Poly[(6-carboxy-picolinato-κO,N,O)(μ(3)-pyridine-2,6-dicarboxyl-ato-κO,N,O:O:O)dysprosium(III)].

In the title complex, [Dy(C(7)H(3)NO(4))(C(7)H(4)NO(4))](n), one of the ligands is fully deprotonated while the second has lost only one H atom. Each Dy(III) ion is coordinated by six O atoms and two N atoms from two pyridine-2,6-dicarboxyl-ate and two 6-carboxy-picolinate ligands, displaying a bicapped trigonal-prismatic geometry. The average Dy-O bond distance is 2.40 Å, some 0.1Å longer than the corresponding Ho-O distance in the isotypic holmium complex. Adjacent Dy(III) ions are linked by the pyridine-2,6-dicarboxyl-ate ligands, forming a layer in (100). These layers are further connected by π-π stacking inter-actions between neighboring pyridyl rings [centroid-centroid distance = 3.827 (3) Å] and C-H⋯O hydrogen-bonding inter-actions, assembling a three-dimensional supra-molecular network. Within each layer, there are other π-π stacking inter-actions between neighboring pyridyl rings [centroid-centroid distance = 3.501 (2) Å] and O-H⋯O and C-H⋯O hydrogen-bonding inter-actions, which further stabilize the structure.

Related literature

For the isotypic holmium analogue, see: Fernandes et al. (2001 ▶). For other related structures, see: Hong (2007 ▶); Huang et al. (2008 ▶); Idrees et al. (2009 ▶); Rafizadeh & Amani (2006 ▶); Thallapally et al. (2008 ▶).

Experimental

Crystal data

[Dy(C7H3NO4)(C7H4NO4)]

M = 493.72

Monoclinic,

a = 12.2151 (14) Å

b = 8.3703 (10) Å

c = 13.4698 (16) Å

β = 102.332 (1)°

V = 1345.4 (3) Å3

Z = 4

Mo Kα radiation

μ = 5.61 mm−1

T = 296 K

0.23 × 0.21 × 0.19 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.359, T max = 0.415

6670 measured reflections

2413 independent reflections

2305 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.051

S = 1.12

2413 reflections

229 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.58 e Å−3

Δρmin = −1.43 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809039075/sj2654sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039075/sj2654Isup2.hkl

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

[Dy(C7H3NO4)(C7H4NO4)]	F(000) = 940
Mr = 493.72	Dx = 2.437 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5626 reflections
a = 12.2151 (14) Å	θ = 2.4–27.8°
b = 8.3703 (10) Å	µ = 5.61 mm−1
c = 13.4698 (16) Å	T = 296 K
β = 102.332 (1)°	Block, colourless
V = 1345.4 (3) Å3	0.23 × 0.21 × 0.19 mm
Z = 4

Bruker APEXII area-detector diffractometer	2413 independent reflections
Radiation source: fine-focus sealed tube	2305 reflections with I > 2σ(I)
graphite	Rint = 0.024
φ and ω scans	θmax = 25.2°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→12
Tmin = 0.359, Tmax = 0.415	k = −8→10
6670 measured reflections	l = −16→16

