Acta Cryst. (2007). E63, m1628 [ doi:10.1107/S1600536807021885 ]
The title complex, [Mn(C5H3N6)2(H2O)2], possesses a crystallographically imposed center of symmetry occupied by an MnII ion, which is coordinated by four N atoms from two 5-(pyrimidin-2-yl)tetrazolate ligands [Mn-N = 2.2066 (13) and 2.2731 (15) Å] and two water molecules [Mn-O = 2.1868 (14) Å] in a distorted octahedral geometry. In the crystal structure, intermolecular O-H
N hydrogen bonds link the complexes into two-dimensional sheets parallel to the bc plane.
The ligand, 2-(1H-tetrazol-5-yl)pyrimidine (L) was synthesized according to the literature method (Demko & Sharpless, 2001). A mixture of MnCl2.4H2O (40 mg, 0.2 mmol) and ligand L (60 mg, 0.4 mmol) in water (10 ml) was placed in a Teflon-lined stainless-steel Parr bomb that was heated at 393 K for 48 h. Colorless crystals were collected after the bomb allowed to cool to room temperature spontaneously. Yield, 40%.
The C-bound H atoms were placed in calculated positions (C—H 0.93 Å) and treated in the subsequent refinement as riding atoms, with Uiso(H) = 1.2 Ueq(C). Two H atoms of the water molecule were located in Fourier difference map and refined with bond restraints O—H = 0.84 (1) Å, and with Uiso(H) = 1.5 Ueq(O).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
![[Figure 1]](./cv2240fig1thm.gif)
| Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level [symmetry code: (A) 1 - x, 2 - y, - z]. |
![[Figure 2]](./cv2240fig2thm.gif)
| Fig. 2. Two-dimensional hydrogen-bonded network. |
| [Mn(C5H3N6)2(H2O)2] | F(000) = 390 |
| Mr = 385.24 | Dx = 1.685 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 5442 reflections |
| a = 8.0084 (16) Å | θ = 3.0–27.5° |
| b = 13.095 (3) Å | µ = 0.91 mm−1 |
| c = 7.2958 (15) Å | T = 293 K |
| β = 97.18 (3)° | Block, colourless |
| V = 759.1 (3) Å3 | 0.16 × 0.14 × 0.02 mm |
| Z = 2 |
| Bruker SMART CCD area-detector diffractometer | 1737 independent reflections |
| Radiation source: fine-focus sealed tube | 1431 reflections with I > 2σ(I) |
| graphite | Rint = 0.043 |
| φ and ω scans | θmax = 27.5°, θmin = 3.0° |
| Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −10→10 |
| Tmin = 0.929, Tmax = 1.000 | k = −17→16 |
| 7203 measured reflections | l = −9→9 |
| 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)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0335P)2 + 0.1658P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max = 0.001 |
| 1737 reflections | Δρmax = 0.30 e Å−3 |
| 122 parameters | Δρmin = −0.23 e Å−3 |
| 2 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.020 (3) |
| [Mn(C5H3N6)2(H2O)2] | V = 759.1 (3) Å3 |
| Mr = 385.24 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.0084 (16) Å | µ = 0.91 mm−1 |
| b = 13.095 (3) Å | T = 293 K |
