Poly[[diaqua-bis-(μ-oxalato-κ(4)O(1),O(2):O(1'),O(2'))bis-(μ(3)-5-oxidopyridin-1-ium-3-carboxyl-ato-κ(3)O(3):O(3'):O(5))diholmium(III)] dihydrate].

In the title compound, {[Ho(2)(C(6)H(4)NO(3))(2)(C(2)O(4))(2)(H(2)O)(2)]·2H(2)O}(n), the Ho(III) atom is coordinated by three O atoms from three 5-hy-droxy-nicotinate ligands, four O atoms from two oxalate ligands, each lying on an inversion center, and one water mol-ecule in a distorted square-anti-prismatic geometry. The 5-hy-droxy-nicotinate ligand is protonated at the N atom and deprotonated at the hy-droxy group. The Ho(III) atoms are bridged by the carboxyl-ate and phenolate O atoms, forming a three-dimensional framework. N-H⋯O and O-H⋯O hydrogen bonds, as well as π-π inter-actions between the pyridine rings [centroid-centroid distance = 3.794 (2) Å], are observed.

Related literature

For background to the applications of compounds with metal-organic framework structures, see: Allendorf et al. (2009 ▶); Choi et al. (2008 ▶); Dang et al. (2010 ▶); Ishikawa et al. (2005 ▶); Lazare et al. (2010 ▶); Shimomura et al. (2010 ▶); Thallapally et al. (2010 ▶). For related structures, see: Zhang et al. (2012 ▶).

Experimental

Crystal data

[Ho2(C6H4NO3)2(C2O4)2(H2O)2]·2H2O

M = 854.16

Triclinic,

a = 7.7786 (16) Å

b = 8.0562 (17) Å

c = 9.505 (2) Å

α = 110.912 (3)°

β = 96.862 (3)°

γ = 95.770 (3)°

V = 545.8 (2) Å3

Z = 1

Mo Kα radiation

μ = 7.30 mm−1

T = 173 K

0.18 × 0.16 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.354, T max = 0.669

4550 measured reflections

2295 independent reflections

2160 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.016

wR(F 2) = 0.038

S = 1.05

2295 reflections

192 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.57 e Å−3

Δρmin = −0.49 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812032916/hy2567sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032916/hy2567Isup2.hkl

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

[Ho2(C6H4NO3)2(C2O4)2(H2O)2]·2H2O	Z = 1
Mr = 854.16	F(000) = 404
Triclinic, P1	Dx = 2.599 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7786 (16) Å	Cell parameters from 4550 reflections
b = 8.0562 (17) Å	θ = 2.3–27.0°
c = 9.505 (2) Å	µ = 7.30 mm−1
α = 110.912 (3)°	T = 173 K
β = 96.862 (3)°	Block, colorless
γ = 95.770 (3)°	0.18 × 0.16 × 0.06 mm
V = 545.8 (2) Å3

Bruker APEXII CCD diffractometer	2295 independent reflections
Radiation source: fine-focus sealed tube	2160 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
φ and ω scans	θmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.354, Tmax = 0.669	k = −10→10
4550 measured reflections	l = −12→12

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)] = 0.016	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.038	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.016P)2 + 0.6363P] where P = (Fo2 + 2Fc2)/3
2295 reflections	(Δ/σ)max = 0.001
192 parameters	Δρmax = 0.57 e Å−3
5 restraints	Δρmin = −0.49 e Å−3

