catena-Poly[[diaqua­manganese(II)]-μ-pyridine-2,4,6-tricarboxyl­ato-κ5N,O2,O6:O4,O4′]

Fu, D.-W.; Xu, H.-J.

doi:10.1107/S1600536807058102

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m35

https://doi.org/10.1107/S1600536807058102

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catena-Poly[[diaquamanganese(II)]-μ-pyridine-2,4,6-tricarboxylato-κ⁵N,O²,O⁶:O⁴,O^4′]

Da-Wei Fu ^a and Hai-Jun Xu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: xuhj@seu.edu.cn

(Received 7 November 2007; accepted 12 November 2007; online 6 December 2007)

In the title compound, [Mn(C₈H₂NO₆)(H₂O)₂]_n, each pyridine-2,4,6-tricarboxylate (tpc) ligand bridges two Mn^II ions with the formation of polymeric chains located on a twofold rotation axis. Each Mn^II ion is coordinated by two O and one N atoms from one tpc ligand, two O atoms from another ligand and two water molecules in a distorted pentagonal–bipyramidal geometry. The Mn—N [2.243 (2) Å] and Mn—O [2.206 (2)–2.3123 (16) Å] bond lengths are normal. The coordinated water molecules link neighbouring polymeric chains via O—H⋯O hydrogen bonds into a two-dimensional framework parallel to the bc plane.

Related literature

For the structures and potential applications of inorganic–organic hybrid coordination polymers, see: Evans & Lin (2002 ); Gao et al. (2005 ); Kil & Myunghyun (2000 ). For the structures and properties of compounds containing pyridine-2,4,6-tricarboxylicate, see: Mehmet et al. (2006 ); Moulton & Zaworotko (2001 ); Sujit et al. (2004 ); Syper et al. (1980 ).

Experimental

Crystal data

[Mn(C₈H₂NO₆)(H₂O)₂]
M_r = 299.08
Monoclinic, C 2/c
a = 11.406 (2) Å
b = 9.1463 (18) Å
c = 10.155 (2) Å
β = 107.76 (3)°
V = 1008.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.35 mm⁻¹
T = 293 (2) K
0.15 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.874, T_max = 1.000 (expected range = 0.817–0.935)
5072 measured reflections
1155 independent reflections
1109 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.089
S = 1.01
1155 reflections
84 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯O3ⁱ	0.96	2.02	2.853 (2)	144
O1W—H1WC⋯O1ⁱⁱ	0.96	2.18	2.858 (2)	127
O1W—H1WC⋯O4ⁱⁱⁱ	0.96	2.18	3.000 (2)	142
Symmetry codes: (i) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) -x, -y, -z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807058102/cv2352sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807058102/cv2352Isup2.hkl

checkCIF report

Comment top

The construction of inorganic-organic hybrid coordination polymers has been a field of rapid growth in supramolecular and material chemistry because of the formation of fascinating structures and their potential application such as ion-exchange, adsorption, catalytic, fluorescence and magnetic materials (Moulton et al., 2001; Evans et al., 2002; Kil et al., 2000). Pyridine-2, 4, 6-tricarboxylic acid (H₃tpc) is a good building unit for constructing MOFs due to the existence of both N and O atoms in the ligands, which are used along with bridging ligand to bind metal centres, which can link 3 d, 4f, and 3 d-4f metal ions. However, there are only several of reports on the infinite one-dimensional, two-dimensional and three-dimensional coordination solids assembled by H₃tpc (Gao et al., 2005); Mehmet et al., 2006); Sujit et al., 2004). In this paper, we report the crystal structure of the title compound prepared from MnCl₂.4H₂O and pyridine-2, 4, 6-tricarboxylic acid.

In (I) (Fig. 1), each metal ion is heptacoordinated and exhibits a distorted pentagonal bipyramidal geometry, in which the tpc^3- ligand is bonded equatorially through the pyridine-2, 4, 6-tricarboxylic acid (NO₄ donor set), while two water molecules occupy the axial sites. Each carboxylic acid group at the 2, 6-position of the tpcH₃ ligand is only bound to one metal ion and the carboxylic groups at the 4-position adopt chelate mode. The coordinated water molecules link two neighboring one-dimensional chains by the intermolecular hydrogen bonds to form two-dimensional framework (Fig.2).

