Poly[(μ6-6-oxidopyridinium-2-carboxyl­ato)caesium]

Kang, S.K.; Shim, Y.S.

doi:10.1107/S1600536811031874

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page m1237

doi:10.1107/S1600536811031874

Open

access

Poly[(μ₆-6-oxidopyridinium-2-carboxylato)caesium]

Sung Kwon Kang ^a ^* and Yong Suk Shim ^a

^aDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea
^*Correspondence e-mail: skkang@cnu.ac.kr

(Received 6 August 2011; accepted 6 August 2011; online 17 August 2011)

The asymmetric unit of the polymeric title salt, [Cs(C₆H₄NO₃)]_n, comprises a Cs⁺ cation and a 6-oxidopyridinium-2-carboxylate anion. The Cs⁺ cation is six-coordinated by O atoms derived from two oxido and four carboxylate O atoms; each O atom in the anion bridges two Cs⁺ cations. In the crystal, intermolecular N—H⋯O hydrogen bonding is present and contributes to the stability of the three-dimensional network generated by the bridging O atoms.

Related literature

For general background to pyridine carboxylic complexes, see: Kang (2011 ); Lee & Kang (2010 ); Hong et al. (2008 ). For the Cs—O bond lengths in caesium aryloxide complexes, see: Ungaro et al. (1994 ); Clark et al. (1998 ); Weinert et al. (2003 ).

Experimental

Crystal data

[Cs(C₆H₄NO₃)]
M_r = 271.01
Monoclinic, P 2₁ /c
a = 8.1746 (3) Å
b = 7.5513 (2) Å
c = 12.3843 (4) Å
β = 91.889 (1)°
V = 764.05 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.8 mm⁻¹
T = 296 K
0.10 × 0.07 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.654, T_max = 0.745
6897 measured reflections
1822 independent reflections
1592 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.072
S = 1.00
1822 reflections
104 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.19 e Å⁻³
Δρ_min = −1.14 e Å⁻³

Table 1
Selected bond lengths (Å)

Cs1—O9ⁱ	2.938 (2)
Cs1—O10ⁱⁱ	2.991 (3)
Cs1—O9	3.070 (3)
Cs1—O10ⁱⁱⁱ	3.105 (3)
Cs1—O11^iv	3.147 (2)
Cs1—O11^v	3.317 (2)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O11^vi	0.78 (3)	2.15 (3)	2.915 (4)	168 (3)
Symmetry code: (vi) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2010 )'; software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811031874/tk2776sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811031874/tk2776Isup2.hkl

checkCIF report

Comment top

During studies of lanthanide complexes of picolinic acid and their derivatives due to their interesting photoluminescent properties (Kang, 2011; Lee & Kang, 2010; Hong et al., 2008), the title compound was obtained as a side-product.

The asymmetric unit of the title compound, [Cs(C₆H₄NO₃)]_n, comprises a Cs⁺ cation and a carboxylatooxidopyridinium anion. The Cs⁺ cation is coordinated to the two oxide O atoms and four carboxylate-O atoms (Fig. 1). The Cs—O bond distances lie within the range 2.938 (2) - 3.317 (2) Å (Table 1). The observed Cs—O distances are a little longer than those observed in caesium picrate complexes and caesium phenoxide complexes (Ungaro et al., 1994: Clark et al., 1998; Weinert et al., 2003). The dihedral angle between the pyridine ring and the carboxylate group is 6.95 (19) °. In the crystal structure, the Cs atoms are linked by O atoms of the anionic ligands to form a three-dimensional network (Fig. 2) with additional stability provided by intermolecular N—H···O hydrogen bonding (Table 2).

Related literature top

For general background to pyridine carboxylic complexes, see: Kang (2011); Lee & Kang (2010); Hong et al. (2008). For the Cs—O bond distances in caesium aryloxide complexes, see: Ungaro et al. (1994); Clark et al. (1998); Weinert et al. (2003).