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.051	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0241P)2 + 1.92P] where P = (Fo2 + 2Fc2)/3
2413 reflections	(Δ/σ)max = 0.002
229 parameters	Δρmax = 0.58 e Å−3
1 restraint	Δρmin = −1.43 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Dy1	0.197015 (13)	0.232131 (18)	0.818183 (11)	0.00903 (7)
C2	0.5158 (3)	0.5574 (5)	0.8746 (3)	0.0243 (9)
H2	0.5247	0.6677	0.8750	0.029*
C3	0.4095 (3)	0.4901 (4)	0.8567 (3)	0.0184 (8)
C4	0.4836 (3)	0.2361 (4)	0.8735 (3)	0.0187 (8)
C1	0.6084 (3)	0.4572 (5)	0.8919 (3)	0.0282 (9)
H1	0.6805	0.4990	0.9030	0.034*
C5	0.5912 (3)	0.2933 (5)	0.8922 (3)	0.0274 (9)
H5	0.6518	0.2233	0.9049	0.033*
N1	0.3933 (2)	0.3321 (3)	0.8555 (2)	0.0136 (6)
C6	0.3019 (3)	0.5872 (4)	0.8367 (3)	0.0201 (8)
O1	0.2131 (2)	0.5091 (3)	0.82690 (18)	0.0180 (6)
O2	0.3085 (3)	0.7328 (3)	0.8293 (3)	0.0452 (10)
C7	0.4611 (3)	0.0608 (4)	0.8716 (3)	0.0203 (8)
O4	0.3508 (2)	0.0270 (3)	0.8468 (2)	0.0202 (6)
O3	0.5333 (2)	−0.0385 (3)	0.8889 (3)	0.0368 (8)
C13	0.2072 (3)	0.1845 (4)	1.0625 (2)	0.0128 (7)
C8	0.1581 (3)	0.0254 (4)	1.0222 (2)	0.0122 (7)
O5	0.2310 (2)	0.2782 (3)	0.9969 (2)	0.0200 (6)
N2	0.1355 (2)	0.0186 (3)	0.9205 (2)	0.0107 (6)
C11	0.0664 (3)	−0.2478 (4)	0.9275 (3)	0.0171 (8)
H11	0.0339	−0.3386	0.8937	0.021*
C12	0.0876 (3)	−0.1133 (4)	0.8745 (2)	0.0115 (7)
O7	0.1092 (2)	0.0071 (3)	0.72203 (17)	0.0148 (5)
O6	0.2198 (2)	0.2145 (3)	1.15526 (19)	0.0184 (6)
C14	0.0590 (3)	−0.0988 (4)	0.7607 (2)	0.0115 (7)
C9	0.1386 (3)	−0.1020 (4)	1.0812 (3)	0.0152 (7)
H9	0.1539	−0.0945	1.1517	0.018*
C10	0.0953 (3)	−0.2420 (4)	1.0324 (3)	0.0183 (8)
H10	0.0858	−0.3317	1.0703	0.022*
O8	−0.0153 (2)	−0.1898 (3)	0.71176 (18)	0.0171 (5)
H2A	0.334 (3)	0.822 (3)	0.838 (3)	0.026*

	U11	U22	U33	U12	U13	U23
Dy1	0.00974 (11)	0.00762 (10)	0.01008 (11)	−0.00032 (5)	0.00291 (7)	0.00052 (5)
C2	0.026 (2)	0.0179 (19)	0.030 (2)	−0.0111 (16)	0.0069 (17)	−0.0045 (16)
C3	0.022 (2)	0.0131 (17)	0.0203 (19)	−0.0011 (15)	0.0048 (15)	0.0002 (14)
C4	0.015 (2)	0.0168 (18)	0.024 (2)	−0.0005 (14)	0.0039 (16)	−0.0011 (14)
C1	0.019 (2)	0.025 (2)	0.040 (3)	−0.0099 (16)	0.0056 (18)	−0.0064 (17)
C5	0.015 (2)	0.023 (2)	0.042 (3)	−0.0006 (16)	0.0021 (18)	−0.0035 (18)
N1	0.0122 (15)	0.0120 (14)	0.0171 (15)	−0.0013 (12)	0.0043 (12)	0.0005 (11)
C6	0.025 (2)	0.0145 (18)	0.0207 (19)	0.0017 (15)	0.0048 (16)	0.0005 (14)
O1	0.0183 (14)	0.0111 (13)	0.0251 (14)	−0.0001 (10)	0.0057 (11)	0.0010 (9)
O2	0.039 (2)	0.0065 (14)	0.088 (3)	−0.0048 (12)	0.009 (2)	0.0015 (15)
C7	0.016 (2)	0.0165 (18)	0.029 (2)	0.0006 (15)	0.0053 (16)	−0.0004 (15)
O4	0.0121 (13)	0.0105 (12)	0.0378 (16)	−0.0023 (10)	0.0048 (11)	0.0001 (10)
O3	0.0185 (15)	0.0197 (15)	0.070 (2)	0.0055 (12)	0.0043 (15)	0.0011 (14)
C13	0.0114 (17)	0.0152 (17)	0.0122 (18)	0.0025 (13)	0.0031 (14)	0.0011 (13)
C8	0.0097 (17)	0.0157 (17)	0.0124 (17)	0.0037 (13)	0.0049 (13)	−0.0021 (13)
O5	0.0295 (16)	0.0178 (13)	0.0137 (14)	−0.0094 (11)	0.0066 (12)	−0.0016 (10)
N2	0.0102 (14)	0.0123 (14)	0.0102 (14)	−0.0009 (11)	0.0036 (11)	−0.0004 (11)
C11	0.024 (2)	0.0125 (17)	0.017 (2)	−0.0039 (13)	0.0096 (17)	−0.0024 (13)
C12	0.0103 (17)	0.0112 (16)	0.0143 (17)	−0.0011 (13)	0.0053 (13)	0.0000 (13)
O7	0.0177 (13)	0.0146 (12)	0.0131 (12)	−0.0036 (10)	0.0054 (10)	−0.0004 (9)
O6	0.0262 (15)	0.0182 (13)	0.0119 (13)	−0.0017 (11)	0.0064 (11)	−0.0037 (10)
C14	0.0093 (17)	0.0120 (16)	0.0139 (17)	0.0019 (13)	0.0043 (13)	−0.0033 (13)
C9	0.0166 (18)	0.0191 (18)	0.0107 (17)	0.0001 (14)	0.0044 (14)	0.0015 (13)
C10	0.019 (2)	0.0191 (18)	0.018 (2)	−0.0012 (14)	0.0068 (16)	0.0061 (13)
O8	0.0159 (13)	0.0198 (13)	0.0163 (13)	−0.0061 (11)	0.0052 (10)	−0.0045 (10)

