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accesscatena-Poly[manganese(II)-(μ2-3,5-di-2-pyridyl-1,2,4-triazolato)-μ2-formato]
aDepartment of Chemistry and Chemical Engineering, Southeast University, Nanjing, People's Republic of China, and bDepartment of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, People's Republic of China
*Correspondence e-mail: cep02chl@yahoo.com.cn
Owing to the presence of crystallographic twofold rotation axes (site symmetry 2, Wyckoff letters e and f), the of the title compound, [Mn(C12H8N5)(CHO2)]n, contains one-half of an MnII cation, one-half of a bpt anion (Hbpt is 3,5-di-2-pyridyl-4H-1,2,4-triazole) and one-half of a formate anion. The bpt and formate ligands occupy the same C2 symmetry, while the MnII ion resides on another crystallographic twofold rotation axis. Each bpt ligand acts as a cis-bis-chelate to ligate two MnII ions into a one-dimensional chain running along the crystallographic 41 screw axis. Adjacent MnII ions are further bridged by a μ2-formate ligand, completing the distorted octahedral coordination geometry of the cation.
Related literature
For related literature, see: Zhang (2005![[Zhang, X.-M. (2005). Coord. Chem. Rev. 249, 1201-1219.]](../../../../../../logos/arrows/e_arr.gif "Zhang, X.-M. (2005). Coord. Chem. Rev. 249, 1201-1219.")
); Chen & Tong (2007). For related structures, see: Cheng et al. (2007a,b).
![[Scheme 1]](si2099scheme1.gif)
Experimental
Crystal data
|
Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks I, global. DOI: 10.1107/S160053680802299X/si2099sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S160053680802299X/si2099Isup2.hkl
A mixture of 4-cyanopyridine (0.416 g, 4.0 mmol), 80% hydrazine hydrate (2 ml), Mn(HCOO)2.2H2O (0.181 g, 1 mmol) and DMF (6 ml) was heated in a 15-ml Teflon-lined autoclave at 180° for 3 days, followed by slow cooling (5° h-1) to room temperature. The resulting mixture was washed with water, and pale-yellow block crystals were collected and dried in air [yield 1.0% (3.2 mg) based on MnII].
H atoms were positioned geometrically and refined using a riding model with constraint distances C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./si2099fig1thm.gif) | Fig. 1. The one-dimensional chain of the title compound with 30% thermal ellipsoids. All the hydrogen atoms are omitted for clarity. Symmetry codes: a: 5/4 - x, -1/4 - y, 1/4 - z; b: 3/2 - x, y, 1/2 - z; c: 1/4 + x, -1/4 - y, -1/4 + z; d: x, -y, 1/2 - z. |
| [Mn(C12H8N5)(CHO2)] | Dx = 1.570 Mg m−3 |
| Mr = 322.20 | Mo Kα radiation, λ = 0.71073 Å |
| Tetragonal, I41/acd | Cell parameters from 810 reflections |
| Hall symbol: -I 4bd 2c | θ = 2.5–28.0° |
| a = 19.124 (5) Å | µ = 0.98 mm−1 |
| c = 14.9120 (4) Å | T = 293 K |
| V = 5454 (2) Å3 | Needle-like, yellow |
| Z = 16 | 0.15 × 0.09 × 0.06 mm |
| F(000) = 2608 |
| Bruker APEX CCD diffractometer | 1346 independent reflections |
| Radiation source: fine-focus sealed tube | 1225 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.054 |
| ϕ and ω scans | θmax = 26.0°, θmin = 2.1° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −23→18 |
| Tmin = 0.867, Tmax = 0.944 | k = −23→23 |
| 14412 measured reflections | l = −18→17 |
| 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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.121 | H-atom parameters constrained |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0491P)2 + 25.4234P] where P = (Fo2 + 2Fc2)/3 |
| 1346 reflections | (Δ/σ)max < 0.001 |
| 97 parameters | Δρmax = 0.39 e Å−3 |
| 0 restraints | Δρmin = −0.37 e Å−3 |
| [Mn(C12H8N5)(CHO2)] | Z = 16 |
| Mr = 322.20 | Mo Kα radiation |
| Tetragonal, I41/acd | µ = 0.98 mm−1 |
