Poly[diaqua-μ(2)-oxalato-di-μ(2)-pyrimidine-2-carboxyl-ato-dimanganese(II)].

Abstract

In the title compound, [Mn(2)(C(2)O(4))(C(5)H(3)N(2)O(2))(2)(H(2)O)(2)](n), the Mn(II) atom exhibits a distorted octa-hedral coordination geometry, with the centrosymmetric oxalate anion and the monoanionic pyrimidine-2-carboxyl-ate ligands generating a two-dimensional honeycomb network with a (6,3)-topology.

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Poly[diaqua-l2-oxalato-di-l2-pyrimidine-
2-carboxylato-dimanganese(II)]
Antonio Rodrı ´guez-Die ´guez,a* Hakima Aouryaghal,b
A. J. Motaaand Enrique Colacioa
aDepartamento de Quı ´mica Inorga ´nica, Facultad de Ciencias, Universidad de
Granada, c/ Severo Ochoa s/n, 18071 Granada, Spain, andbDepartement de
Chimie, Universite ´ Abdelmalek Essaadi, Faculte ´ de Sciences, PO 2121, Te ´touan,
Morocco
Correspondence e-mail: antonio5@ugr.es
Received 17 January 2008; accepted 24 January 2008
Key indicators: single-crystal X-ray study; T = 150 K; mean ?(C–C) = 0.003 A ˚;
R factor = 0.025; wR factor = 0.063; data-to-parameter ratio = 11.8.
In the title compound, [Mn2(C2O4)(C5H3N2O2)2(H2O)2]n, the
MnIIatom 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: Rodrı ´guez-
Die ´guez, Salinas-Castillo et al. (2007). For related literature,
see: Rodrı ´guez-Die ´guez, Cano et al. (2007).
Experimental
Crystal data
[Mn2(C2O4)(C5H3N2O2)2(H2O)2]
Mr= 480.12
Monoclinic, P21=n
a = 7.5447 (7) A˚
b = 11.1944 (11) A˚
c = 9.7259 (10) A˚
? = 102.4220 (10)?
V = 802.20 (14) A˚3
Z = 2
Mo K? radiation
? = 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)
Tmin= 0.714, Tmax= 0.773
(expected range = 0.665–0.720)
5847 measured reflections
1495 independent reflections
1389 reflections with I > 2?(I)
Rint= 0.019
Refinement
R[F2> 2?(F2)] = 0.025
wR(F2) = 0.062
S = 1.11
1495 reflections
127 parameters
H-atom parameters constrained
??max= 0.41 e A˚?3
??min= ?0.21 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
O1W—H2WB???O2Bi
O1W—H1WA???N5ii
Symmetry codes: (i) ?x;?y þ 1;?z þ 1; (ii) ?x þ1
D—HH???AD???AD—H???A
0.80
0.77
2.05
2.05
2.847 (2)
2.815 (2)
170
171
2;y ?1
2;?z þ3
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).
Financial support from MEC Spain (project No. CTQ2005/
0935) is gratefully acknowledged.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: SU2042).
References
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Rodrı ´guez-Die ´guez, A., Cano, J., Kiveka ¨s, R., Debdoubi, A. & Colacio, E.
(2007). Inorg. Chem. pp. 2503–2510.
Rodrı ´guez-Die ´guez, A., Salinas-Castillo, A., Galli, S., Masciocchi, N.,
Gutie ´rrez-Zorrilla, J. M., Vitoria, P. & Colacio, E. (2007). Dalton Trans.
pp. 1821–1828.
Sheldrick, G. M. (2004). SADABS. University of Go ¨ttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Westrip, S. P. (2008). publCIF. In preparation.
metal-organic compounds
m618
Rodrı ´guez-Die ´guez et al.
doi:10.1107/S1600536808002687
Acta Cryst. (2008). E64, m618
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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supplementary materials

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supplementary materials
sup-1
Acta Cryst. (2008). E64, m618 [ doi:10.1107/S1600536808002687 ]
Poly[diaqua- 2-oxalato-di- 2-pyrimidine-2-carboxylato-dimanganese(II)]
A. Rodríguez-Diéguez, H. Aouryaghal, A. J. Mota and E. Colacio
Comment
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 co-
ordination 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.
Experimental
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.
Refinement
The water H atoms were located in a difference Fourier map and refined as riding atoms with O—H = 0.77 and 0.80 Å
and Uiso(H) = 1.2Ueq(O). The pyrimidine H atoms were positioned geometrically and treated as riding atoms with C—H
= 0.93 Å, and Uiso(H) = 1.2Ueq(C).
Figures
Fig. 1. The molecular structure of the asymmetric unit of [Mn2(pymca)2(ox)(H2O)2]n, show-
ing the atom labels. Thermal ellipsoids are drawn at the 50% probability level. H atoms are
represented as spheres of arbitrary radii.

