metal-organic compounds
Tetraaquabis[2-(pyridin-4-yl-κN)pyrimidine-5-carboxylato]zinc
aDepartment of Chemistry, CICECO, University of Aveiro, 3810-193 Portugal
*Correspondence e-mail: zlin@ua.pt
In the title complex, [Zn(C10H6N3O2)2(H2O)4], the ZnII ion lies on an inversion center and is coordinated in a slightly distorted octahedral geometry by two N atoms from two 2-(pyridin-4-yl)pyrimidine-5-carboxylate ligands and four water molecules. In the symmetry-unique part of the molecule, the pyridine and pyrimidine rings form a dihedral angle of 7.0 (1)°. In the crystal, the coordinating water molecules act as donor groups and carboxylate O atoms act as acceptors in O—H⋯O hydrogen bonds, forming a three-dimensional network.
Related literature
For a general background to supramolecular chemistry, see: Collet et al. (1996). For general syntheses and applications of MOFs, see: Sen et al. (2012); Saha et al. (2012). For a related structure, see: Piao & Xuan (2011).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S160053681204411X/lh5541sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681204411X/lh5541Isup2.hkl
To prepare the complex we followed a routine hydrothermal process. Zn(NO3)2 hydrate and 2-pyridin-4-ylpyrimidine-5-carboxylic acid were mixed in a 1:1 ratio, and kept in a reaction bomb at 433 K for 2 days in autogenously created pressure. After cooling to room temperature colourless block-shaped crystals were obtained. Yield ca. 45% (based on metal). The crystals were collected by filtration, washed thoroughly with water and dried in ambient conditions.
The hydrogen atoms of the C—H bonds were placed at calculated positions and refined as riding atoms, with C—H = 0.95 Å with Uiso(H) =1.2Ueq(C) of the atom to which they are attached. The positions of the hydrogen atoms of the water molecules were discernible in difference Fourier maps and they were included in the structure
with individual isotropic thermal parameters and refined with an O—H distance restraint of 0.83 (2) Å.Data collection: SMART (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level [Symmetry code: (i) -x,-y, -z]. | |
Fig. 2. Part of the crystal structure showing the three-dimensional hydrogen-bonded network. |
[Zn(C10H6N3O2)2(H2O)4] | Z = 1 |
Mr = 537.79 | F(000) = 276 |
Triclinic, P1 | Dx = 1.781 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.2764 (7) Å | Cell parameters from 246 reflections |
b = 6.9208 (7) Å | θ = 2.6–27.6° |
c = 12.7810 (17) Å | µ = 1.29 mm−1 |
α = 99.676 (7)° | T = 150 K |
β = 92.638 (7)° | Block, colourless |
γ = 112.639 (5)° | 0.26 × 0.20 × 0.04 mm |
V = 501.36 (10) Å3 |
Bruker SMART CCD diffractometer | 2184 independent reflections |
Radiation source: fine-focus sealed tube | 2030 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
fine–focus sealed tube scans | θmax = 27.4°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −8→8 |
Tmin = 0.730, Tmax = 0.950 | k = −8→8 |