Dy1—O8i	2.266 (2)	O2—H2A	0.811 (19)
Dy1—O6ii	2.314 (3)	C7—O3	1.198 (5)
Dy1—O1	2.328 (2)	C7—O4	1.347 (4)
Dy1—O5	2.385 (3)	C13—O6	1.251 (4)
Dy1—O7	2.405 (2)	C13—O5	1.261 (4)
Dy1—N2	2.469 (3)	C13—C8	1.513 (5)
Dy1—N1	2.488 (3)	C8—N2	1.341 (4)
Dy1—O4	2.513 (2)	C8—C9	1.381 (5)
C2—C1	1.388 (6)	N2—C12	1.338 (4)
C2—C3	1.389 (6)	C11—C10	1.382 (6)
C2—H2	0.9300	C11—C12	1.387 (5)
C3—N1	1.336 (4)	C11—H11	0.9300
C3—C6	1.519 (5)	C12—C14	1.502 (5)
C4—N1	1.344 (5)	O7—C14	1.253 (4)
C4—C5	1.371 (6)	O6—Dy1iii	2.314 (3)
C4—C7	1.492 (5)	C14—O8	1.257 (4)
C1—C5	1.388 (6)	C9—C10	1.392 (5)
C1—H1	0.9300	C9—H9	0.9300
C5—H5	0.9300	C10—H10	0.9300
C6—O2	1.226 (4)	O8—Dy1iv	2.266 (2)
C6—O1	1.250 (5)
O8i—Dy1—O6ii	95.01 (9)	C1—C5—H5	120.5
O8i—Dy1—O1	77.91 (9)	C3—N1—C4	118.4 (3)
O6ii—Dy1—O1	80.18 (9)	C3—N1—Dy1	117.9 (2)
O8i—Dy1—O5	94.91 (9)	C4—N1—Dy1	123.6 (2)
O6ii—Dy1—O5	153.60 (9)	O2—C6—O1	125.5 (4)
O1—Dy1—O5	78.08 (8)	O2—C6—C3	118.5 (4)
O8i—Dy1—O7	79.79 (9)	O1—C6—C3	115.9 (3)
O6ii—Dy1—O7	76.74 (8)	C6—O1—Dy1	126.0 (2)
O1—Dy1—O7	146.15 (8)	C6—O2—H2A	159 (3)
O5—Dy1—O7	129.18 (8)	O3—C7—O4	124.0 (3)
O8i—Dy1—N2	84.53 (9)	O3—C7—C4	123.6 (4)
O6ii—Dy1—N2	141.40 (9)	O4—C7—C4	112.4 (3)
O1—Dy1—N2	136.47 (9)	C7—O4—Dy1	124.8 (2)
O5—Dy1—N2	64.02 (8)	O6—C13—O5	125.3 (3)
O7—Dy1—N2	65.15 (8)	O6—C13—C8	119.3 (3)
O8i—Dy1—N1	143.55 (10)	O5—C13—C8	115.4 (3)
O6ii—Dy1—N1	79.66 (9)	N2—C8—C9	122.2 (3)
O1—Dy1—N1	65.64 (9)	N2—C8—C13	112.5 (3)
O5—Dy1—N1	77.84 (10)	C9—C8—C13	125.3 (3)
O7—Dy1—N1	132.22 (9)	C13—O5—Dy1	126.2 (2)
N2—Dy1—N1	121.72 (9)	C12—N2—C8	118.8 (3)
O8i—Dy1—O4	153.64 (9)	C12—N2—Dy1	119.6 (2)
O6ii—Dy1—O4	92.28 (9)	C8—N2—Dy1	121.3 (2)
O1—Dy1—O4	128.35 (8)	C10—C11—C12	117.6 (3)
O5—Dy1—O4	89.58 (9)	C10—C11—H11	121.2
O7—Dy1—O4	77.30 (8)	C12—C11—H11	121.2
N2—Dy1—O4	74.15 (9)	N2—C12—C11	122.9 (3)
N1—Dy1—O4	62.74 (8)	N2—C12—C14	112.9 (3)
C1—C2—C3	118.9 (3)	C11—C12—C14	124.2 (3)
C1—C2—H2	120.6	C14—O7—Dy1	122.1 (2)
C3—C2—H2	120.6	C13—O6—Dy1iii	166.3 (2)
N1—C3—C2	122.2 (3)	O7—C14—O8	125.0 (3)
N1—C3—C6	114.1 (3)	O7—C14—C12	116.9 (3)
C2—C3—C6	123.7 (3)	O8—C14—C12	118.1 (3)
N1—C4—C5	122.8 (3)	C8—C9—C10	118.2 (3)
N1—C4—C7	116.3 (3)	C8—C9—H9	120.9
C5—C4—C7	120.8 (3)	C10—C9—H9	120.9
C2—C1—C5	118.7 (4)	C11—C10—C9	120.1 (3)
C2—C1—H1	120.7	C11—C10—H10	120.0
C5—C1—H1	120.7	C9—C10—H10	120.0
C4—C5—C1	119.0 (4)	C14—O8—Dy1iv	146.8 (2)
C4—C5—H5	120.5