Experimental top

Europium trichloride solution was prepared by dissolving EuCl₃ 6H₂O (0.37 g, 1.0 mmol; Aldrich) in absolute ethanol (20 ml) at room temperature with stirring. The ligand solution was prepared by dissolving 6-hydroxypicolinic acid (0.56 g, 4.0 mmol; Aldrich) in absolute ethanol (30 ml) at room temperature. The pH of the ligand solution was adjusted to about 6 with 2 N CsOH solution. The Eu solution was added drop wise and slowly to the ligand solution. The reaction mixture was stirred for 2 h at room temperature. Colourless crystals of (I) were obtained at room temperature over a period of a few weeks. The complex was recrystallized from distilled water.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2010)'; software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of (l), showing the atom-numbering scheme and 20% probability ellipsoids. [Symmetry code: (i) -x + 1, y + 1/2, -z + 1/2; (ii) -x + 1, y - 1/2, -z + 1/2; (iii) x, -y + 1/2, z - 1/2; (iv) x + 1, -y + 1/2, z - 1/2; (v) -x, y - 1/2, -z + 1/2].
	Fig. 2. The three-dimensional framework of (I).

Poly[(µ₆-6-oxidopyridinium-2-carboxylato)caesium] top

Crystal data top

[Cs(C₆H₄NO₃)]	F(000) = 504
M_r = 271.01	D_x = 2.356 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3429 reflections
a = 8.1746 (3) Å	θ = 2.5–28.3°
b = 7.5513 (2) Å	µ = 4.8 mm⁻¹
c = 12.3843 (4) Å	T = 296 K
β = 91.889 (1)°	Block, colourless
V = 764.05 (4) Å³	0.1 × 0.07 × 0.06 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1592 reflections with I > 2σ(I)
ϕ and ω scans	R_int = 0.072
Absorption correction: multi-scan (SADABS; Bruker, 2002)	θ_max = 28.3°, θ_min = 2.5°
T_min = 0.654, T_max = 0.745	h = −3→10
6897 measured reflections	k = −10→7
1822 independent reflections	l = −15→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.0401P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.072	(Δ/σ)_max = 0.001
S = 1.00	Δρ_max = 1.19 e Å⁻³
1822 reflections	Δρ_min = −1.14 e Å⁻³
104 parameters