Related literature top

For the structures and potential applications of inorganic–organic hybrid coordination polymers, see: Evans & Lin (2002); Gao et al. (2005); Kil & Myunghyun (2000). For the structures and properties of compounds containing pyridine-2,4,6-tricarboxylic acids, see: Mehmet et al. (2006); Moulton & Zaworotko (2001); Sujit et al. (2004); Syper et al. (1980).

Experimental top

The ligand, tpcH₃, was synthesized according to the reported literature (Syper et al., 1980). A mixture of tpcH₃(25 mg, 0.12 mmol), MnCl₂.4H₂O (45 mg, 0.22 mmol), five drops of EtOH, a few drops of water and two drops of hydrochloric acidsealed in a glass tube was kept at 160 °C. Yellow crystals suitable for X-ray analysis were obtained after 4 days.

Structure description top

For the structures and potential applications of inorganic–organic hybrid coordination polymers, see: Evans & Lin (2002); Gao et al. (2005); Kil & Myunghyun (2000). For the structures and properties of compounds containing pyridine-2,4,6-tricarboxylic acids, see: Mehmet et al. (2006); Moulton & Zaworotko (2001); Sujit et al. (2004); Syper et al. (1980).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 1999).

Figures top

	Fig. 1. A portion of polymeric chain in (I), showing the atomic numbering scheme and displacement ellipoids drawn at the 30% probability level [symmetry codes: (A) -x, y, 1/2 - z; (B) x, y + 1, z; (C) -x, y + 1, 1/2 - z].
	Fig. 2. A portion of the crystal packing viewed along the a axis. Dashed lines denote O—H···O hydrogen bonds. H atoms were omitted for clarity.

catena-Poly[[diaquamanganese(II)]-µ-pyridine-2,4,6-tricarboxylato- κ⁵N,O²,O⁶:O⁴,O^4'] top

Crystal data top

[Mn(C₈H₂NO₆)(H₂O)₂]	F(000) = 600
M_r = 299.08	D_x = 1.969 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5380 reflections
a = 11.406 (2) Å	θ = 3.2–27.5°
b = 9.1463 (18) Å	µ = 1.35 mm⁻¹
c = 10.155 (2) Å	T = 293 K
β = 107.76 (3)°	Block, colorless
V = 1008.9 (3) Å³	0.15 × 0.05 × 0.05 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	1155 independent reflections
Radiation source: fine-focus sealed tube	1109 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.874, T_max = 1.000	l = −13→13
5072 measured reflections

Refinement top

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0473P)² + 2.4P] where P = (F_o² + 2F_c²)/3
1155 reflections	(Δ/σ)_max < 0.001
84 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

[Mn(C₈H₂NO₆)(H₂O)₂]	V = 1008.9 (3) Å³
M_r = 299.08	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 11.406 (2) Å	µ = 1.35 mm⁻¹
b = 9.1463 (18) Å	T = 293 K
c = 10.155 (2) Å	0.15 × 0.05 × 0.05 mm
β = 107.76 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1155 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1109 reflections with I > 2σ(I)
T_min = 0.874, T_max = 1.000	R_int = 0.023
5072 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.01	Δρ_max = 0.45 e Å⁻³
1155 reflections	Δρ_min = −0.49 e Å⁻³
84 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.

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.

