Acta Cryst. (2007). E63, m2543 [ doi:10.1107/S1600536807044066 ]
![[mu]](/logos/entities/mu_rmgif.gif)
2-azido-![[kappa]](/logos/entities/kappa_rmgif.gif)
2N1:N3)(2-3,5-di-2-pyridyl-1,2,4-triazole-4N1,N5:N2,N3)manganese(II)]In the crystal structure of the polymeric title compound, [Mn2(N3)2(C12H8N5)2]n, the MnII atom exists in an octahedral geometry owing to coordination by four N atoms from two 3,5-bis(pyridin-2-yl)-1,2,4-triazolate ligands and by two azide ligands. The heterocyclic ligand binds in a chelating mode. The bidentate bridging mode of both anions leads to a linear ribbon motif.
A mixture of manganese sulfate monohydrate (0.169 g, 1 mmol), sodium azide (0.065 g, 1 mmol) 3,5-bis(pyridin-2-yl)-1,2,4-triazole (0.223 g, 1 mmol) and methanol (10 ml) was heated in a Teflon-lined stainless steel autoclave (25 ml) for 120 h at 393 K, after which the autoclave was cooled to room temperature over a period of 8 h at a rate of 10 K h−1. Pale yellow block single crystals of (I) were collected in about 15% yield. Elemental analysis, calcd (%) for C12H8MnN8: C, 45.16; H, 2.53; N, 35.11; found (%): C, 45.19; H, 2.50; N, 35.07.
All other H atoms were positioned geometrically and refined as riding, with C–H distances of 0.93 Å and Uiso(H) = 1.2 Ueq(C).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
![[Figure 1]](./ng2325fig1thm.gif)
| Fig. 1. The asymmetric unit of (I), showing displacement ellipsoids drawn at the 30% probability level for non-H atoms. Hydrogen atoms have been omitted. Symmetry codes: (i) −x, y − 1/2, −z; (ii) 1 − x, y-1/2,-z. |
![[Figure 2]](./ng2325fig2thm.gif)
| Fig. 2. 3-D Packing diagram of title complex; Hydrogen atoms have been omitted. |
| [Mn2(N3)2(C12H8N5)2] | F000 = 322 |
| Mr = 638.38 | Dx = 1.660 Mg m−3 |
| Monoclinic, P21 | Mo Kα radiation λ = 0.71073 Å |
| a = 8.6965 (9) Å | Cell parameters from 2337 reflections |
| b = 6.5597 (7) Å | θ = 1.8–27.0º |
| c = 11.8601 (13) Å | µ = 1.04 mm−1 |
| β = 109.245 (2)º | T = 293 (2) K |
| V = 638.77 (12) Å3 | Block, pale yellow |
| Z = 1 | 0.31 × 0.26 × 0.22 mm |
| Bruker APEX area-detector diffractometer | 2337 independent reflections |
| Radiation source: fine-focus sealed tube | 2207 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.019 |
| T = 293(2) K | θmax = 27.0º |
| φ and ω scans | θmin = 1.8º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→11 |
| Tmin = 0.732, Tmax = 0.796 | k = −6→8 |
| 3598 measured reflections | l = −15→11 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.0334P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.076 | (Δ/σ)max = 0.001 |
| S = 1.05 | Δρmax = 0.40 e Å−3 |
| 2337 reflections | Δρmin = −0.23 e Å−3 |
| 190 parameters | Extinction correction: none |
| 1 restraint | Absolute structure: Flack (1983), with 825 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.02 (2) |
| Secondary atom site location: difference Fourier map |
