 (2)	0.0084 (5)
C9	0.4854 (3)	0.4971 (3)	0.5697 (2)	0.0101 (5)
Eu1	0.797021 (16)	0.810935 (14)	0.626500 (11)	0.00700 (5)
N1	0.6745 (3)	0.6119 (3)	1.1836 (2)	0.0112 (4)
O1	0.8197 (2)	0.8624 (2)	0.85299 (16)	0.0118 (4)
O2	0.7395 (3)	1.0258 (2)	1.03073 (16)	0.0141 (4)
O3	0.7803 (3)	0.2743 (2)	0.92694 (18)	0.0225 (5)
H3A	0.7713	0.2035	0.9698	0.034*
O4	0.7120 (2)	0.9644 (2)	0.45635 (16)	0.0117 (4)
O5	0.5274 (2)	0.9519 (2)	0.65247 (17)	0.0138 (4)
O6	0.9752 (2)	0.6961 (2)	0.45804 (16)	0.0103 (3)
O7	0.8889 (2)	0.5283 (2)	0.63432 (17)	0.0120 (4)
O8	0.5549 (2)	0.6147 (2)	0.66268 (16)	0.0117 (4)
O9	0.6111 (2)	0.6314 (2)	0.42511 (16)	0.0138 (4)
O10	1.1269 (2)	0.8348 (2)	0.70926 (19)	0.0138 (4)
O11	0.9123 (3)	1.1139 (2)	0.7043 (2)	0.0161 (4)
H1	0.645 (4)	0.622 (4)	1.257 (3)	0.025 (9)*
H7	1.179 (5)	0.876 (4)	0.667 (4)	0.032 (11)*
H8	1.168 (5)	0.893 (4)	0.794 (4)	0.038 (10)*
H9	0.937 (5)	1.181 (5)	0.654 (4)	0.050 (12)*
H10	0.874 (5)	1.164 (4)	0.760 (4)	0.027 (10)*

	U11	U22	U33	U12	U13	U23
C1	0.0109 (12)	0.0101 (11)	0.0078 (12)	−0.0005 (9)	0.0008 (9)	0.0036 (9)
C2	0.0096 (12)	0.0113 (11)	0.0076 (12)	−0.0008 (9)	0.0007 (9)	0.0037 (9)
C3	0.0162 (13)	0.0124 (12)	0.0073 (12)	0.0010 (10)	0.0041 (9)	0.0035 (9)
C4	0.0177 (13)	0.0096 (12)	0.0118 (13)	0.0024 (10)	0.0037 (10)	0.0034 (9)
C5	0.0191 (14)	0.0104 (12)	0.0127 (13)	0.0025 (10)	0.0051 (10)	0.0060 (9)
C6	0.0151 (13)	0.0080 (11)	0.0101 (12)	−0.0007 (10)	0.0036 (9)	0.0015 (9)
C7	0.0127 (12)	0.0076 (11)	0.0106 (12)	0.0009 (9)	0.0053 (9)	0.0025 (9)
C8	0.0074 (12)	0.0105 (11)	0.0078 (11)	0.0007 (9)	0.0009 (9)	0.0030 (9)
C9	0.0080 (12)	0.0138 (12)	0.0103 (13)	0.0028 (10)	0.0037 (9)	0.0045 (9)
Eu1	0.00918 (8)	0.00665 (7)	0.00609 (7)	0.00141 (4)	0.00295 (4)	0.00217 (4)
N1	0.0159 (11)	0.0124 (10)	0.0056 (10)	−0.0002 (9)	0.0039 (8)	0.0014 (8)
O1	0.0162 (9)	0.0119 (8)	0.0077 (9)	−0.0008 (7)	0.0031 (7)	0.0027 (6)
O2	0.0256 (10)	0.0077 (8)	0.0102 (9)	0.0014 (7)	0.0067 (7)	0.0019 (7)
O3	0.0487 (14)	0.0073 (9)	0.0173 (10)	0.0068 (9)	0.0196 (9)	0.0049 (7)
O4	0.0101 (9)	0.0144 (9)	0.0126 (9)	0.0033 (7)	0.0047 (7)	0.0052 (7)