| a = 19.124 (5) Å | T = 293 K |
| c = 14.9120 (4) Å | 0.15 × 0.09 × 0.06 mm |
| V = 5454 (2) Å3 |
| Bruker APEX CCD diffractometer | 1346 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 1225 reflections with I > 2σ(I) |
| Tmin = 0.867, Tmax = 0.944 | Rint = 0.054 |
| 14412 measured reflections |
| R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
| wR(F2) = 0.121 | H-atom parameters constrained |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0491P)2 + 25.4234P] where P = (Fo2 + 2Fc2)/3 |
| 1346 reflections | Δρmax = 0.39 e Å−3 |
| 97 parameters | Δρmin = −0.37 e Å−3 |
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 | 0.69057 (3) | −0.05943 (3) | 0.1250 | 0.0215 (2) | |
| C1 | 0.56957 (19) | −0.11100 (19) | −0.0239 (2) | 0.0318 (8) | |
| H1A | 0.6082 | −0.1244 | −0.0576 | 0.038* | |
| C2 | 0.5042 (2) | −0.1237 (2) | −0.0580 (2) | 0.0402 (10) | |
| H2A | 0.4989 | −0.1454 | −0.1134 | 0.048* | |
| C3 | 0.4464 (2) | −0.1038 (2) | −0.0088 (3) | 0.0431 (10) | |
| H3A | 0.4015 | −0.1118 | −0.0305 | 0.052* | |
| C4 | 0.45662 (19) | −0.0717 (2) | 0.0735 (2) | 0.0358 (9) | |
| H4A | 0.4187 | −0.0579 | 0.1082 | 0.043* | |
| C5 | 0.52424 (17) | −0.06066 (18) | 0.1029 (2) | 0.0259 (7) | |
| C6 | 0.54152 (16) | −0.02572 (17) | 0.1886 (2) | 0.0214 (7) | |
| C7 | 0.7500 | 0.0594 (3) | 0.0000 | 0.0300 (11) | |
| H7A | 0.7500 | 0.1080 | 0.0000 | 0.036* | |
| N1 | 0.58042 (15) | −0.08037 (14) | 0.05536 (18) | 0.0250 (6) | |
| N2 | 0.60816 (13) | −0.01663 (13) | 0.20974 (16) | 0.0196 (6) | |
| N3 | 0.4964 (2) | 0.0000 | 0.2500 | 0.0272 (9) | |
| O1 | 0.70537 (14) | 0.03180 (15) | 0.0481 (2) | 0.0501 (8) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn1 | 0.0221 (3) | 0.0221 (3) | 0.0203 (4) | 0.0017 (3) | 0.00432 (19) | −0.00432 (19) |
| C1 | 0.0325 (19) | 0.041 (2) | 0.0219 (17) | 0.0094 (16) | −0.0010 (15) | −0.0133 (15) |
| C2 | 0.041 (2) | 0.051 (2) | 0.0280 (18) | 0.0110 (19) | −0.0106 (17) | −0.0199 (18) |
| C3 | 0.033 (2) | 0.060 (3) | 0.037 (2) | 0.0061 (18) | −0.0149 (17) | −0.019 (2) |
| C4 | 0.0266 (19) | 0.048 (2) | 0.0325 (19) | 0.0032 (16) | −0.0025 (16) | −0.0150 (17) |
| C5 | 0.0272 (18) | 0.0303 (18) | 0.0202 (16) | 0.0008 (14) | −0.0028 (13) | −0.0057 (14) |
| C6 | 0.0210 (16) | 0.0264 (17) | 0.0167 (14) | 0.0000 (13) | −0.0021 (12) | −0.0049 (13) |
| C7 | 0.032 (3) | 0.023 (2) | 0.035 (3) | 0.000 | 0.001 (2) | 0.000 |
| N1 | 0.0279 (15) | 0.0275 (15) | 0.0197 (14) | 0.0018 (12) | −0.0009 (11) | −0.0086 (11) |
| N2 | 0.0225 (14) | 0.0210 (14) | 0.0154 (12) | −0.0015 (10) | −0.0012 (11) | −0.0058 (10) |
| N3 | 0.0205 (19) | 0.039 (2) | 0.0217 (18) | 0.000 | 0.000 | −0.0090 (17) |
| O1 | 0.0370 (16) | 0.0438 (16) | 0.069 (2) | 0.0047 (13) | 0.0165 (15) | 0.0253 (15) |
| Mn1—O1 | 2.107 (3) | C3—H3A | 0.9300 |
| Mn1—O1i | 2.107 (3) | C4—C5 | 1.382 (5) |
| Mn1—N2i | 2.180 (3) | C4—H4A | 0.9300 |
| Mn1—N2 | 2.180 (3) | C5—N1 | 1.341 (4) |
| Mn1—N1 | 2.382 (3) | C5—C6 | 1.480 (4) |
| Mn1—N1i | 2.382 (3) | C6—N2 | 1.324 (4) |
| C1—N1 | 1.335 (4) | C6—N3 | 1.350 (4) |
| C1—C2 | 1.372 (5) | C7—O1 | 1.234 (3) |
| C1—H1A | 0.9300 | C7—O1ii | 1.234 (3) |
| C2—C3 | 1.379 (5) | C7—H7A | 0.9300 |
| C2—H2A | 0.9300 | N2—N2iii | 1.359 (5) |
| C3—C4 | 1.386 (5) | N3—C6iii | 1.350 (4) |
| O1—Mn1—O1i | 94.23 (17) | C2—C3—H3A | 120.6 |
| O1—Mn1—N2i | 103.46 (11) | C4—C3—H3A | 120.6 |
| O1i—Mn1—N2i | 95.84 (10) | C5—C4—C3 | 118.7 (3) |
| O1—Mn1—N2 | 95.84 (10) | C5—C4—H4A | 120.6 |
| O1i—Mn1—N2 | 103.46 (11) | C3—C4—H4A | 120.6 |
| N2i—Mn1—N2 | 151.55 (13) | N1—C5—C4 | 122.6 (3) |
| O1—Mn1—N1 | 91.19 (11) | N1—C5—C6 | 113.9 (3) |
| O1i—Mn1—N1 | 172.74 (12) | C4—C5—C6 | 123.5 (3) |
