research communications
κO4)manganese(II)
of tetraaquabis(pyrimidin-1-ium-4,6-diolato-aCarlson School of Chemistry and Biochemistry, Clark University, 950 Main St, Worcester, MA 01610, USA, and bDepartment of Chemistry, Howard University, Washington, DC 20059, USA
*Correspondence e-mail: fgreenaway@clarku.edu
The MnII ion in the structure of the mononuclear title compound, [Mn(C4H3N2O2)2(H2O)4], is situated on an inversion center and is coordinated by two O atoms from two deprotonated 4,6-dihydroxypyrimidine ligands and by four O atoms from water molecules giving rise to a slightly distorted octahedral coordination sphere. The complex includes an intramolecular hydrogen bond between an aqua ligand and the non-protonated N ring atom. The extended structure is stabilized by intermolecular hydrogen bonds between aqua ligands, by hydrogen bonds between N and O atoms of the ligands of adjacent molecules, and by hydrogen bonds between aqua ligands and the non-coordinating O atom of an adjacent molecule.
CCDC reference: 1539878
1. Chemical context
H-tautomeric forms of 4,6-dihydroxypyrimidine (DHP) are known to exist and are associated with low ). Although crystal structures have been reported where cobalt(II) and nickel(II) are coordinated by the 4,6-dihydroxypyrimidine ligand through a ring nitrogen atom (Huang et al., 2005; Wang et al., 2006), prior to this report no complexes with ligation through a phenolate oxygen atom have been reported even though this mode of coordination does occur in complexes of 3,6-dihydroxypyridizine (Shennara et al., 2015).
energies (Katrusiak & Katrusiak, 20032. Structural commentary
Crystallographic analysis reveals that the title compound consists of a centrosymmetric mononuclear [Mn(C4H3N2O2)2(H2O)4] complex in which the MnII ion is in an O6 environment that is close to octahedral. Two deprotonated 4,6-dihydroxypyrimidine ligands coordinate through the phenolate oxygen atom (O1) at axial positions, while four water molecules occupy the equatorial sites (Fig. 1). The bond lengths in the pyrimidine ligand are very similar to those found for the Co and Ni complexes in which, however, ligation to the metal is through a nitrogen atom. For all three complexes, the structures indicate a zwitterionic form of the ligand resulting from transfer of a proton from the hydroxyl group to a ring nitrogen atom. Others have reported variability in the H-tautomeric forms of 4,6-dihydroxypyrimidine associated with low energies (Katrusiak & Katrusiak, 2003). The structure of the complex includes an intramolecular hydrogen bond between an aqua ligand (O2W) and the non-protonated N3 ring atom (N2) (Table 1).
3. Supramolecular features
Intermolecular hydrogen bonds between the aqua ligands of adjacent molecules are present. Hydrogen bonds also occur between the non-coordinating NH+ and O− atoms of two DHP ligands in adjacent molecules and between an aqua ligand and the non-coordinating oxygen atom of an adjacent molecule (Table 1). This gives rise to a complex three-dimensional network, which is best analyzed in terms of graph-set theory (Etter et al., 1990). There are four interpenetrating chains of hydrogen bonds. The first has a C(4)[R22(8)] motif and is shown in Fig. 1. The second has a C(6)[R11(6)R22(8)] motif and is shown in Fig. 2. The chain depicted in Fig. 3 has a C(6)[R32(8)] motif and is duplicated in two mutually perpendicular directions, thus making up four chains altogether. The overall packing is shown in Fig. 4.
4. Database survey
A search in the Cambridge Structural Database (CSD version 5.37; Groom et al., 2016) for structures of manganese of 4,6-dihydroxypyrimidines revealed that no such structures exist, although there are twelve examples of manganese complexes of 2,4-dihydroxypyrimidine derivatives (CSD codes AMPTMN, AQAPAK, ICESEQ, IMEGAJ, JIRNUU, NOPSER, OFUDAU, QOSDOT, QOSNOD, RAGLAO, TAGVOM, and ZOGFOQ).
5. Synthesis and crystallization
0.5 mM aqueous solutions of the ligand and anhydrous MnCl2, both purchased from Aldrich, were adjusted to pH 5.5 with NaOH/HCl and then mixed together in a 1:2 stoichiometry. The solutions were left to crystallize slowly at room temperature. Light-yellow crystals formed over two weeks. Room-temperature X-band EPR spectra of powdered crystals exhibited a single broad line centered at a g-value of near to 2.0 with a peak-to-peak line width of 660 G, the breadth of which indicates Mn⋯Mn magnetic interactions, although not as strong as in the related maleic hydrazide (MH), Mn(MH)2(H2O)4, complex, for which a line width of 920 G was found (Shennara et al., 2015). EPR spectra of aqueous solutions of the title complex had g = 2.006 and Aiso(Mn) = 95.2 G, similar to that of the Mn(MH)2 complex
6. Refinement
Crystal data, data collection and structure . All H atoms were positioned geometrically and refined as riding: C—H = 0.95 Å with Uiso(H) = 1.2Ueq(C). N—H and O—H hydrogen atoms were refined isotropically without restrictions on the bond lengths. Four reflections which were obvious outliers were omitted from the (132, 163, 100, 011).