8143 measured reflections | l = −16→16 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0522P)2 + 0.1478P] where P = (Fo2 + 2Fc2)/3 |
2184 reflections | (Δ/σ)max < 0.001 |
176 parameters | Δρmax = 1.05 e Å−3 |
4 restraints | Δρmin = −0.61 e Å−3 |
[Zn(C10H6N3O2)2(H2O)4] | γ = 112.639 (5)° |
Mr = 537.79 | V = 501.36 (10) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.2764 (7) Å | Mo Kα radiation |
b = 6.9208 (7) Å | µ = 1.29 mm−1 |
c = 12.7810 (17) Å | T = 150 K |
α = 99.676 (7)° | 0.26 × 0.20 × 0.04 mm |
β = 92.638 (7)° |
Bruker SMART CCD diffractometer | 2184 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2030 reflections with I > 2σ(I) |
Tmin = 0.730, Tmax = 0.950 | Rint = 0.032 |
8143 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 4 restraints |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 1.05 e Å−3 |
2184 reflections | Δρmin = −0.61 e Å−3 |
176 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn | 0.0000 | 0.0000 | 0.0000 | 0.01467 (13) | |
O1 | 0.1899 (3) | −0.1897 (2) | −0.03156 (12) | 0.0170 (3) | |
H1A | 0.129 (5) | −0.303 (3) | −0.0767 (17) | 0.028 (7)* | |
H1B | 0.238 (6) | −0.227 (6) | 0.0190 (19) | 0.051 (10)* | |
O2 | 0.2499 (3) | 0.2665 (3) | −0.05357 (13) | 0.0196 (3) | |
H2A | 0.184 (5) | 0.334 (5) | −0.080 (2) | 0.044 (9)* | |
H2B | 0.365 (4) | 0.265 (5) | −0.082 (2) | 0.046 (10)* | |
N3 | 0.1681 (3) | 0.1214 (3) | 0.16096 (14) | 0.0152 (4) | |
C4 | 0.0418 (4) | 0.1047 (3) | 0.24398 (17) | 0.0165 (4) | |
H4 | −0.1216 | 0.0610 | 0.2296 | 0.020* | |
C5 | 0.1386 (4) | 0.1481 (3) | 0.34911 (16) | 0.0159 (4) | |
H5 | 0.0430 | 0.1334 | 0.4053 | 0.019* | |
C6 | 0.3782 (4) | 0.2137 (3) | 0.37137 (16) | 0.0138 (4) | |
C7 | 0.5107 (4) | 0.2394 (3) | 0.28616 (17) | 0.0167 (4) | |
H7 | 0.6751 | 0.2890 | 0.2985 | 0.020* | |
C8 | 0.3995 (4) | 0.1916 (3) | 0.18334 (17) | 0.0173 (4) | |
H8 | 0.4914 | 0.2094 | 0.1259 | 0.021* | |
C9 | 0.4895 (4) | 0.2521 (3) | 0.48227 (16) | 0.0148 (4) | |
N10 | 0.3511 (3) | 0.2432 (3) | 0.56043 (14) | 0.0167 (4) | |
C11 | 0.4536 (4) | 0.2753 (3) | 0.65945 (17) | 0.0169 (4) | |
H11 | 0.3620 | 0.2685 | 0.7169 | 0.020* | |
C12 | 0.6871 (4) | 0.3180 (3) | 0.68231 (16) | 0.0146 (4) | |
C13 | 0.8139 (4) | 0.3264 (4) | 0.59538 (17) | 0.0179 (4) | |
H13 | 0.9751 | 0.3571 | 0.6078 | 0.022* | |
N14 | 0.7165 (3) | 0.2928 (3) | 0.49487 (14) | 0.0179 (4) | |
C15 | 0.7950 (4) | 0.3495 (3) | 0.79525 (16) | 0.0166 (4) | |
O16 | 1.0133 (3) | 0.4300 (3) | 0.81382 (12) | 0.0203 (3) | |
O17 | 0.6557 (3) | 0.2901 (3) | 0.86250 (12) | 0.0214 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.01318 (19) | 0.0201 (2) | 0.01366 (19) | 0.00978 (14) | 0.00064 (12) | 0.00383 (13) |
O1 | 0.0168 (7) | 0.0215 (8) | 0.0163 (8) | 0.0118 (7) | −0.0000 (6) | 0.0033 (6) |
O2 | 0.0167 (8) | 0.0232 (9) | 0.0225 (8) | 0.0101 (7) | 0.0040 (6) | 0.0086 (6) |
N3 | 0.0151 (8) | 0.0197 (9) | 0.0140 (8) | 0.0103 (7) | 0.0014 (7) | 0.0033 (7) |
C4 | 0.0140 (10) | 0.0187 (11) | 0.0192 (10) | 0.0090 (8) | 0.0020 (8) | 0.0038 (8) |