| c = 7.2958 (15) Å | 0.16 × 0.14 × 0.02 mm |
| β = 97.18 (3)° |
| Bruker SMART CCD area-detector diffractometer | 1737 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 1998) | 1431 reflections with I > 2σ(I) |
| Tmin = 0.929, Tmax = 1.000 | Rint = 0.043 |
| 7203 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.076 | Δρmax = 0.30 e Å−3 |
| S = 1.03 | Δρmin = −0.23 e Å−3 |
| 1737 reflections | Absolute structure: ? |
| 122 parameters | Flack parameter: ? |
| 2 restraints | Rogers parameter: ? |
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 | ||
| Mn1 | 0.5000 | 1.0000 | 0.0000 | 0.03101 (14) | |
| N1 | 0.54376 (17) | 1.16630 (9) | −0.00415 (17) | 0.0303 (3) | |
| N2 | 0.65673 (19) | 1.23355 (10) | −0.05190 (19) | 0.0359 (3) | |
| N3 | 0.5993 (2) | 1.32610 (10) | −0.02615 (19) | 0.0388 (4) | |
| N4 | 0.4487 (2) | 1.32100 (10) | 0.03793 (19) | 0.0368 (3) | |
| N5 | 0.27899 (18) | 1.07056 (10) | 0.12166 (18) | 0.0348 (3) | |
| N6 | 0.1532 (2) | 1.23123 (13) | 0.1739 (2) | 0.0466 (4) | |
| C1 | 0.4187 (2) | 1.22145 (11) | 0.0503 (2) | 0.0297 (3) | |
| C2 | 0.2734 (2) | 1.17322 (12) | 0.1182 (2) | 0.0320 (4) | |
| C3 | 0.1543 (3) | 1.02274 (16) | 0.1923 (3) | 0.0495 (5) | |
| H3A | 0.1547 | 0.9518 | 0.1987 | 0.059* | |
| C4 | 0.0256 (3) | 1.07621 (19) | 0.2555 (3) | 0.0618 (6) | |
| H4A | −0.0606 | 1.0430 | 0.3060 | 0.074* | |
| C5 | 0.0292 (3) | 1.18049 (19) | 0.2413 (3) | 0.0578 (6) | |
| H5A | −0.0586 | 1.2178 | 0.2803 | 0.069* | |
| O1W | 0.64119 (17) | 0.99277 (8) | 0.27633 (16) | 0.0359 (3) | |
| H1WA | 0.623 (3) | 0.9423 (12) | 0.340 (3) | 0.054* | |
| H1WB | 0.632 (3) | 1.0442 (12) | 0.344 (3) | 0.054* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn1 | 0.0393 (2) | 0.01818 (19) | 0.0371 (2) | −0.00146 (14) | 0.01063 (15) | −0.00165 (12) |
| N1 | 0.0360 (8) | 0.0227 (7) | 0.0333 (7) | −0.0030 (5) | 0.0083 (6) | 0.0001 (5) |
| N2 | 0.0446 (9) | 0.0262 (7) | 0.0376 (7) | −0.0071 (6) | 0.0081 (6) | 0.0014 (5) |
| N3 | 0.0563 (10) | 0.0219 (7) | 0.0377 (8) | −0.0059 (6) | 0.0042 (7) | 0.0025 (5) |
| N4 | 0.0507 (9) | 0.0219 (7) | 0.0365 (8) | 0.0035 (6) | 0.0008 (6) | −0.0005 (5) |
| N5 | 0.0359 (8) | 0.0335 (7) | 0.0360 (7) | −0.0051 (6) | 0.0086 (6) | −0.0034 (5) |
| N6 | 0.0388 (10) | 0.0556 (10) | 0.0456 (9) | 0.0139 (7) | 0.0056 (7) | −0.0070 (7) |
| C1 | 0.0385 (9) | 0.0229 (8) | 0.0268 (7) | 0.0035 (6) | 0.0007 (6) | −0.0017 (5) |
| C2 | 0.0338 (9) | 0.0339 (9) | 0.0276 (8) | 0.0040 (7) | 0.0011 (6) | −0.0044 (6) |
| C3 | 0.0447 (12) | 0.0544 (12) | 0.0511 (11) | −0.0160 (9) | 0.0125 (9) | −0.0017 (8) |
| C4 | 0.0387 (13) | 0.0904 (18) | 0.0594 (13) | −0.0148 (11) | 0.0181 (10) | −0.0052 (11) |
| C5 | 0.0347 (12) | 0.0875 (17) | 0.0521 (12) | 0.0108 (11) | 0.0093 (9) | −0.0123 (10) |
| O1W | 0.0492 (8) | 0.0222 (6) | 0.0373 (7) | −0.0026 (5) | 0.0095 (5) | 0.0003 (4) |