details are summarized in Table 2
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Supporting information
CCDC reference: 1539878
https://doi.org/10.1107/S2056989017004649/wm5373sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017004649/wm5373Isup2.hkl
Data collection: APEX2 (Bruker, 2005); cell
APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Mn(C4H3N2O2)2(H2O)4] | F(000) = 358 |
Mr = 349.17 | Dx = 1.766 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.2156 (5) Å | Cell parameters from 2512 reflections |
b = 14.0812 (14) Å | θ = 2.7–31.2° |
c = 9.0595 (9) Å | µ = 1.05 mm−1 |
β = 99.366 (2)° | T = 120 K |
V = 656.48 (11) Å3 | Block, yellow |
Z = 2 | 0.55 × 0.41 × 0.40 mm |
Bruker APEXII CCD diffractometer | 1752 reflections with I > 2σ(I) |
ω scans | Rint = 0.016 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 31.2°, θmin = 2.9° |
Tmin = 0.614, Tmax = 0.746 | h = −7→7 |
2971 measured reflections | k = −18→18 |
1848 independent reflections | l = −3→12 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.033P)2 + 0.3858P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
1848 reflections | Δρmax = 0.48 e Å−3 |
117 parameters | Δρmin = −0.32 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. |
x | y | z | Uiso*/Ueq | ||
Mn | 0.500000 | 0.500000 | 0.500000 | 0.00759 (9) | |
O1 | 0.25688 (17) | 0.38379 (6) | 0.56407 (10) | 0.01144 (18) | |
O2 | −0.08946 (18) | 0.07807 (6) | 0.62265 (10) | 0.01204 (18) | |
O1W | 0.17104 (18) | 0.54921 (7) | 0.33556 (11) | 0.01243 (18) | |
H1W1 | 0.114 (5) | 0.5129 (16) | 0.271 (3) | 0.029 (6)* | |
H1W2 | 0.045 (5) | 0.5682 (17) | 0.370 (3) | 0.040 (7)* | |
O2W | 0.6010 (2) | 0.40720 (7) | 0.32982 (11) | 0.0164 (2) | |
H2W1 | 0.562 (5) | 0.3534 (18) | 0.353 (3) | 0.037 (6)* | |
H2W2 | 0.702 (5) | 0.4026 (17) | 0.267 (3) | 0.035 (6)* | |
N1 | 0.2263 (2) | 0.10486 (8) | 0.48187 (11) | 0.0094 (2) | |
H1N | 0.219 (5) | 0.0429 (18) | 0.453 (3) | 0.033 (6)* | |
N2 | 0.4089 (2) | 0.25411 (8) | 0.45266 (11) | 0.0102 (2) | |
C1 | 0.2421 (2) | 0.29415 (9) | 0.54070 (13) | 0.0084 (2) | |
C2 | 0.0651 (2) | 0.23594 (9) | 0.60057 (13) | 0.0101 (2) | |
H2A | −0.049639 | 0.263207 | 0.660180 | 0.012* | |
C3 | 0.0573 (2) | 0.13885 (9) | 0.57302 (13) | 0.0090 (2) | |
C4 | 0.3920 (2) | 0.16342 (9) | 0.42645 (13) | 0.0102 (2) | |
H4A | 0.503298 | 0.136653 | 0.364320 | 0.012* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn | 0.00731 (13) | 0.00453 (14) | 0.01196 (13) | −0.00112 (8) | 0.00470 (9) | −0.00066 (8) |
O1 | 0.0118 (4) | 0.0049 (4) | 0.0192 (4) | −0.0018 (3) | 0.0074 (3) | −0.0011 (3) |
O2 | 0.0165 (4) | 0.0057 (4) | 0.0163 (4) | −0.0030 (3) | 0.0097 (3) | −0.0001 (3) |
O1W | 0.0105 (4) | 0.0099 (5) | 0.0173 (4) | 0.0014 (3) | 0.0032 (3) | −0.0025 (3) |
O2W | 0.0242 (5) | 0.0076 (5) | 0.0219 (5) | −0.0037 (4) | 0.0172 (4) | −0.0024 (3) |
N1 | 0.0123 (5) | 0.0051 (5) | 0.0121 (4) | −0.0013 (3) | 0.0058 (4) | −0.0019 (3) |
N2 | 0.0096 (5) | 0.0085 (5) | 0.0134 (4) | −0.0014 (3) | 0.0050 (4) | −0.0002 (4) |
C1 | 0.0073 (5) | 0.0070 (5) | 0.0110 (4) | −0.0006 (4) | 0.0018 (4) | 0.0000 (4) |