| N2i—Mn1—N1 | 87.58 (9) | N2—C6—N3 | 114.0 (3) |
| N2—Mn1—N1 | 71.13 (9) | N2—C6—C5 | 118.6 (3) |
| O1—Mn1—N1i | 172.74 (12) | N3—C6—C5 | 127.4 (3) |
| O1i—Mn1—N1i | 91.19 (11) | O1—C7—O1ii | 129.3 (5) |
| N2i—Mn1—N1i | 71.13 (9) | O1—C7—H7A | 115.3 |
| N2—Mn1—N1i | 87.58 (9) | O1ii—C7—H7A | 115.3 |
| N1—Mn1—N1i | 83.84 (14) | C1—N1—C5 | 117.8 (3) |
| N1—C1—C2 | 123.2 (3) | C1—N1—Mn1 | 126.6 (2) |
| N1—C1—H1A | 118.4 | C5—N1—Mn1 | 115.5 (2) |
| C2—C1—H1A | 118.4 | C6—N2—N2iii | 105.75 (17) |
| C1—C2—C3 | 119.0 (3) | C6—N2—Mn1 | 120.59 (19) |
| C1—C2—H2A | 120.5 | N2iii—N2—Mn1 | 133.48 (7) |
| C3—C2—H2A | 120.5 | C6—N3—C6iii | 100.6 (4) |
| C2—C3—C4 | 118.7 (4) | C7—O1—Mn1 | 139.8 (3) |
| Symmetry codes: (i) y+3/4, x−3/4, −z+1/4; (ii) −x+3/2, y, −z; (iii) x, −y, −z+1/2. |
Experimental details
| Crystal data | |
| Chemical formula | [Mn(C12H8N5)(CHO2)] |
| Mr | 322.20 |
| Crystal system, space group | Tetragonal, I41/acd |
| Temperature (K) | 293 |
| a, c (Å) | 19.124 (5), 14.9120 (4) |
| V (Å3) | 5454 (2) |
| Z | 16 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.98 |
| Crystal size (mm) | 0.15 × 0.09 × 0.06 |
| Data collection | |
| Diffractometer | Bruker APEX CCD diffractometer |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
| Tmin, Tmax | 0.867, 0.944 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 14412, 1346, 1225 |
| Rint | 0.054 |
| (sin θ/λ)max (Å−1) | 0.617 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.121, 1.09 |
| No. of reflections | 1346 |
| No. of parameters | 97 |
| H-atom treatment | H-atom parameters constrained |
| w = 1/[σ2(Fo2) + (0.0491P)2 + 25.4234P] where P = (Fo2 + 2Fc2)/3 | |
| Δρmax, Δρmin (e Å−3) | 0.39, −0.37 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors thank the Program for Young Excellent Talents in Southeast University for financial support.
References
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Chen, X.-M. & Tong, M.-L. (2007). Acc. Chem. Res. 40, 162–170. Web of Science CrossRef PubMed CAS Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Recently, solvothermal in situ ligand reactions have been a rapidly growing field concerning with the formation of in situ generated mixed-ligand coordination polymers that can not be easily obtained: a. one-pot synthesis of some unusual organic ligands that are inaccessible or not easily obtainable via conventional methods, and b. which are very promising as a bridge between coordination and synthetic organic chemistry (Zhang, 2005; Chen & Tong, 2007). During our research of the reaction mechanisms of different organonitriles with hydrazine hydrate (Cheng et al., 2007a,b), a new one-dimensional mixed-ligand polymeric manganese(II) complex, [Mn(bpt)0.5(HCOO)0.5]n (Hbpt = 3,5-bis(2-pyridyl)-4H-1,2,4-triazole) has been synthesized and characterized by single-crystal X-ray diffraction.
The asymmetric unit of the title compound contains half a MnII cation, half a bpt and half a formato anion. In the compound, the MnII ion lies on a twofold rotation axis, at position (x, 1/4 + x, 1/8), Wyckoff letter f. Neighboring twofold rotation axes in the high symmetric space group I 41/a 2/c 2/d, running through atoms C7, H7A in the formato anion and through atom N3 of the triazole group, at positions (3/4, 3/4 + x, 0) and (x, 0, 1/4), respectively, both with Wyckoff letter e. The MnII ion displays a slightly distorted octahedral geometry, being surrounded by two chelating bpt ligands and two oxygen atoms from two µ2-formato ligands, linking the half molecules in the complex to a one-dimensional chain extending along the crystallographic 41-screw axis. The shortest Mn···Mn distance in the chain is 4.366 (5) Å.