Poly[diaqua-μ2-oxalato-di-μ2-pyrimidine-2-carboxyl­ato-dimanganese(II)]

Rodríguez-Diéguez, A.; Aouryaghal, H.; Mota, A.J.; Colacio, E.

doi:10.1107/S1600536808002687

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page m618

doi:10.1107/S1600536808002687

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Poly[diaqua-μ₂-oxalato-di-μ₂-pyrimidine-2-carboxylato-dimanganese(II)]

Antonio Rodríguez-Diéguez,^a ^* Hakima Aouryaghal,^b A. J. Mota ^a and Enrique Colacio ^a

^aDepartamento de Química Inorgánica, Facultad de Ciencias, Universidad de Granada, c/ Severo Ochoa s/n, 18071 Granada, Spain, and ^bDepartement de Chimie, Université Abdelmalek Essaadi, Faculté de Sciences, PO 2121, Tétouan, Morocco
^*Correspondence e-mail: antonio5@ugr.es

(Received 17 January 2008; accepted 24 January 2008; online 2 April 2008)

In the title compound, [Mn₂(C₂O₄)(C₅H₃N₂O₂)₂(H₂O)₂]_n, the Mn^II atom exhibits a distorted octahedral coordination geometry, with the centrosymmetric oxalate anion and the monoanionic pyrimidine-2-carboxylate ligands generating a two-dimensional honeycomb network with a (6,3)-topology.

Related literature

For the preparation of 2-cyanopyrimidine, see: Rodríguez-Diéguez, Salinas-Castillo et al. (2007 ). For related literature, see: Rodríguez-Diéguez, Cano et al. (2007 ).

Experimental

Crystal data

[Mn₂(C₂O₄)(C₅H₃N₂O₂)₂(H₂O)₂]
M_r = 480.12
Monoclinic, P 2₁ /n
a = 7.5447 (7) Å
b = 11.1944 (11) Å
c = 9.7259 (10) Å
β = 102.4220 (10)°
V = 802.20 (14) Å³
Z = 2
Mo Kα radiation
μ = 1.64 mm⁻¹
T = 150 (2) K
0.22 × 0.21 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.714, T_max = 0.773 (expected range = 0.665–0.720)
5847 measured reflections
1495 independent reflections
1389 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.062
S = 1.11
1495 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2WB⋯O2Bⁱ	0.80	2.05	2.847 (2)	170
O1W—H1WA⋯N5ⁱⁱ	0.77	2.05	2.815 (2)	171
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808002687/su2042sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808002687/su2042Isup2.hkl

checkCIF report

Comment top

The title compound constitutes a new member of a series of honeycomb type compounds previously reported by us (Rodríguez-Diéguez, Cano et al., 2007).

The asymmetric unit of the title compound is illustrated in Fig. 1. The Mn(II) atom exhibits a distorted octahedral coordination geometry built by one pyrimidine-2-carboxylato ligand, half of an oxalic acid ligand and one water molecule. The compound can be described by Mn(pyrimidine-2-carboxylato) chains linked by oxalate ligands to obtain a bidimensional coordination polymer. Each Mn(II) is connected to three Mn atoms through two pyrimidine-2-carboxylato ligands and one oxalate ligand, generating a two-dimensional honeycomb network with a (6,3) topology (Fig. 2). The shortest perpendicular distance between symmetry related pyrimidine rings is ca 3.41 Å.

Related literature top

For the preparation of 2-cyanopyrimidine, see: Rodríguez-Diéguez, Salinas-Castillo et al. (2007). For related literature, see: Rodríguez-Diéguez, Cano et al. (2007).

Experimental top

The multitopic bridging ligand 2-carboxy-pyrimidine (H-pymca) was prepared by basic hydrolysis of 2-cyanopyrimidine with KOH and further neutralization with 2 N HCl. The title compound was obtained by the reaction of a mixture of two solutions. The first contained pyrimidine-2-carboxylato (17.1 mg) and MnCl₂.4(H₂O) (8.67 mg) in water/MeOH (10 ml). The second was formed by addition of MnCl₂.4(H₂O) (8.67 mg) to a solution of sodium oxalate (9.23 mg) in water (10 ml). These two solutions were then mixed and stirred for 2 h to give a pale-yellow solution. After standing at room temperature for several days prismatic yellow crystals appeared.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. The molecular structure of the asymmetric unit of [Mn₂(pymca)₂(ox)(H₂O)₂]_n, showing the atom labels. Thermal ellipsoids are drawn at the 50% probability level. H atoms are represented as spheres of arbitrary radii.
	Fig. 2. A view down the a axis of the crystal structure of [Mn₂(pymca)₂(ox)(H₂O)₂]_n, showing the environment of the manganese atoms and the bidimensional (6,3) net topology. The H atoms have been omitted for clarity.