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O4v	0.81 (2)	1.73 (2)	2.518 (3)	164 (5)
O2—H2A···O3v	0.81 (2)	2.65 (3)	3.303 (4)	139 (4)
C9—H9···O1iii	0.93	2.42	3.332 (4)	165
C1—H1···O5vi	0.93	2.42	3.123 (5)	133
C2—H2···O3v	0.93	2.47	3.393 (5)	174

Table 1

Selected bond lengths (Å)

Dy1—O8i	2.266 (2)
Dy1—O6ii	2.314 (3)
Dy1—O1	2.328 (2)
Dy1—O5	2.385 (3)
Dy1—O7	2.405 (2)
Dy1—N2	2.469 (3)
Dy1—N1	2.488 (3)
Dy1—O4	2.513 (2)

Symmetry codes: (i) ; (ii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O4iii	0.811 (19)	1.73 (2)	2.518 (3)	164 (5)
O2—H2A⋯O3iii	0.811 (19)	2.65 (3)	3.303 (4)	139 (4)
C9—H9⋯O1iv	0.93	2.42	3.332 (4)	165
C1—H1⋯O5v	0.93	2.42	3.123 (5)	133
C2—H2⋯O3iii	0.93	2.47	3.393 (5)	174

Symmetry code: (iii) ; (iv) ; (v) .