| [Mn2(N3)2(C12H8N5)2] | V = 638.77 (12) Å3 |
| Mr = 638.38 | Z = 1 |
| Monoclinic, P21 | Mo Kα |
| a = 8.6965 (9) Å | µ = 1.04 mm−1 |
| b = 6.5597 (7) Å | T = 293 (2) K |
| c = 11.8601 (13) Å | 0.31 × 0.26 × 0.22 mm |
| β = 109.245 (2)º |
| Bruker APEX area-detector diffractometer | 2337 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2207 reflections with I > 2σ(I) |
| Tmin = 0.732, Tmax = 0.796 | Rint = 0.019 |
| 3598 measured reflections |
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.076 | Δρmax = 0.40 e Å−3 |
| S = 1.05 | Δρmin = −0.23 e Å−3 |
| 2337 reflections | Absolute structure: Flack (1983), with 825 Friedel pairs |
| 190 parameters | Flack parameter: 0.02 (2) |
| 1 restraint |
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 | 0.20518 (4) | 0.28461 (8) | 0.01852 (3) | 0.02671 (12) | |
| C1 | 0.2386 (4) | −0.0499 (5) | −0.1771 (3) | 0.0378 (8) | |
| H1A | 0.2845 | −0.1357 | −0.1123 | 0.045* | |
| C2 | 0.2498 (4) | −0.1043 (6) | −0.2863 (3) | 0.0432 (9) | |
| H2A | 0.3023 | −0.2240 | −0.2948 | 0.052* | |
| C3 | 0.1817 (4) | 0.0222 (6) | −0.3828 (3) | 0.0433 (9) | |
| H3A | 0.1896 | −0.0090 | −0.4572 | 0.052* | |
| C4 | 0.1025 (4) | 0.1938 (6) | −0.3673 (3) | 0.0398 (8) | |
| H4A | 0.0545 | 0.2800 | −0.4316 | 0.048* | |
| C5 | 0.0938 (3) | 0.2397 (5) | −0.2553 (3) | 0.0301 (8) | |
| C6 | 0.0090 (3) | 0.4189 (5) | −0.2304 (2) | 0.0279 (6) | |
| C7 | −0.1260 (4) | 0.6830 (5) | −0.2408 (3) | 0.0271 (6) | |
| C8 | −0.2227 (4) | 0.8677 (5) | −0.2788 (3) | 0.0298 (7) | |
| C9 | −0.2739 (4) | 0.9397 (6) | −0.3957 (3) | 0.0412 (8) | |
| H9A | −0.2508 | 0.8674 | −0.4556 | 0.049* | |
| C10 | −0.3587 (5) | 1.1186 (6) | −0.4209 (3) | 0.0492 (10) | |
| H10A | −0.3943 | 1.1689 | −0.4985 | 0.059* | |
| C11 | −0.3914 (4) | 1.2242 (6) | −0.3312 (3) | 0.0475 (9) | |
| H11A | −0.4469 | 1.3477 | −0.3463 | 0.057* | |
| C12 | −0.3394 (4) | 1.1413 (6) | −0.2185 (3) | 0.0418 (8) | |
| H12A | −0.3627 | 1.2112 | −0.1579 | 0.050* | |
| N1 | 0.0114 (3) | 0.4542 (4) | −0.1192 (2) | 0.0277 (6) | |
| N2 | −0.0767 (3) | 0.6266 (4) | −0.1258 (2) | 0.0272 (6) | |
| N3 | −0.0742 (3) | 0.5565 (4) | −0.3107 (2) | 0.0311 (6) | |
| N4 | 0.1652 (3) | 0.1196 (4) | −0.1599 (2) | 0.0305 (6) | |
| N5 | −0.2582 (3) | 0.9683 (4) | −0.1913 (2) | 0.0315 (6) | |
| N6 | 0.3757 (3) | 0.4973 (5) | −0.0301 (3) | 0.0504 (8) | |
| N7 | 0.4788 (3) | 0.5367 (4) | −0.0680 (2) | 0.0302 (6) | |
| N8 | 0.5818 (3) | 0.5817 (5) | −0.1066 (3) | 0.0400 (7) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn1 | 0.0275 (2) | 0.0289 (2) | 0.0258 (2) | 0.0011 (2) | 0.01163 (15) | 0.0022 (2) |
| C1 | 0.0392 (18) | 0.0314 (19) | 0.0395 (18) | 0.0030 (16) | 0.0084 (15) | 0.0001 (15) |
| C2 | 0.0461 (19) | 0.035 (2) | 0.048 (2) | 0.0058 (17) | 0.0147 (16) | −0.0104 (17) |
| C3 | 0.053 (2) | 0.048 (2) | 0.0321 (18) | 0.0030 (18) | 0.0171 (16) | −0.0110 (16) |