O5	0.0154 (9)	0.0194 (9)	0.0107 (9)	0.0078 (7)	0.0051 (7)	0.0088 (7)
O6	0.0128 (9)	0.0080 (8)	0.0129 (9)	0.0032 (7)	0.0067 (7)	0.0049 (6)
O7	0.0170 (9)	0.0095 (8)	0.0131 (9)	0.0045 (7)	0.0096 (7)	0.0047 (7)
O8	0.0125 (9)	0.0142 (9)	0.0082 (9)	−0.0020 (7)	0.0027 (7)	0.0020 (7)
O9	0.0173 (10)	0.0148 (9)	0.0098 (9)	−0.0066 (7)	0.0049 (7)	0.0038 (7)
O10	0.0118 (9)	0.0165 (9)	0.0123 (10)	−0.0015 (8)	0.0031 (7)	0.0016 (8)
O11	0.0274 (12)	0.0109 (9)	0.0122 (10)	0.0002 (8)	0.0090 (8)	0.0035 (8)

C1—O1	1.246 (3)	C9—O9iii	1.266 (3)
C1—O2	1.258 (3)	C9—C9iii	1.546 (5)
C1—C2	1.515 (3)	Eu1—O1	2.3333 (16)
C2—C6	1.384 (3)	Eu1—O5	2.4025 (18)
C2—C3	1.385 (3)	Eu1—O7	2.4348 (16)
C3—C4	1.395 (3)	Eu1—O6	2.4433 (17)
C3—H3	0.9300	Eu1—O4	2.4539 (17)
C4—O3	1.341 (3)	Eu1—O11	2.4776 (18)
C4—C5	1.383 (3)	Eu1—O9	2.4899 (17)
C5—N1	1.344 (3)	Eu1—O10	2.5118 (19)
C5—H5	0.9300	Eu1—O8	2.5142 (16)
C6—N1	1.328 (3)	N1—H1	0.83 (3)
C6—H6	0.9300	O3—H3A	0.8200
C7—O5i	1.246 (3)	O5—C7i	1.246 (3)
C7—O4	1.252 (3)	O7—C8ii	1.241 (3)
C7—C7i	1.569 (5)	O9—C9iii	1.266 (3)
C8—O7ii	1.241 (3)	O10—H7	0.76 (4)
C8—O6	1.260 (3)	O10—H8	0.92 (4)
C8—C8ii	1.562 (5)	O11—H9	0.89 (4)
C9—O8	1.238 (3)	O11—H10	0.74 (4)
O1—C1—O2	125.5 (2)	O1—Eu1—O8	75.12 (6)
O1—C1—C2	117.7 (2)	O5—Eu1—O8	68.60 (6)
O2—C1—C2	116.8 (2)	O7—Eu1—O8	66.05 (6)
C6—C2—C3	119.3 (2)	O6—Eu1—O8	117.53 (5)
C6—C2—C1	119.8 (2)	O4—Eu1—O8	115.81 (6)
C3—C2—C1	120.9 (2)	O11—Eu1—O8	138.86 (6)
C2—C3—C4	120.1 (2)	O9—Eu1—O8	64.36 (5)
C2—C3—H3	119.9	O10—Eu1—O8	129.19 (6)
C4—C3—H3	119.9	O1—Eu1—C7i	100.78 (6)
O3—C4—C5	123.0 (2)	O5—Eu1—C7i	20.20 (6)
O3—C4—C3	118.5 (2)	O7—Eu1—C7i	140.16 (6)
C5—C4—C3	118.5 (2)	O6—Eu1—C7i	120.37 (6)
N1—C5—C4	119.3 (2)	O4—Eu1—C7i	48.67 (6)
N1—C5—H5	120.4	O11—Eu1—C7i	78.99 (6)
C4—C5—H5	120.4	O9—Eu1—C7i	70.91 (6)
N1—C6—C2	119.0 (2)	O10—Eu1—C7i	148.31 (6)
N1—C6—H6	120.5	O8—Eu1—C7i	77.75 (6)
C2—C6—H6	120.5	O1—Eu1—C7	125.61 (6)
O5i—C7—O4	125.9 (2)	O5—Eu1—C7	48.20 (6)
O5i—C7—C7i	116.6 (3)	O7—Eu1—C7	141.25 (6)
O4—C7—C7i	117.5 (3)	O6—Eu1—C7	93.32 (6)
O7ii—C8—O6	125.7 (2)	O4—Eu1—C7	20.65 (6)
O7ii—C8—C8ii	117.4 (3)	O11—Eu1—C7	75.30 (6)