| Mn1—O1W | 2.1868 (14) | N5—C2 | 1.345 (2) |
| Mn1—O1Wi | 2.1868 (14) | N6—C2 | 1.329 (2) |
| Mn1—N1 | 2.2066 (13) | N6—C5 | 1.338 (3) |
| Mn1—N1i | 2.2066 (13) | C1—C2 | 1.464 (2) |
| Mn1—N5i | 2.2731 (15) | C3—C4 | 1.373 (3) |
| Mn1—N5 | 2.2731 (15) | C3—H3A | 0.9300 |
| N1—C1 | 1.335 (2) | C4—C5 | 1.370 (3) |
| N1—N2 | 1.3394 (18) | C4—H4A | 0.9300 |
| N2—N3 | 1.3181 (19) | C5—H5A | 0.9300 |
| N3—N4 | 1.349 (2) | O1W—H1WA | 0.830 (9) |
| N4—C1 | 1.331 (2) | O1W—H1WB | 0.844 (9) |
| N5—C3 | 1.335 (2) | ||
| O1W—Mn1—O1Wi | 180.00 (5) | C3—N5—Mn1 | 128.04 (13) |
| O1W—Mn1—N1 | 89.47 (4) | C2—N5—Mn1 | 115.14 (11) |
| O1Wi—Mn1—N1 | 90.53 (4) | C2—N6—C5 | 115.28 (18) |
| O1W—Mn1—N1i | 90.53 (4) | N4—C1—N1 | 111.16 (15) |
| O1Wi—Mn1—N1i | 89.47 (4) | N4—C1—C2 | 127.15 (15) |
| N1—Mn1—N1i | 180.0 | N1—C1—C2 | 121.67 (13) |
| O1W—Mn1—N5i | 90.24 (5) | N6—C2—N5 | 126.13 (16) |
| O1Wi—Mn1—N5i | 89.76 (5) | N6—C2—C1 | 119.56 (15) |
| N1—Mn1—N5i | 105.25 (5) | N5—C2—C1 | 114.29 (14) |
| N1i—Mn1—N5i | 74.75 (5) | N5—C3—C4 | 121.32 (19) |
| O1W—Mn1—N5 | 89.76 (5) | N5—C3—H3A | 119.3 |
| O1Wi—Mn1—N5 | 90.24 (5) | C4—C3—H3A | 119.3 |
| N1—Mn1—N5 | 74.75 (5) | C5—C4—C3 | 117.3 (2) |
| N1i—Mn1—N5 | 105.25 (5) | C5—C4—H4A | 121.4 |
| N5i—Mn1—N5 | 180.0 | C3—C4—H4A | 121.4 |
| C1—N1—N2 | 106.15 (13) | N6—C5—C4 | 123.15 (19) |
| C1—N1—Mn1 | 113.79 (10) | N6—C5—H5A | 118.4 |
| N2—N1—Mn1 | 140.00 (11) | C4—C5—H5A | 118.4 |
| N3—N2—N1 | 107.96 (14) | Mn1—O1W—H1WA | 116.2 (15) |
| N2—N3—N4 | 110.30 (12) | Mn1—O1W—H1WB | 115.5 (15) |
| C1—N4—N3 | 104.43 (13) | H1WA—O1W—H1WB | 106 (2) |
| C3—N5—C2 | 116.81 (16) | ||
| O1W—Mn1—N1—C1 | −94.61 (11) | N3—N4—C1—C2 | 178.01 (14) |
| O1Wi—Mn1—N1—C1 | 85.39 (11) | N2—N1—C1—N4 | 0.21 (17) |
| N5i—Mn1—N1—C1 | 175.28 (10) | Mn1—N1—C1—N4 | −177.47 (9) |
| N5—Mn1—N1—C1 | −4.72 (10) | N2—N1—C1—C2 | −178.20 (13) |
| O1W—Mn1—N1—N2 | 88.86 (16) | Mn1—N1—C1—C2 | 4.12 (18) |
| O1Wi—Mn1—N1—N2 | −91.14 (16) | C5—N6—C2—N5 | 1.0 (3) |
| N5i—Mn1—N1—N2 | −1.25 (16) | C5—N6—C2—C1 | −177.15 (16) |
| N5—Mn1—N1—N2 | 178.75 (16) | C3—N5—C2—N6 | −1.9 (2) |
| C1—N1—N2—N3 | −0.03 (16) | Mn1—N5—C2—N6 | 176.97 (13) |
| Mn1—N1—N2—N3 | 176.67 (11) | C3—N5—C2—C1 | 176.30 (15) |
| N1—N2—N3—N4 | −0.16 (18) | Mn1—N5—C2—C1 | −4.78 (17) |
| N2—N3—N4—C1 | 0.28 (18) | N4—C1—C2—N6 | 0.7 (2) |
| O1W—Mn1—N5—C3 | −86.51 (15) | N1—C1—C2—N6 | 178.89 (14) |
| O1Wi—Mn1—N5—C3 | 93.49 (15) | N4—C1—C2—N5 | −177.63 (14) |
| N1—Mn1—N5—C3 | −176.02 (16) | N1—C1—C2—N5 | 0.5 (2) |
| N1i—Mn1—N5—C3 | 3.98 (16) | C2—N5—C3—C4 | 1.0 (3) |
| O1W—Mn1—N5—C2 | 94.72 (11) | Mn1—N5—C3—C4 | −177.80 (14) |
| O1Wi—Mn1—N5—C2 | −85.28 (11) | N5—C3—C4—C5 | 0.7 (3) |
| N1—Mn1—N5—C2 | 5.20 (11) | C2—N6—C5—C4 | 0.9 (3) |
| N1i—Mn1—N5—C2 | −174.80 (11) | C3—C4—C5—N6 | −1.8 (3) |