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

	x	y	z	U_iso*/U_eq
Mn1	0.0000	0.57159 (4)	0.2500	0.02459 (17)
O1	−0.06002 (17)	0.34882 (16)	0.31586 (18)	0.0349 (4)
O1W	−0.14376 (17)	0.58998 (18)	0.04818 (18)	0.0365 (4)
H1WB	−0.2176	0.5432	0.0532	0.055*
H1WC	−0.1160	0.5432	−0.0215	0.055*
O3	0.20027 (14)	−0.15346 (16)	0.04948 (16)	0.0281 (3)
O4	0.13754 (15)	−0.34426 (15)	0.14530 (17)	0.0291 (4)
N1	0.0000	−0.1832 (2)	0.2500	0.0195 (5)
C1	0.0000	0.2830 (3)	0.2500	0.0239 (6)
C2	0.0000	0.1182 (3)	0.2500	0.0192 (5)
C3	0.07379 (18)	0.0412 (2)	0.1868 (2)	0.0201 (4)
H3A	0.1239	0.0901	0.1441	0.024*
C4	0.07040 (17)	−0.1104 (2)	0.18927 (19)	0.0187 (4)
C5	0.14191 (18)	−0.2120 (2)	0.1247 (2)	0.0206 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0370 (3)	0.0115 (2)	0.0320 (3)	0.000	0.0205 (2)	0.000
O1	0.0548 (10)	0.0144 (7)	0.0455 (9)	0.0032 (6)	0.0302 (8)	−0.0026 (6)
O1W	0.0445 (10)	0.0296 (8)	0.0384 (9)	−0.0064 (7)	0.0174 (8)	−0.0046 (7)
O3	0.0368 (8)	0.0203 (7)	0.0383 (8)	−0.0020 (6)	0.0280 (7)	−0.0003 (6)
O4	0.0412 (8)	0.0149 (7)	0.0425 (9)	0.0005 (6)	0.0293 (7)	−0.0012 (6)
N1	0.0271 (11)	0.0121 (10)	0.0246 (11)	0.000	0.0159 (9)	0.000
C1	0.0344 (15)	0.0116 (12)	0.0267 (13)	0.000	0.0111 (11)	0.000
C2	0.0263 (13)	0.0115 (11)	0.0219 (12)	0.000	0.0104 (10)	0.000
C3	0.0262 (9)	0.0144 (8)	0.0245 (9)	−0.0017 (7)	0.0151 (8)	0.0001 (7)
C4	0.0237 (9)	0.0148 (9)	0.0217 (9)	0.0001 (7)	0.0130 (7)	−0.0009 (7)
C5	0.0243 (9)	0.0169 (9)	0.0247 (9)	0.0001 (7)	0.0138 (7)	−0.0029 (7)

Geometric parameters (Å, º) top

Mn1—O1Wⁱ	2.206 (2)	O4—Mn1^iv	2.2807 (15)
Mn1—O1W	2.206 (2)	N1—C4ⁱ	1.331 (2)
Mn1—N1ⁱⁱ	2.243 (2)	N1—C4	1.331 (2)
Mn1—O4ⁱⁱⁱ	2.2807 (15)	N1—Mn1^iv	2.243 (2)
Mn1—O4ⁱⁱ	2.2807 (15)	C1—O1ⁱ	1.248 (2)
Mn1—O1	2.3123 (16)	C1—C2	1.507 (4)
Mn1—O1ⁱ	2.3123 (16)	C2—C3ⁱ	1.395 (2)
O1—C1	1.248 (2)	C2—C3	1.395 (2)
O1W—H1WB	0.9600	C3—C4	1.387 (3)
O1W—H1WC	0.9600	C3—H3A	0.9300
O3—C5	1.274 (2)	C4—C5	1.511 (2)
O4—C5	1.232 (2)