O6—C8—C8ii	116.9 (3)	O9—Eu1—C7	62.82 (6)
O8—C9—O9iii	126.9 (2)	O10—Eu1—C7	132.68 (6)
O8—C9—C9iii	118.7 (3)	O8—Eu1—C7	98.11 (6)
O9iii—C9—C9iii	114.4 (3)	C7i—Eu1—C7	28.45 (8)
O1—Eu1—O5	80.96 (6)	O1—Eu1—C8ii	102.84 (6)
O1—Eu1—O7	85.97 (6)	O5—Eu1—C8ii	146.68 (6)
O5—Eu1—O7	134.62 (6)	O7—Eu1—C8ii	19.51 (6)
O1—Eu1—O6	138.32 (6)	O6—Eu1—C8ii	47.81 (6)
O5—Eu1—O6	140.49 (6)	O4—Eu1—C8ii	119.19 (6)
O7—Eu1—O6	67.29 (5)	O11—Eu1—C8ii	135.25 (6)
O1—Eu1—O4	137.52 (6)	O9—Eu1—C8ii	71.90 (6)
O5—Eu1—O4	67.69 (6)	O10—Eu1—C8ii	67.29 (6)
O7—Eu1—O4	136.49 (6)	O8—Eu1—C8ii	80.29 (6)
O6—Eu1—O4	75.83 (6)	C7i—Eu1—C8ii	142.17 (6)
O1—Eu1—O11	76.53 (6)	C7—Eu1—C8ii	129.65 (6)
O5—Eu1—O11	78.03 (7)	C6—N1—C5	123.8 (2)
O7—Eu1—O11	140.07 (7)	C6—N1—H1	120 (2)
O6—Eu1—O11	103.48 (6)	C5—N1—H1	116 (2)
O4—Eu1—O11	69.67 (6)	C1—O1—Eu1	158.00 (17)
O1—Eu1—O9	139.48 (6)	C4—O3—H3A	109.5
O5—Eu1—O9	83.77 (6)	C7—O4—Eu1	115.60 (15)
O7—Eu1—O9	78.60 (6)	C7i—O5—Eu1	118.04 (15)
O6—Eu1—O9	67.69 (6)	C8—O6—Eu1	118.79 (14)
O4—Eu1—O9	66.30 (6)	C8ii—O7—Eu1	119.54 (15)
O11—Eu1—O9	135.93 (6)	C9—O8—Eu1	118.26 (15)
O1—Eu1—O10	75.35 (6)	C9iii—O9—Eu1	120.53 (15)
O5—Eu1—O10	143.27 (6)	Eu1—O10—H7	111 (3)
O7—Eu1—O10	71.49 (6)	Eu1—O10—H8	119 (2)
O6—Eu1—O10	66.30 (6)	H7—O10—H8	105 (3)
O4—Eu1—O10	113.98 (6)	Eu1—O11—H9	125 (3)
O11—Eu1—O10	69.47 (7)	Eu1—O11—H10	116 (3)
O9—Eu1—O10	131.87 (6)	H9—O11—H10	109 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O9iv	0.83 (3)	1.84 (3)	2.662 (3)	172 (3)
O3—H3A···O2v	0.82	1.73	2.543 (2)	169
O10—H7···O4vi	0.76 (4)	2.26 (4)	3.016 (2)	168 (4)
O10—H8···O2vii	0.92 (4)	1.85 (4)	2.759 (3)	170 (3)
O11—H9···O6vi	0.88 (4)	1.90 (4)	2.771 (3)	170 (4)
O11—H10···O3viii	0.74 (4)	2.04 (4)	2.776 (3)	172 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O9i	0.83 (3)	1.84 (3)	2.662 (3)	172 (3)
O3—H3A⋯O2ii	0.82	1.73	2.543 (2)	169
O10—H7⋯O4iii	0.76 (4)	2.26 (4)	3.016 (2)	168 (4)
O10—H8⋯O2iv	0.92 (4)	1.85 (4)	2.759 (3)	170 (3)
O11—H9⋯O6iii	0.88 (4)	1.90 (4)	2.771 (3)	170 (4)
O11—H10⋯O3v	0.74 (4)	2.04 (4)	2.776 (3)	172 (4)

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