| N3—N4—C1—N1 | −0.30 (17) |
| Symmetry codes: (i) −x+1, −y+2, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1WA···N4ii | 0.83 (1) | 1.94 (1) | 2.7673 (18) | 172 (2) |
| O1W—H1WB···N3iii | 0.84 (1) | 1.98 (1) | 2.8171 (17) | 173 (2) |
| Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+5/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1WA···N4i | 0.83 (1) | 1.94 (1) | 2.7673 (18) | 172 (2) |
| O1W—H1WB···N3ii | 0.84 (1) | 1.98 (1) | 2.8171 (17) | 173 (2) |
| Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+5/2, z+1/2. |
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5-Substituted 1H-tetrazole ligands are often used in metal-organic complexes. With N-heterocyclic substituents, most of metal complexes were structurally characterized, in which 2-position N-containing derivatives always give mono-nuclear complexes. Such as, diaquabis[5-(pyridyl-2-yl)tetrazolato]manganese(II), diaquabis[5-(pyridyl-2-yl)tetrazolato]copper(II), diaquabis[5-(pyridyl-2-yl)tetrazolato]zinc(II), diaquabis[5-(pyrazin-2-yl)tetrazolato]zinc(II) and diaquabis[5-(pyrazin-2-yl)tetrazolato]manganese(II) (Wang et al., 2003; Mo et al., 2004; Rodríguez et al., 2005; Luo et al., 2006; Peng et al., 2007). Herein, 2-(1H-tetrazol-5-yl)pyrimidine (L) ligands were used to give a similar mono-nuclear Mn(II) complex, diaquabis[5-(pyrimidin-2-yl)tetrazolato]manganese(II) (I). With this ligand, two two-dimensional Co(II) and Fe(II) complexes were reported recently (Rodríguez et al., 2005).
In the title complex (I), the central Mn(II) ion is located on an inversion center and coordinated by two deprotonated bidentate L ligands via one of the pyrimidinyl nitrogen and the tetrazole nitrogen in the 1-position and two water molecules with a transoid pseudo-octahedral geometry geometry (Fig. 1). The structure is similar to those of diaquabis[5-(pyridyl-2-yl)tetrazolato]manganese(II), diaquabis[5-(pyridyl-2-yl)tetrazolato]copper(II), diaquabis[5-(pyridyl-2-yl)tetrazolato]zinc(II), diaquabis[5-(pyrazin-2-yl)tetrazolato]zinc(II), diaquabis[5-(pyrazin-2-yl)tetrazolato]manganese(II) (Wang et al., 2003; Mo et al., 2004; Rodríguez et al., 2005; Luo et al., 2006; Peng et al., 2007).
An interesting aspect of the structure is the way in which the mononuclear units are interlinked via hydrogen bonds into a two-dimensional network. As shown in Fig. 2, each coordinated water molecule of a mononuclear unit interlinks with the tetrazole rings from two neighboring mononuclear units through O—H···N hydrogen bond, and each tetrazole ring forms two O—H···N hydrogen bonds via the nitrogen atoms at 3- and 4-positions with also two adjacent molecules. Thus, each unit forms a total of eight hydrogen bonds with its four neighbors. The related hydrogen bond parameters are listed in the Table.