| C4 | 0.0419 (18) | 0.046 (2) | 0.0304 (17) | 0.0092 (16) | 0.0112 (15) | 0.0016 (15) |
| C5 | 0.0306 (14) | 0.032 (2) | 0.0277 (14) | 0.0035 (13) | 0.0100 (12) | −0.0002 (12) |
| C6 | 0.0285 (15) | 0.0312 (18) | 0.0261 (15) | 0.0018 (13) | 0.0119 (12) | −0.0001 (13) |
| C7 | 0.0259 (14) | 0.0311 (17) | 0.0256 (15) | 0.0003 (13) | 0.0104 (12) | −0.0005 (12) |
| C8 | 0.0281 (15) | 0.0306 (16) | 0.0317 (16) | −0.0023 (13) | 0.0113 (13) | 0.0007 (13) |
| C9 | 0.049 (2) | 0.042 (2) | 0.0333 (17) | 0.0043 (18) | 0.0149 (15) | 0.0046 (16) |
| C10 | 0.055 (2) | 0.049 (2) | 0.040 (2) | 0.008 (2) | 0.0101 (18) | 0.0164 (17) |
| C11 | 0.050 (2) | 0.033 (2) | 0.057 (2) | 0.0087 (16) | 0.0147 (18) | 0.0102 (16) |
| C12 | 0.0446 (19) | 0.034 (2) | 0.048 (2) | 0.0056 (16) | 0.0171 (17) | −0.0014 (16) |
| N1 | 0.0283 (13) | 0.0302 (15) | 0.0286 (13) | 0.0021 (11) | 0.0148 (10) | 0.0009 (11) |
| N2 | 0.0248 (12) | 0.0300 (15) | 0.0282 (13) | 0.0021 (11) | 0.0106 (10) | 0.0027 (11) |
| N3 | 0.0363 (14) | 0.0314 (15) | 0.0275 (13) | 0.0038 (12) | 0.0133 (11) | 0.0021 (11) |
| N4 | 0.0329 (13) | 0.0275 (15) | 0.0305 (14) | 0.0015 (12) | 0.0098 (11) | 0.0016 (11) |
| N5 | 0.0350 (14) | 0.0289 (15) | 0.0326 (14) | 0.0023 (12) | 0.0140 (12) | 0.0003 (12) |
| N6 | 0.0377 (16) | 0.050 (2) | 0.068 (2) | −0.0082 (15) | 0.0233 (15) | 0.0086 (17) |
| N7 | 0.0313 (13) | 0.0225 (13) | 0.0353 (14) | 0.0001 (11) | 0.0089 (12) | 0.0024 (11) |
| N8 | 0.0380 (15) | 0.0431 (19) | 0.0441 (17) | −0.0086 (13) | 0.0207 (13) | −0.0045 (14) |
| Mn1—N2i | 2.208 (2) | C7—N2 | 1.340 (4) |
| Mn1—N1 | 2.221 (2) | C7—N3 | 1.351 (4) |
| Mn1—N8ii | 2.240 (3) | C7—C8 | 1.459 (4) |
| Mn1—N6 | 2.245 (3) | C8—N5 | 1.348 (4) |
| Mn1—N5i | 2.289 (3) | C8—C9 | 1.392 (4) |
| Mn1—N4 | 2.299 (3) | C9—C10 | 1.365 (5) |
| C1—N4 | 1.331 (4) | C9—H9A | 0.9300 |
| C1—C2 | 1.377 (5) | C10—C11 | 1.375 (5) |
| C1—H1A | 0.9300 | C10—H10A | 0.9300 |
| C2—C3 | 1.380 (5) | C11—C12 | 1.374 (5) |
| C2—H2A | 0.9300 | C11—H11A | 0.9300 |
| C3—C4 | 1.363 (5) | C12—N5 | 1.319 (4) |
| C3—H3A | 0.9300 | C12—H12A | 0.9300 |
| C4—C5 | 1.389 (4) | N1—N2 | 1.354 (3) |
| C4—H4A | 0.9300 | N2—Mn1iii | 2.208 (2) |
| C5—N4 | 1.351 (4) | N5—Mn1iii | 2.289 (3) |
| C5—C6 | 1.468 (4) | N6—N7 | 1.157 (4) |
| C6—N1 | 1.333 (4) | N7—N8 | 1.170 (4) |
| C6—N3 | 1.339 (4) | N8—Mn1iv | 2.240 (3) |
| N2i—Mn1—N1 | 104.67 (9) | N2—C7—C8 | 120.1 (3) |
| N2i—Mn1—N8ii | 87.13 (10) | N3—C7—C8 | 126.5 (3) |
| N1—Mn1—N8ii | 162.01 (9) | N5—C8—C9 | 121.5 (3) |
| N2i—Mn1—N6 | 160.37 (11) | N5—C8—C7 | 115.1 (3) |
| N1—Mn1—N6 | 84.57 (10) | C9—C8—C7 | 123.5 (3) |
| N8ii—Mn1—N6 | 88.54 (11) | C10—C9—C8 | 118.8 (3) |
| N2i—Mn1—N5i | 73.88 (9) | C10—C9—H9A | 120.6 |
| N1—Mn1—N5i | 105.95 (9) | C8—C9—H9A | 120.6 |
| N8ii—Mn1—N5i | 90.21 (10) | C9—C10—C11 | 119.9 (3) |
| N6—Mn1—N5i | 87.01 (11) | C9—C10—H10A | 120.1 |