O1Wⁱ—Mn1—O1W	171.25 (9)	Mn1—O1W—H1WB	109.4
O1Wⁱ—Mn1—N1ⁱⁱ	85.63 (4)	Mn1—O1W—H1WC	109.4
O1W—Mn1—N1ⁱⁱ	85.63 (4)	H1WB—O1W—H1WC	109.5
O1Wⁱ—Mn1—O4ⁱⁱⁱ	87.89 (7)	C5—O4—Mn1^iv	118.68 (12)
O1W—Mn1—O4ⁱⁱⁱ	89.16 (7)	C4ⁱ—N1—C4	119.9 (2)
N1ⁱⁱ—Mn1—O4ⁱⁱⁱ	70.28 (4)	C4ⁱ—N1—Mn1^iv	120.03 (11)
O1Wⁱ—Mn1—O4ⁱⁱ	89.16 (7)	C4—N1—Mn1^iv	120.03 (11)
O1W—Mn1—O4ⁱⁱ	87.89 (7)	O1—C1—O1ⁱ	122.3 (3)
N1ⁱⁱ—Mn1—O4ⁱⁱ	70.28 (4)	O1—C1—C2	118.85 (13)
O4ⁱⁱⁱ—Mn1—O4ⁱⁱ	140.55 (7)	O1ⁱ—C1—C2	118.85 (13)
O1Wⁱ—Mn1—O1	90.01 (6)	C3ⁱ—C2—C3	119.3 (2)
O1W—Mn1—O1	97.71 (6)	C3ⁱ—C2—C1	120.33 (12)
N1ⁱⁱ—Mn1—O1	151.78 (4)	C3—C2—C1	120.33 (12)
O4ⁱⁱⁱ—Mn1—O1	81.72 (5)	C4—C3—C2	118.18 (17)
O4ⁱⁱ—Mn1—O1	137.62 (5)	C4—C3—H3A	120.9
O1Wⁱ—Mn1—O1ⁱ	97.71 (6)	C2—C3—H3A	120.9
O1W—Mn1—O1ⁱ	90.01 (6)	N1—C4—C3	122.19 (17)
N1ⁱⁱ—Mn1—O1ⁱ	151.78 (4)	N1—C4—C5	112.04 (16)
O4ⁱⁱⁱ—Mn1—O1ⁱ	137.62 (5)	C3—C4—C5	125.77 (16)
O4ⁱⁱ—Mn1—O1ⁱ	81.72 (5)	O4—C5—O3	124.75 (17)
O1—Mn1—O1ⁱ	56.44 (8)	O4—C5—C4	118.36 (17)
C1—O1—Mn1	90.64 (14)	O3—C5—C4	116.86 (16)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O3^v	0.96	2.02	2.853 (2)	144
O1W—H1WC···O1^vi	0.96	2.18	2.858 (2)	127
O1W—H1WC···O4^vii	0.96	2.18	3.000 (2)	142

Symmetry codes: (v) x−1/2, y+1/2, z; (vi) x, −y+1, z−1/2; (vii) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	[Mn(C₈H₂NO₆)(H₂O)₂]
M_r	299.08
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	11.406 (2), 9.1463 (18), 10.155 (2)
β (°)	107.76 (3)
V (Å³)	1008.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.35
Crystal size (mm)	0.15 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury2
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.874, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5072, 1155, 1109
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.089, 1.01
No. of reflections	1155
No. of parameters	84
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.49

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O3ⁱ	0.96	2.02	2.853 (2)	143.5
O1W—H1WC···O1ⁱⁱ	0.96	2.18	2.858 (2)	126.6
O1W—H1WC···O4ⁱⁱⁱ	0.96	2.18	3.000 (2)	142.3

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

Acknowledgements

HJX acknowledges a Start-up Grant from Southeast University, China.

References

Evans, O. R. & Lin, W. B. (2002). Acc. Chem. Res. 35, 511–522. Web of Science CrossRef PubMed CAS Google Scholar
Gao, H.-L., Ding, B., Yi, L., Cheng, P., Liao, D.-Z., Yan, S.-P. & Jiang, Z.-H. (2005). Inorg. Chem. Commun. 8, 151–154. Web of Science CSD CrossRef CAS Google Scholar
Kil, S. M. & Myunghyun, P. S. (2000). J. Am. Chem. Soc. 122, 6834–6840. Google Scholar
Mehmet, V., Yigit, K. B., Brian, M. & John, C. M. (2006). Cryst. Growth & Des., 6, 63–69. Google Scholar
Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev. 101, 1629–1658. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Version 1.4.0. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1999). SHELXTL/PC. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sujit, K. G., Savitha, G. & Parimal, K. B. (2004). Inorg. Chem. 43, 5495–5497. Web of Science PubMed Google Scholar
Syper, L., Kloc, K. & Mlochowski, J. (1980). Tetrahedron, 36, 123–129. CrossRef CAS Web of Science Google Scholar

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