Crystal data top

[Cs(C₆H₄NO₃)]	V = 764.05 (4) Å³
M_r = 271.01	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1746 (3) Å	µ = 4.8 mm⁻¹
b = 7.5513 (2) Å	T = 296 K
c = 12.3843 (4) Å	0.1 × 0.07 × 0.06 mm
β = 91.889 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1822 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1592 reflections with I > 2σ(I)
T_min = 0.654, T_max = 0.745	R_int = 0.072
6897 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 1.19 e Å⁻³
1822 reflections	Δρ_min = −1.14 e Å⁻³
104 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cs1	0.51201 (2)	0.14792 (3)	0.127051 (18)	0.04196 (11)
N2	0.0320 (3)	0.2743 (4)	0.4216 (2)	0.0304 (5)
H2	0.088 (4)	0.348 (4)	0.446 (3)	0.028 (9)*
C3	0.1062 (3)	0.1326 (4)	0.3746 (3)	0.0291 (6)
C4	0.0159 (4)	−0.0019 (5)	0.3335 (3)	0.0402 (8)
H4	0.0655	−0.0992	0.3023	0.048*
C5	−0.1567 (4)	0.0085 (5)	0.3391 (3)	0.0474 (9)
H5	−0.221	−0.0826	0.3102	0.057*
C6	−0.2296 (4)	0.1484 (5)	0.3857 (3)	0.0444 (9)
H6	−0.343	0.152	0.3888	0.053*
C7	−0.1347 (3)	0.2903 (5)	0.4302 (3)	0.0334 (7)
C8	0.2926 (3)	0.1403 (4)	0.3700 (3)	0.0298 (6)
O9	0.3603 (3)	0.0066 (3)	0.3335 (2)	0.0487 (6)
O10	0.3588 (2)	0.2803 (4)	0.3984 (2)	0.0536 (7)
O11	−0.1942 (2)	0.4235 (3)	0.4750 (2)	0.0498 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.03869 (13)	0.03507 (16)	0.05252 (19)	−0.00018 (7)	0.00759 (9)	−0.00010 (9)
N2	0.0203 (10)	0.0308 (14)	0.0402 (16)	−0.0019 (10)	0.0026 (9)	−0.0062 (12)
C3	0.0234 (12)	0.0316 (16)	0.0324 (17)	0.0012 (10)	0.0034 (10)	0.0006 (12)
C4	0.0313 (14)	0.0409 (19)	0.049 (2)	−0.0026 (12)	0.0044 (12)	−0.0145 (16)
C5	0.0316 (15)	0.049 (2)	0.061 (3)	−0.0137 (14)	−0.0003 (14)	−0.0201 (18)
C6	0.0216 (13)	0.056 (2)	0.055 (2)	−0.0055 (12)	0.0003 (13)	−0.0125 (17)
C7	0.0209 (11)	0.0393 (17)	0.0401 (19)	0.0013 (11)	0.0030 (10)	−0.0036 (15)
C8	0.0226 (12)	0.0325 (17)	0.0346 (18)	0.0020 (10)	0.0045 (10)	0.0017 (12)
O9	0.0321 (11)	0.0421 (14)	0.0725 (19)	0.0074 (10)	0.0112 (10)	−0.0090 (13)
O10	0.0235 (9)	0.0383 (14)	0.099 (2)	−0.0025 (9)	0.0070 (11)	−0.0189 (15)
O11	0.0244 (10)	0.0483 (15)	0.0772 (19)	0.0022 (10)	0.0070 (10)	−0.0231 (14)

Geometric parameters (Å, º) top

Cs1—O9ⁱ	2.938 (2)	C5—C6	1.352 (5)
Cs1—O10ⁱⁱ	2.991 (3)	C5—H5	0.93
Cs1—O9	3.070 (3)	C6—C7	1.423 (4)
Cs1—O10ⁱⁱⁱ	3.105 (3)	C6—H6	0.93
Cs1—O11^iv	3.147 (2)	C7—O11	1.254 (4)
Cs1—O11^v	3.317 (2)	C8—O10	1.234 (4)
N2—C3	1.370 (4)	C8—O9	1.244 (4)
N2—C7	1.376 (3)	O9—Cs1ⁱⁱ	2.938 (2)
N2—H2	0.78 (3)	O10—Cs1ⁱ	2.991 (3)
C3—C4	1.345 (4)	O10—Cs1^vi	3.105 (3)
C3—C8	1.527 (4)	O11—Cs1^vii	3.147 (2)
C4—C5	1.418 (4)	O11—Cs1^viii	3.317 (2)
C4—H4	0.93