| N2i—Mn1—N4 | 110.94 (9) | C11—C10—H10A | 120.1 |
| N1—Mn1—N4 | 73.20 (9) | C12—C11—C10 | 117.9 (3) |
| N8ii—Mn1—N4 | 90.03 (10) | C12—C11—H11A | 121.1 |
| N6—Mn1—N4 | 88.19 (11) | C10—C11—H11A | 121.1 |
| N5i—Mn1—N4 | 175.18 (10) | N5—C12—C11 | 123.8 (3) |
| N4—C1—C2 | 123.2 (3) | N5—C12—H12A | 118.1 |
| N4—C1—H1A | 118.4 | C11—C12—H12A | 118.1 |
| C2—C1—H1A | 118.4 | C6—N1—N2 | 105.3 (2) |
| C1—C2—C3 | 118.7 (3) | C6—N1—Mn1 | 113.65 (19) |
| C1—C2—H2A | 120.7 | N2—N1—Mn1 | 137.63 (19) |
| C3—C2—H2A | 120.7 | C7—N2—N1 | 105.9 (2) |
| C4—C3—C2 | 118.9 (3) | C7—N2—Mn1iii | 113.8 (2) |
| C4—C3—H3A | 120.6 | N1—N2—Mn1iii | 137.99 (19) |
| C2—C3—H3A | 120.6 | C6—N3—C7 | 100.9 (2) |
| C3—C4—C5 | 119.8 (3) | C1—N4—C5 | 118.0 (3) |
| C3—C4—H4A | 120.1 | C1—N4—Mn1 | 126.9 (2) |
| C5—C4—H4A | 120.1 | C5—N4—Mn1 | 112.7 (2) |
| N4—C5—C4 | 121.4 (3) | C12—N5—C8 | 118.2 (3) |
| N4—C5—C6 | 114.9 (3) | C12—N5—Mn1iii | 127.3 (2) |
| C4—C5—C6 | 123.7 (3) | C8—N5—Mn1iii | 113.7 (2) |
| N1—C6—N3 | 114.5 (3) | N7—N6—Mn1 | 154.2 (3) |
| N1—C6—C5 | 119.6 (3) | N6—N7—N8 | 178.3 (4) |
| N3—C6—C5 | 125.9 (2) | N7—N8—Mn1iv | 126.1 (2) |
| N2—C7—N3 | 113.3 (3) |
| Symmetry codes: (i) −x, y−1/2, −z; (ii) −x+1, y−1/2, −z; (iii) −x, y+1/2, −z; (iv) −x+1, y+1/2, −z. |
The authors acknowledge financial support by the Natural Science Foundation of China (grant No. 20561001) and the Patent Special Foundation of the Ministry of Education of Guangxi Province (grant No. 2006–26).
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1,2,4-triazole derivatives are a class of azole compounds that can act as either 2,4- or 1,2-bridging nitrogen donor ligands. 3,5-bis(pyridin-2-yl)-1,2,4-triazole can act as tetradentate ligands and are therefore very suitable for studying exchange-coupled pairs of transition-metal ions. (Prins et al., 1995; Chen et al., 2006). However, only small part of mononuclear and dinuclear complexes were characterized by X-ray crystallography. On the other hand, azide was widely used to connect metal ions, and the correlation between the structure and magnetic properties of different coordination modes was observed (Wang et al., 2006). In this paper, solvothermal technique has been successfully applied in the Mn2+/bpt−/N3− system to synthesize the title compound.
There are one MnII atom, one bpt− ligand and one azide ligand in the asymmetric unit. The MnII atom has an octahedral environment, formed by four N atoms from two different bpt− ligand and two N atoms belonging to two azide ligands. The bpt− ligand binds to manganese in a cis-bis(chelate) mode, through two pyridine and two triazole nitrogen atoms, linking the MnII atoms into a helical chain that runs along the b axis. Each pair of MnII ions from adjacent chains are additionally bridged by two azide lingds in the EE mode and further linked the [Mn(bpt)]+ chains into a two-dimensional (4,4) net.