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Fig. 2. A view down the a axis of the crystal structure of [Mn2(pymca)2(ox)(H2O)2]n, show-
ing 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)]
Crystal data
[Mn2(C2O4)(C5H3N2O2)2(H2O)2]
F000 = 480
Dx = 1.988 Mg m−3
Mo Kα radiation
λ = 0.71073 Å
Cell parameters from 3384 reflections
θ = 2.8–28.9º
µ = 1.64 mm−1
T = 150 (2) K
Prismatic, yellow
Mr = 480.12
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 7.5447 (7) Å
b = 11.1944 (11) Å
c = 9.7259 (10) Å
β = 102.4220 (10)º
V = 802.20 (14) Å3
Z = 2
0.22 × 0.21 × 0.20 mm
Data collection
Bruker SMART APEX CCD area-detector
diffractometer
Monochromator: graphite
T = 150(2) K
φ and ω scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
Tmin = 0.714, Tmax = 0.774
5847 measured reflections
1495 independent reflections
1389 reflections with I > 2σ(I)
Rint = 0.019
θmax = 25.5º
θmin = 2.8º
h = −9→9
k = −13→13
l = −11→11
Refinement
Refinement on F2
Secondary atom site location: difference Fourier map
Least-squares matrix: full
Hydrogen site location: inferred from neighbouring
sites
R[F2 > 2σ(F2)] = 0.025
H-atom parameters constrained
wR(F2) = 0.062
w = 1/[σ2(Fo2) + (0.0274P)2 + 0.6516P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.41 e Å−3
Δρmin = −0.21 e Å−3
S = 1.11
1495 reflections
127 parameters

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Primary atom site location: structure-invariant direct
methods
Extinction correction: none
Special details
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 mat-
rix. 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, convention-
al 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)
x
0.22294 (4)
0.2376 (2)
0.1555 (3)
0.0850
0.1735 (3)
0.1164
0.2805 (3)
0.2929
0.3670 (2)
0.3405 (3)
0.4354 (3)
0.3827 (2)
0.5576 (2)
0.4755 (2)
0.30121 (19)
0.5504 (3)
−0.0119 (2)
−0.0848
0.0167
y
0.67224 (3)
0.87496 (16)
0.94939 (19)
0.9174
1.07187 (19)
1.1230
1.1150 (2)
1.1972
1.04205 (16)
0.92559 (18)
0.83993 (18)
0.73395 (13)
0.88282 (13)
0.64691 (13)
0.48353 (13)
0.54766 (18)
0.64879 (13)
0.6091
0.6192
z
0.51301 (3)
0.49706 (17)
0.3937 (2)
0.3117
0.4065 (2)
0.3353
0.5301 (2)
0.5428
0.63259 (18)
0.6111 (2)
0.7255 (2)
0.71406 (16)
0.81900 (15)
0.43885 (16)
0.56335 (16)
0.4641 (2)
0.60530 (15)
0.5523
0.6778
Uiso*/Ueq
0.01810 (12)
0.0170 (4)
0.0224 (5)
0.027*
0.0230 (5)
0.028*
0.0229 (5)
0.027*
0.0196 (4)
0.0166 (4)
0.0182 (4)
0.0251 (4)
0.0224 (3)
0.0230 (3)
0.0217 (3)
0.0185 (4)
0.0219 (3)
0.026*
0.026*
Mn1
N1
C2
H2
C3
H3
C4
H4
N5
C6
C7
O8
O9
O1B
O2B
C3B
O1W
H2WB
H1WA
Atomic displacement parameters (Å2)
U11
0.01820 (19)
0.0170 (9)
0.0235 (11)
0.0250 (11)
0.0259 (11)
0.0219 (9)
0.0162 (10)
0.0185 (10)
U22
0.01263 (18)
0.0150 (9)
0.0219 (11)
0.0198 (11)
0.0165 (11)
0.0166 (9)
0.0162 (10)
0.0184 (11)
U33
0.01991 (19)
0.0171 (9)
0.0194 (10)
0.0229 (11)
0.0257 (11)
0.0187 (9)
0.0170 (10)
0.0167 (10)
U12
0.00050 (12)
0.0001 (7)
−0.0003 (9)
0.0005 (9)
−0.0010 (9)
−0.0014 (7)
0.0002 (8)
0.0026 (8)
U13
−0.00384 (13)
−0.0008 (7)
−0.0009 (9)
0.0024 (9)
0.0044 (9)
0.0007 (7)
0.0026 (8)
0.0016 (8)
U23
−0.00014 (12)
−0.0001 (6)
0.0000 (9)
0.0033 (9)
0.0013 (9)
−0.0005 (7)
−0.0002 (8)
−0.0003 (8)
Mn1
N1
C2
C3
C4
N5
C6
C7