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	0.6934 (4)	1.2898 (4)	1.1270 (3)	0.0109 (5)
C2	0.7746 (4)	0.4547 (4)	0.2648 (3)	0.0123 (6)
C3	0.7041 (4)	0.5062 (4)	0.3987 (3)	0.0117 (6)
H3	0.5989	0.4387	0.4032	0.014*
C4	0.7864 (4)	0.6576 (4)	0.5285 (3)	0.0124 (6)
C5	0.9393 (4)	0.7518 (4)	0.5123 (3)	0.0158 (6)
H5	0.9999	0.8543	0.5962	0.019*
C6	0.9258 (4)	0.5562 (4)	0.2565 (4)	0.0162 (6)
H6	0.9743	0.5245	0.1651	0.019*
C7	0.9532 (4)	0.9560 (4)	1.0490 (3)	0.0106 (6)
C8	0.4187 (4)	0.9302 (4)	0.4887 (3)	0.0116 (6)
Ho1	0.647369 (16)	0.971506 (16)	0.803507 (14)	0.00854 (5)
N1	1.0014 (3)	0.6993 (4)	0.3802 (3)	0.0168 (5)
O1	0.7614 (3)	1.2593 (3)	1.0082 (2)	0.0162 (5)
O2	0.4346 (3)	0.8128 (3)	0.8643 (2)	0.0136 (4)
O3	0.7231 (3)	0.7072 (3)	0.6565 (2)	0.0150 (4)
O4	0.7922 (3)	0.8943 (3)	1.0004 (2)	0.0133 (4)
O5	0.9595 (3)	1.0464 (3)	0.8342 (2)	0.0123 (4)
O6	0.4182 (3)	0.8477 (3)	0.5761 (2)	0.0161 (4)
O7	0.7033 (3)	1.0868 (3)	0.6190 (2)	0.0135 (4)
O8	0.4335 (3)	1.1739 (3)	0.8101 (3)	0.0197 (5)
O9	0.3549 (5)	0.5133 (4)	0.1651 (4)	0.0462 (8)
H1	1.102 (3)	0.760 (4)	0.373 (4)	0.011 (8)*
H7	0.489 (6)	1.275 (4)	0.822 (6)	0.061 (17)*
H8	0.363 (6)	1.155 (7)	0.866 (5)	0.065 (17)*
H9	0.331 (8)	0.448 (7)	0.216 (6)	0.08 (2)*
H10	0.269 (6)	0.501 (9)	0.096 (5)	0.09 (2)*

	U11	U22	U33	U12	U13	U23
C1	0.0095 (13)	0.0105 (13)	0.0124 (14)	0.0018 (10)	0.0013 (10)	0.0039 (11)
C2	0.0128 (14)	0.0109 (14)	0.0113 (14)	0.0000 (11)	0.0015 (11)	0.0027 (11)
C3	0.0087 (14)	0.0118 (14)	0.0147 (14)	0.0008 (10)	0.0034 (11)	0.0046 (11)
C4	0.0136 (14)	0.0110 (14)	0.0126 (14)	0.0038 (11)	0.0029 (11)	0.0037 (11)
C5	0.0135 (15)	0.0159 (15)	0.0141 (15)	−0.0008 (11)	0.0017 (11)	0.0020 (12)
C6	0.0149 (15)	0.0161 (15)	0.0143 (15)	−0.0008 (12)	0.0039 (11)	0.0020 (12)
C7	0.0123 (14)	0.0095 (13)	0.0088 (13)	0.0042 (11)	0.0022 (10)	0.0012 (11)
C8	0.0096 (14)	0.0128 (14)	0.0115 (14)	0.0002 (11)	0.0017 (10)	0.0038 (11)
Ho1	0.00804 (7)	0.00981 (7)	0.00735 (7)	−0.00004 (5)	−0.00004 (4)	0.00353 (5)
N1	0.0126 (13)	0.0181 (13)	0.0151 (13)	−0.0051 (10)	0.0041 (10)	0.0022 (11)
O1	0.0163 (11)	0.0151 (11)	0.0127 (10)	−0.0024 (8)	0.0061 (8)	−0.0002 (9)
O2	0.0108 (10)	0.0137 (10)	0.0141 (10)	−0.0019 (8)	−0.0005 (8)	0.0045 (8)
O3	0.0173 (11)	0.0149 (10)	0.0106 (10)	0.0019 (8)	0.0050 (8)	0.0015 (8)
O4	0.0108 (10)	0.0185 (11)	0.0109 (10)	0.0007 (8)	0.0001 (8)	0.0069 (8)
O5	0.0105 (10)	0.0159 (10)	0.0101 (10)	0.0012 (8)	0.0004 (8)	0.0052 (8)
O6	0.0170 (11)	0.0165 (11)	0.0148 (11)	−0.0054 (8)	−0.0047 (8)	0.0103 (9)
O7	0.0108 (10)	0.0189 (11)	0.0115 (10)	−0.0019 (8)	−0.0010 (8)	0.0086 (8)
O8	0.0220 (13)	0.0232 (13)	0.0201 (12)	0.0096 (10)	0.0087 (9)	0.0122 (10)
O9	0.056 (2)	0.0259 (15)	0.055 (2)	0.0023 (14)	−0.0118 (17)	0.0206 (15)