C2 | 0.0101 (5) | 0.0074 (6) | 0.0143 (5) | −0.0010 (4) | 0.0063 (4) | −0.0002 (4) |
C3 | 0.0091 (5) | 0.0082 (6) | 0.0106 (4) | −0.0007 (4) | 0.0040 (4) | 0.0002 (4) |
C4 | 0.0108 (5) | 0.0090 (6) | 0.0118 (5) | −0.0009 (4) | 0.0049 (4) | 0.0007 (4) |
Mn—O2W | 2.1510 (10) | O2W—H2W2 | 0.84 (2) |
Mn—O2Wi | 2.1510 (10) | N1—C4 | 1.3491 (15) |
Mn—O1W | 2.1934 (10) | N1—C3 | 1.3871 (14) |
Mn—O1Wi | 2.1935 (10) | N1—H1N | 0.91 (2) |
Mn—O1 | 2.2050 (9) | N2—C4 | 1.2993 (16) |
Mn—O1i | 2.2050 (9) | N2—C1 | 1.3917 (15) |
O1—C1 | 1.2801 (15) | C1—C2 | 1.4074 (16) |
O2—C3 | 1.2778 (14) | C2—C3 | 1.3892 (17) |
O1W—H1W1 | 0.80 (3) | C2—H2A | 0.9500 |
O1W—H1W2 | 0.82 (3) | C4—H4A | 0.9500 |
O2W—H2W1 | 0.82 (3) | ||
O2W—Mn—O2Wi | 180.0 | Mn—O2W—H2W1 | 106.3 (17) |
O2W—Mn—O1W | 87.76 (4) | Mn—O2W—H2W2 | 141.9 (16) |
O2Wi—Mn—O1W | 92.24 (4) | H2W1—O2W—H2W2 | 108 (2) |
O2W—Mn—O1Wi | 92.25 (4) | C4—N1—C3 | 121.20 (10) |
O2Wi—Mn—O1Wi | 87.75 (4) | C4—N1—H1N | 118.5 (14) |
O1W—Mn—O1Wi | 180.0 | C3—N1—H1N | 120.1 (15) |
O2W—Mn—O1 | 87.49 (4) | C4—N2—C1 | 118.21 (10) |
O2Wi—Mn—O1 | 92.51 (4) | O1—C1—N2 | 117.88 (10) |
O1W—Mn—O1 | 89.62 (4) | O1—C1—C2 | 122.43 (11) |
O1Wi—Mn—O1 | 90.38 (4) | N2—C1—C2 | 119.69 (11) |
O2W—Mn—O1i | 92.51 (4) | C3—C2—C1 | 120.38 (11) |
O2Wi—Mn—O1i | 87.49 (4) | C3—C2—H2A | 119.8 |
O1W—Mn—O1i | 90.38 (4) | C1—C2—H2A | 119.8 |
O1Wi—Mn—O1i | 89.62 (4) | O2—C3—N1 | 116.96 (11) |
O1—Mn—O1i | 180.0 | O2—C3—C2 | 126.70 (11) |
C1—O1—Mn | 135.24 (8) | N1—C3—C2 | 116.34 (10) |
Mn—O1W—H1W1 | 116.9 (17) | N2—C4—N1 | 124.15 (11) |
Mn—O1W—H1W2 | 115.8 (18) | N2—C4—H4A | 117.9 |
H1W1—O1W—H1W2 | 105 (2) | N1—C4—H4A | 117.9 |
Mn—O1—C1—N2 | −1.40 (18) | C4—N1—C3—O2 | −178.77 (11) |
Mn—O1—C1—C2 | 178.55 (9) | C4—N1—C3—C2 | 1.38 (17) |
C4—N2—C1—O1 | −178.88 (11) | C1—C2—C3—O2 | 178.56 (12) |
C4—N2—C1—C2 | 1.17 (17) | C1—C2—C3—N1 | −1.61 (17) |
O1—C1—C2—C3 | −179.55 (11) | C1—N2—C4—N1 | −1.49 (18) |
N2—C1—C2—C3 | 0.39 (18) | C3—N1—C4—N2 | 0.19 (19) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O2ii | 0.80 (3) | 2.03 (3) | 2.8152 (14) | 170 (2) |
O1W—H1W2···O1iii | 0.82 (3) | 1.90 (3) | 2.7127 (13) | 176 (3) |
O2W—H2W1···N2 | 0.82 (3) | 1.91 (3) | 2.6929 (14) | 159 (2) |
O2W—H2W2···O2iv | 0.84 (2) | 1.85 (2) | 2.6754 (13) | 167 (2) |
N1—H1N···O2v | 0.91 (2) | 1.92 (2) | 2.7966 (14) | 162 (2) |
Symmetry codes: (ii) x, −y+1/2, z−1/2; (iii) −x, −y+1, −z+1; (iv) x+1, −y+1/2, z−1/2; (v) −x, −y, −z+1. |
Acknowledgements
Data were collected by Matthias Zeller of Youngstown State University, Youngstown, Ohio, USA, on an X-ray diffractometer funded by NSF grant 0087210, Ohio Board of Regents Grant CAP-491, and by Youngstown State University. RJB is grateful to NSF award 1205608, Partnership for Reduced Dimensional Materials for partial funding of this research.
Funding information
Funding for this research was provided by: National Science Foundation, Division of Chemistryhttps://doi.org/10.13039/100000165 (award Nos. 0087210, 1205608); Ohio Board of Regentshttps://doi.org/10.13039/100005171 (award No. CAP-491).
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