Poly[diaqua-µ₂-oxalato-di-µ₂-pyrimidine-2-carboxylato-dimanganese(II)] top

Crystal data top

[Mn₂(C₂O₄)(C₅H₃N₂O₂)₂(H₂O)₂]	F(000) = 480
M_r = 480.12	D_x = 1.988 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3384 reflections
a = 7.5447 (7) Å	θ = 2.8–28.9°
b = 11.1944 (11) Å	µ = 1.64 mm⁻¹
c = 9.7259 (10) Å	T = 150 K
β = 102.422 (1)°	Prismatic, yellow
V = 802.20 (14) Å³	0.22 × 0.21 × 0.20 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1495 independent reflections
Radiation source: fine-focus sealed tube	1389 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→9
T_min = 0.714, T_max = 0.774	k = −13→13
5847 measured reflections	l = −11→11

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.062	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0274P)² + 0.6516P] where P = (F_o² + 2F_c²)/3
1495 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

[Mn₂(C₂O₄)(C₅H₃N₂O₂)₂(H₂O)₂]	V = 802.20 (14) Å³
M_r = 480.12	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5447 (7) Å	µ = 1.64 mm⁻¹
b = 11.1944 (11) Å	T = 150 K
c = 9.7259 (10) Å	0.22 × 0.21 × 0.20 mm
β = 102.422 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1495 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1389 reflections with I > 2σ(I)
T_min = 0.714, T_max = 0.774	R_int = 0.019
5847 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.062	H-atom parameters constrained
S = 1.11	Δρ_max = 0.41 e Å⁻³
1495 reflections	Δρ_min = −0.21 e Å⁻³
127 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	0.22294 (4)	0.67224 (3)	0.51301 (3)	0.01810 (12)
N1	0.2376 (2)	0.87496 (16)	0.49706 (17)	0.0170 (4)
C2	0.1555 (3)	0.94939 (19)	0.3937 (2)	0.0224 (5)
H2	0.0850	0.9174	0.3117	0.027*
C3	0.1735 (3)	1.07187 (19)	0.4065 (2)	0.0230 (5)
H3	0.1164	1.1230	0.3353	0.028*
C4	0.2805 (3)	1.1150 (2)	0.5301 (2)	0.0229 (5)
H4	0.2929	1.1972	0.5428	0.027*
N5	0.3670 (2)	1.04205 (16)	0.63259 (18)	0.0196 (4)
C6	0.3405 (3)	0.92559 (18)	0.6111 (2)	0.0166 (4)
C7	0.4354 (3)	0.83993 (18)	0.7255 (2)	0.0182 (4)
O8	0.3827 (2)	0.73395 (13)	0.71406 (16)	0.0251 (4)
O9	0.5576 (2)	0.88282 (13)	0.81900 (15)	0.0224 (3)
O1B	0.4755 (2)	0.64691 (13)	0.43885 (16)	0.0230 (3)
O2B	0.30121 (19)	0.48353 (13)	0.56335 (16)	0.0217 (3)
C3B	0.5504 (3)	0.54766 (18)	0.4641 (2)	0.0185 (4)
O1W	−0.0119 (2)	0.64879 (13)	0.60530 (15)	0.0219 (3)
H2WB	−0.0848	0.6091	0.5523	0.026*
H1WA	0.0167	0.6192	0.6778	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.01820 (19)	0.01263 (18)	0.01991 (19)	0.00050 (12)	−0.00384 (13)	−0.00014 (12)
N1	0.0170 (9)	0.0150 (9)	0.0171 (9)	0.0001 (7)	−0.0008 (7)	−0.0001 (6)
C2	0.0235 (11)	0.0219 (11)	0.0194 (10)	−0.0003 (9)	−0.0009 (9)	0.0000 (9)
C3	0.0250 (11)	0.0198 (11)	0.0229 (11)	0.0005 (9)	0.0024 (9)	0.0033 (9)
C4	0.0259 (11)	0.0165 (11)	0.0257 (11)	−0.0010 (9)	0.0044 (9)	0.0013 (9)
N5	0.0219 (9)	0.0166 (9)	0.0187 (9)	−0.0014 (7)	0.0007 (7)	−0.0005 (7)
C6	0.0162 (10)	0.0162 (10)	0.0170 (10)	0.0002 (8)	0.0026 (8)	−0.0002 (8)
C7	0.0185 (10)	0.0184 (11)	0.0167 (10)	0.0026 (8)	0.0016 (8)	−0.0003 (8)
O8	0.0297 (9)	0.0157 (8)	0.0241 (8)	−0.0014 (6)	−0.0074 (7)	0.0027 (6)
O9	0.0222 (8)	0.0211 (8)	0.0195 (8)	−0.0023 (6)	−0.0054 (6)	0.0001 (6)
O1B	0.0223 (8)	0.0136 (7)	0.0316 (8)	0.0020 (6)	0.0028 (7)	0.0050 (6)
O2B	0.0188 (7)	0.0163 (7)	0.0282 (8)	0.0010 (6)	0.0009 (6)	0.0016 (6)
C3B	0.0172 (10)	0.0151 (10)	0.0191 (10)	−0.0009 (8)	−0.0055 (8)	−0.0017 (8)
O1W	0.0235 (8)	0.0196 (8)	0.0193 (7)	−0.0002 (6)	−0.0028 (6)	0.0028 (6)