C1—O2i	1.259 (4)	C8—O6	1.235 (4)
C1—O1	1.260 (4)	C8—O7v	1.269 (3)
C1—C2ii	1.507 (4)	C8—C8v	1.545 (6)
C2—C3	1.388 (4)	Ho1—O2	2.245 (2)
C2—C6	1.390 (4)	Ho1—O3	2.271 (2)
C2—C1iii	1.507 (4)	Ho1—O7	2.322 (2)
C3—C4	1.414 (4)	Ho1—O4	2.372 (2)
C3—H3	0.9500	Ho1—O5	2.399 (2)
C4—O3	1.311 (4)	Ho1—O1	2.429 (2)
C4—C5	1.400 (4)	Ho1—O8	2.435 (2)
C5—N1	1.340 (4)	Ho1—O6	2.455 (2)
C5—H5	0.9500	N1—H1	0.90 (1)
C6—N1	1.337 (4)	O8—H7	0.85 (1)
C6—H6	0.9500	O8—H8	0.85 (1)
C7—O5iv	1.237 (3)	O9—H9	0.85 (1)
C7—O4	1.266 (4)	O9—H10	0.85 (1)
C7—C7iv	1.559 (6)
O2i—C1—O1	123.0 (3)	O4—Ho1—O5	68.67 (7)
O2i—C1—C2ii	119.6 (3)	O2—Ho1—O1	112.36 (7)
O1—C1—C2ii	117.4 (3)	O3—Ho1—O1	143.48 (8)
C3—C2—C6	119.6 (3)	O7—Ho1—O1	91.68 (7)
C3—C2—C1iii	122.1 (3)	O4—Ho1—O1	75.80 (7)
C6—C2—C1iii	118.3 (3)	O5—Ho1—O1	67.35 (7)
C2—C3—C4	121.0 (3)	O2—Ho1—O8	83.88 (8)
C2—C3—H3	119.5	O3—Ho1—O8	142.95 (8)
C4—C3—H3	119.5	O7—Ho1—O8	75.53 (8)
O3—C4—C5	121.8 (3)	O4—Ho1—O8	130.78 (7)
O3—C4—C3	122.0 (3)	O5—Ho1—O8	126.55 (8)
C5—C4—C3	116.2 (3)	O1—Ho1—O8	71.62 (8)
N1—C5—C4	120.9 (3)	O2—Ho1—O6	74.25 (7)
N1—C5—H5	119.5	O3—Ho1—O6	74.55 (8)
C4—C5—H5	119.5	O7—Ho1—O6	68.06 (7)
N1—C6—C2	118.5 (3)	O4—Ho1—O6	141.48 (7)
N1—C6—H6	120.7	O5—Ho1—O6	132.12 (7)
C2—C6—H6	120.7	O1—Ho1—O6	138.53 (7)
O5iv—C7—O4	126.2 (3)	O8—Ho1—O6	68.47 (8)
O5iv—C7—C7iv	118.1 (3)	C6—N1—C5	123.8 (3)
O4—C7—C7iv	115.7 (3)	C6—N1—H1	117 (2)
O6—C8—O7v	126.3 (3)	C5—N1—H1	119 (2)
O6—C8—C8v	118.0 (3)	C1—O1—Ho1	115.09 (18)
O7v—C8—C8v	115.6 (3)	C1i—O2—Ho1	169.7 (2)
O2—Ho1—O3	88.38 (8)	C4—O3—Ho1	132.61 (19)
O2—Ho1—O7	141.51 (7)	C7—O4—Ho1	118.19 (18)
O3—Ho1—O7	88.96 (8)	C7iv—O5—Ho1	116.85 (18)
O2—Ho1—O4	75.56 (7)	C8—O6—Ho1	115.09 (18)
O3—Ho1—O4	81.26 (8)	C8v—O7—Ho1	119.68 (18)
O7—Ho1—O4	141.63 (7)	Ho1—O8—H7	108 (4)
O2—Ho1—O5	143.17 (7)	Ho1—O8—H8	106 (4)
O3—Ho1—O5	78.02 (7)	H7—O8—H8	126 (5)
O7—Ho1—O5	73.02 (7)	H9—O9—H10	111 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O7vi	0.90 (1)	1.83 (1)	2.727 (3)	171 (3)
O8—H7···O9v	0.85 (1)	1.95 (1)	2.787 (4)	171 (5)
O8—H8···O4i	0.85 (1)	1.96 (1)	2.811 (3)	177 (6)
O9—H9···O3vii	0.85 (1)	2.08 (1)	2.929 (4)	178 (6)
O9—H10···O1v	0.85 (1)	2.48 (6)	3.003 (4)	120 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O7i	0.90 (1)	1.83 (1)	2.727 (3)	171 (3)
O8—H7⋯O9ii	0.85 (1)	1.95 (1)	2.787 (4)	171 (5)
O8—H8⋯O4iii	0.85 (1)	1.96 (1)	2.811 (3)	177 (6)
O9—H9⋯O3iv	0.85 (1)	2.08 (1)	2.929 (4)	178 (6)
O9—H10⋯O1ii	0.85 (1)	2.48 (6)	3.003 (4)	120 (5)

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