C5 | 0.0160 (10) | 0.0186 (11) | 0.0160 (10) | 0.0091 (9) | 0.0040 (8) | 0.0048 (8) |
C6 | 0.0168 (10) | 0.0114 (10) | 0.0157 (10) | 0.0080 (8) | 0.0011 (8) | 0.0036 (7) |
C7 | 0.0132 (10) | 0.0192 (11) | 0.0198 (11) | 0.0088 (9) | 0.0016 (8) | 0.0036 (8) |
C8 | 0.0161 (10) | 0.0213 (11) | 0.0163 (10) | 0.0092 (9) | 0.0035 (8) | 0.0038 (8) |
C9 | 0.0162 (10) | 0.0140 (10) | 0.0166 (10) | 0.0079 (8) | 0.0014 (8) | 0.0044 (8) |
N10 | 0.0160 (9) | 0.0193 (9) | 0.0170 (9) | 0.0089 (7) | 0.0017 (7) | 0.0051 (7) |
C11 | 0.0185 (10) | 0.0178 (11) | 0.0161 (10) | 0.0084 (9) | 0.0022 (8) | 0.0051 (8) |
C12 | 0.0161 (10) | 0.0130 (10) | 0.0174 (10) | 0.0082 (8) | 0.0004 (8) | 0.0046 (8) |
C13 | 0.0158 (10) | 0.0213 (11) | 0.0190 (11) | 0.0100 (9) | 0.0006 (8) | 0.0045 (8) |
N14 | 0.0159 (9) | 0.0225 (10) | 0.0170 (9) | 0.0094 (8) | 0.0008 (7) | 0.0045 (7) |
C15 | 0.0201 (10) | 0.0160 (11) | 0.0177 (10) | 0.0118 (9) | 0.0008 (8) | 0.0030 (8) |
O16 | 0.0170 (7) | 0.0255 (8) | 0.0198 (8) | 0.0100 (7) | −0.0008 (6) | 0.0053 (6) |
O17 | 0.0199 (8) | 0.0330 (9) | 0.0179 (8) | 0.0156 (7) | 0.0040 (6) | 0.0096 (6) |
Zn—O1 | 2.0923 (15) | C6—C7 | 1.394 (3) |
Zn—O1i | 2.0923 (15) | C6—C9 | 1.486 (3) |
Zn—N3i | 2.1419 (17) | C7—C8 | 1.384 (3) |
Zn—N3 | 2.1420 (17) | C7—H7 | 0.9500 |
Zn—O2i | 2.1512 (15) | C8—H8 | 0.9500 |
Zn—O2 | 2.1512 (15) | C9—N14 | 1.338 (3) |
O1—H1A | 0.830 (10) | C9—N10 | 1.348 (3) |
O1—H1B | 0.822 (10) | N10—C11 | 1.336 (3) |
O2—H2A | 0.833 (10) | C11—C12 | 1.385 (3) |
O2—H2B | 0.827 (10) | C11—H11 | 0.9500 |
N3—C8 | 1.341 (3) | C12—C13 | 1.392 (3) |
N3—C4 | 1.347 (3) | C12—C15 | 1.510 (3) |
C4—C5 | 1.383 (3) | C13—N14 | 1.340 (3) |
C4—H4 | 0.9500 | C13—H13 | 0.9500 |
C5—C6 | 1.393 (3) | C15—O16 | 1.257 (3) |
C5—H5 | 0.9500 | C15—O17 | 1.258 (3) |
O1—Zn—O1i | 180.0 | C4—C5—H5 | 120.5 |
O1—Zn—N3i | 88.59 (6) | C6—C5—H5 | 120.5 |
O1i—Zn—N3i | 91.41 (6) | C5—C6—C7 | 118.01 (19) |
O1—Zn—N3 | 91.41 (6) | C5—C6—C9 | 121.15 (18) |
O1i—Zn—N3 | 88.59 (6) | C7—C6—C9 | 120.83 (19) |
N3i—Zn—N3 | 180.0 | C8—C7—C6 | 119.2 (2) |
O1—Zn—O2i | 86.31 (6) | C8—C7—H7 | 120.4 |
O1i—Zn—O2i | 93.69 (6) | C6—C7—H7 | 120.4 |
N3i—Zn—O2i | 91.45 (6) | N3—C8—C7 | 123.13 (19) |
N3—Zn—O2i | 88.55 (6) | N3—C8—H8 | 118.4 |
O1—Zn—O2 | 93.69 (6) | C7—C8—H8 | 118.4 |
O1i—Zn—O2 | 86.31 (6) | N14—C9—N10 | 126.45 (19) |
N3i—Zn—O2 | 88.55 (6) | N14—C9—C6 | 117.08 (18) |
N3—Zn—O2 | 91.45 (6) | N10—C9—C6 | 116.48 (19) |
O2i—Zn—O2 | 180.0 | C11—N10—C9 | 115.59 (19) |
Zn—O1—H1A | 118 (2) | N10—C11—C12 | 123.16 (19) |
Zn—O1—H1B | 118 (2) | N10—C11—H11 | 118.4 |
H1A—O1—H1B | 103 (3) | C12—C11—H11 | 118.4 |
Zn—O2—H2A | 110 (2) | C11—C12—C13 | 116.22 (19) |
Zn—O2—H2B | 125 (2) | C11—C12—C15 | 121.41 (18) |
H2A—O2—H2B | 114 (3) | C13—C12—C15 | 122.36 (19) |
C8—N3—C4 | 117.43 (18) | N14—C13—C12 | 122.3 (2) |
C8—N3—Zn | 121.52 (14) | N14—C13—H13 | 118.8 |
C4—N3—Zn | 120.54 (14) | C12—C13—H13 | 118.8 |
N3—C4—C5 | 123.19 (19) | C9—N14—C13 | 116.28 (18) |
N3—C4—H4 | 118.4 | O16—C15—O17 | 125.88 (19) |