Geometric parameters (Å, º) top

Mn1—O9ⁱ	2.1175 (14)	C4—H4	0.9300
Mn1—O1W	2.1677 (15)	N5—C6	1.329 (3)
Mn1—O8	2.1771 (15)	C6—C7	1.526 (3)
Mn1—O1B	2.1958 (16)	C7—O9	1.244 (3)
Mn1—O2B	2.2196 (15)	C7—O8	1.248 (3)
Mn1—N1	2.2790 (18)	O9—Mn1ⁱⁱ	2.1175 (14)
N1—C6	1.336 (3)	O1B—C3B	1.247 (2)
N1—C2	1.349 (3)	O2B—C3Bⁱⁱⁱ	1.255 (3)
C2—C3	1.381 (3)	C3B—O2Bⁱⁱⁱ	1.255 (3)
C2—H2	0.9300	C3B—C3Bⁱⁱⁱ	1.560 (4)
C3—C4	1.383 (3)	O1W—H2WB	0.8027
C3—H3	0.9300	O1W—H1WA	0.7669
C4—N5	1.344 (3)

O9ⁱ—Mn1—O1W	87.50 (6)	C2—C3—H3	121.5
O9ⁱ—Mn1—O8	177.38 (6)	C4—C3—H3	121.5
O1W—Mn1—O8	90.61 (6)	N5—C4—C3	122.1 (2)
O9ⁱ—Mn1—O1B	93.21 (6)	N5—C4—H4	118.9
O1W—Mn1—O1B	164.73 (6)	C3—C4—H4	118.9
O8—Mn1—O1B	89.08 (6)	C6—N5—C4	116.55 (18)
O9ⁱ—Mn1—O2B	89.85 (6)	N5—C6—N1	126.02 (19)
O1W—Mn1—O2B	89.76 (6)	N5—C6—C7	118.09 (18)
O8—Mn1—O2B	91.96 (5)	N1—C6—C7	115.90 (18)
O1B—Mn1—O2B	74.99 (5)	O9—C7—O8	127.13 (19)
O9ⁱ—Mn1—N1	104.89 (6)	O9—C7—C6	116.64 (18)
O1W—Mn1—N1	101.81 (6)	O8—C7—C6	116.22 (18)
O8—Mn1—N1	73.72 (6)	C7—O8—Mn1	119.06 (13)
O1B—Mn1—N1	92.76 (6)	C7—O9—Mn1ⁱⁱ	137.83 (14)
O2B—Mn1—N1	161.49 (6)	C3B—O1B—Mn1	116.05 (14)
C6—N1—C2	116.64 (18)	C3Bⁱⁱⁱ—O2B—Mn1	115.15 (13)
C6—N1—Mn1	113.21 (13)	O1B—C3B—O2Bⁱⁱⁱ	126.4 (2)
C2—N1—Mn1	130.12 (14)	O1B—C3B—C3Bⁱⁱⁱ	117.0 (2)
N1—C2—C3	121.7 (2)	O2Bⁱⁱⁱ—C3B—C3Bⁱⁱⁱ	116.6 (2)
N1—C2—H2	119.2	Mn1—O1W—H2WB	108.0
C3—C2—H2	119.2	Mn1—O1W—H1WA	109.9
C2—C3—C4	117.0 (2)	H2WB—O1W—H1WA	111.7

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2WB···O2B^iv	0.80	2.05	2.847 (2)	170
O1W—H1WA···N5^v	0.77	2.05	2.815 (2)	171

Symmetry codes: (iv) −x, −y+1, −z+1; (v) −x+1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Mn₂(C₂O₄)(C₅H₃N₂O₂)₂(H₂O)₂]
M_r	480.12
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	7.5447 (7), 11.1944 (11), 9.7259 (10)
β (°)	102.422 (1)
V (Å³)	802.20 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.64
Crystal size (mm)	0.22 × 0.21 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.714, 0.774
No. of measured, independent and observed [I > 2σ(I)] reflections	5847, 1495, 1389
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.607

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.062, 1.11
No. of reflections	1495
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.21

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2WB···O2Bⁱ	0.80	2.05	2.847 (2)	170
O1W—H1WA···N5ⁱⁱ	0.77	2.05	2.815 (2)	171

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+3/2.

Acknowledgements

Financial support from MEC Spain (project No. CTQ2005/0935) is gratefully acknowledged.

References

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Rodríguez-Diéguez, A., Cano, J., Kivekäs, R., Debdoubi, A. & Colacio, E. (2007). Inorg. Chem. pp. 2503–2510. Google Scholar
Rodríguez-Diéguez, A., Salinas-Castillo, A., Galli, S., Masciocchi, N., Gutiérrez-Zorrilla, J. M., Vitoria, P. & Colacio, E. (2007). Dalton Trans. pp. 1821–1828. Google Scholar
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