O9ⁱ—Cs1—O10ⁱⁱ	138.47 (6)	C3—N2—C7	123.8 (3)
O9ⁱ—Cs1—O9	109.46 (5)	C3—N2—H2	118 (3)
O10ⁱⁱ—Cs1—O9	85.35 (7)	C7—N2—H2	119 (3)
O9ⁱ—Cs1—O10ⁱⁱⁱ	96.96 (7)	C4—C3—N2	120.3 (3)
O10ⁱⁱ—Cs1—O10ⁱⁱⁱ	101.48 (6)	C4—C3—C8	123.4 (3)
O9—Cs1—O10ⁱⁱⁱ	131.16 (6)	N2—C3—C8	116.3 (2)
O9ⁱ—Cs1—O11^iv	89.05 (7)	C3—C4—C5	118.3 (3)
O10ⁱⁱ—Cs1—O11^iv	59.91 (6)	C3—C4—H4	120.8
O9—Cs1—O11^iv	140.90 (6)	C5—C4—H4	120.8
O10ⁱⁱⁱ—Cs1—O11^iv	77.13 (6)	C6—C5—C4	121.1 (3)
O9ⁱ—Cs1—O11^v	143.52 (6)	C6—C5—H5	119.4
O10ⁱⁱ—Cs1—O11^v	76.13 (6)	C4—C5—H5	119.4
O9—Cs1—O11^v	78.86 (6)	C5—C6—C7	120.8 (3)
O10ⁱⁱⁱ—Cs1—O11^v	56.95 (6)	C5—C6—H6	119.6
O11^iv—Cs1—O11^v	106.75 (4)	C7—C6—H6	119.6
O9ⁱ—Cs1—O10	74.53 (6)	O11—C7—N2	120.3 (3)
O10ⁱⁱ—Cs1—O10	118.05 (6)	O11—C7—C6	124.1 (3)
O9—Cs1—O10	36.14 (6)	N2—C7—C6	115.6 (3)
O10ⁱⁱⁱ—Cs1—O10	129.22 (5)	O10—C8—O9	127.1 (3)
O11^iv—Cs1—O10	149.72 (6)	O10—C8—C3	116.8 (3)
O11^v—Cs1—O10	101.34 (6)	O9—C8—C3	116.0 (3)
O9ⁱ—Cs1—C7^iv	74.04 (7)	Cs1ⁱⁱ—O9—Cs1	107.94 (7)
O10ⁱⁱ—Cs1—C7^iv	76.81 (7)	Cs1ⁱ—O10—Cs1^vi	78.52 (6)
O9—Cs1—C7^iv	153.81 (6)	Cs1ⁱ—O10—Cs1	91.33 (7)
O10ⁱⁱⁱ—Cs1—C7^iv	72.02 (6)	Cs1^vi—O10—Cs1	136.48 (6)
O11^iv—Cs1—C7^iv	16.91 (7)	Cs1^vii—O11—Cs1^viii	73.25 (4)
O11^v—Cs1—C7^iv	114.40 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O11^ix	0.78 (3)	2.15 (3)	2.915 (4)	168 (3)

Symmetry code: (ix) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cs(C₆H₄NO₃)]
M_r	271.01
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.1746 (3), 7.5513 (2), 12.3843 (4)
β (°)	91.889 (1)
V (Å³)	764.05 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.8
Crystal size (mm)	0.1 × 0.07 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.654, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	6897, 1822, 1592
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.072, 1.00
No. of reflections	1822
No. of parameters	104
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.19, −1.14

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2010)', WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Cs1—O9ⁱ	2.938 (2)	Cs1—O11^iv	3.147 (2)
Cs1—O10ⁱⁱ	2.991 (3)	Cs1—O11^v	3.317 (2)
Cs1—O9	3.070 (3)	C7—O11	1.254 (4)
Cs1—O10ⁱⁱⁱ	3.105 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O11^vi	0.78 (3)	2.15 (3)	2.915 (4)	168 (3)

Symmetry code: (vi) −x, −y+1, −z+1.

References

Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Clark, D. L., Click, D. R., Hollis, R. V., Scott, B. L. & Watkin, J. G. (1998). Inorg. Chem. 37, 5700–5703. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hong, J. H., Oh, Y., Kim, Y., Kang, S. K., Choi, J., Kim, W. S., Lee, J. I., Kim, S. & Hur, N. H. (2008). Cryst. Growth Des. 8, 1364–1371. Google Scholar
Kang, S. K. (2011). Bull. Korean Chem. Soc. 32, 1745–1747. Google Scholar
Lee, T. & Kang, S. K. (2010). Acta Cryst. E66, m1347–m1348. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ungaro, R., Casnati, A., Ugozzoli, F., Pochini, A., Dozol, J.-F., Hill, C. & Rouquette, H. (1994). Angew. Chem. Int. Ed. Engl. 33, 1506–1509. Google Scholar
Weinert, C. S., Fanwick, P. E. & Rothwell, I. P. (2003). Inorg. Chem. 42, 6089–6094. Web of Science CSD CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page m1237

doi:10.1107/S1600536811031874

Open

access