C5—C4—H4 | 118.4 | O16—C15—C12 | 117.94 (18) |
C4—C5—C6 | 118.99 (19) | O17—C15—C12 | 116.18 (19) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O16ii | 0.83 (2) | 1.98 (2) | 2.805 (3) | 175 (3) |
O1—H1B···O17iii | 0.82 (3) | 1.81 (3) | 2.631 (3) | 175 (4) |
O2—H2A···O16iv | 0.83 (4) | 2.04 (4) | 2.840 (3) | 162 (4) |
O2—H2B···O17v | 0.83 (3) | 1.94 (3) | 2.767 (3) | 173 (3) |
Symmetry codes: (ii) x−1, y−1, z−1; (iii) −x+1, −y, −z+1; (iv) x−1, y, z−1; (v) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C10H6N3O2)2(H2O)4] |
Mr | 537.79 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 6.2764 (7), 6.9208 (7), 12.7810 (17) |
α, β, γ (°) | 99.676 (7), 92.638 (7), 112.639 (5) |
V (Å3) | 501.36 (10) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.29 |
Crystal size (mm) | 0.26 × 0.20 × 0.04 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.730, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8143, 2184, 2030 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.647 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.089, 1.14 |
No. of reflections | 2184 |
No. of parameters | 176 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.05, −0.61 |
Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O16i | 0.83 (2) | 1.98 (2) | 2.805 (3) | 175 (3) |
O1—H1B···O17ii | 0.82 (3) | 1.81 (3) | 2.631 (3) | 175 (4) |
O2—H2A···O16iii | 0.83 (4) | 2.04 (4) | 2.840 (3) | 162 (4) |
O2—H2B···O17iv | 0.83 (3) | 1.94 (3) | 2.767 (3) | 173 (3) |
Symmetry codes: (i) x−1, y−1, z−1; (ii) −x+1, −y, −z+1; (iii) x−1, y, z−1; (iv) x, y, z−1. |
Acknowledgements
RS wishes to thank FCT(SFRH/BPD/71798/2010) for a postdoctoral grant.
References
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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.
The aim of designing coordination frameworks is now been motivated through the field of supramolecular chemistry (Collet et al., 1996) and crystal engineering (Sen et al., 2012) from the viewpoints of the development of novel multi-functional MOFs. Fabricating MOFs with the desired properties are now the present day challenges of the chemist. N-Heterocyclic carboxylic acids share a major role in developing MOFs based material synthesis (Sen et al., 2012, Saha et al. 2012). Herein, we wish to report a new compound having an N-heterocyclic carboxylate ligand (2-pyridin-4-ylpyrimidine-5-carboxylato).
The molecular structure of the title compound is shown in Fig. 1. The ZnII ion lies on an inversion center and is coordinated in a slightly distorted octahedral geometry by two N atoms from two 2-pyridin-4-ylpyrimidine-5-carboxylato ligands and four water molecules. The equatorial plane is formed by the four water molecule and the two axial sites are occupied by the N-donor sites of the ligand. In the crystal, O—H···O hydrogen bonds form a three-dimensional network (Fig. 2). The related structure, tetraaquabis[4-(4H-1,2,4-triazol-4-yl)benzoato- κN1]manganese(II) decahydrate, has been published (Piao & Xuan, 2011).