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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1073.
Published online 2008 July 26. doi:  10.1107/S160053680802299X
PMCID: PMC2961983

catena-Poly[manganese(II)-(μ2-3,5-di-2-pyridyl-1,2,4-triazol­ato)-μ2-formato]

Abstract

Owing to the presence of crystallographic twofold rotation axes (site symmetry 2, Wyckoff letters e and f), the asymmetric unit 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 C 2 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 [triangle]); Chen & Tong (2007 [triangle]). For related structures, see: Cheng et al. (2007a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1073-scheme1.jpg

Experimental

Crystal data

  • [Mn(C12H8N5)(CHO2)]
  • M r = 322.20
  • Tetragonal, An external file that holds a picture, illustration, etc.
Object name is e-64-m1073-efi10.jpg
  • a = 19.124 (5) Å
  • c = 14.9120 (4) Å
  • V = 5454 (2) Å3
  • Z = 16
  • Mo Kα radiation
  • μ = 0.98 mm−1
  • T = 293 (2) K
  • 0.15 × 0.09 × 0.06 mm

Data collection

  • Bruker APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2000 [triangle]) T min = 0.867, T max = 0.944
  • 14412 measured reflections
  • 1346 independent reflections
  • 1225 reflections with I > 2σ(I)
  • R int = 0.054

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.121
  • S = 1.09
  • 1346 reflections
  • 97 parameters
  • H-atom parameters constrained
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680802299X/si2099sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680802299X/si2099Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

supplementary crystallographic information

Comment

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.

Experimental

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].

Refinement

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).

Figures

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.

Crystal data

[Mn(C12H8N5)(CHO2)]Z = 16
Mr = 322.20F000 = 2608
Tetragonal, I41/acdDx = 1.570 Mg m3
Hall symbol: -I 4bd 2cMo Kα radiation λ = 0.71073 Å
a = 19.124 (5) ÅCell parameters from 810 reflections
b = 19.124 (5) Åθ = 2.5–28.0º
c = 14.9120 (4) ŵ = 0.98 mm1
α = 90ºT = 293 (2) K
β = 90ºNeedle-like, yellow
γ = 90º0.15 × 0.09 × 0.06 mm
V = 5454 (2) Å3

Data collection

Bruker APEX CCD diffractometer1346 independent reflections
Radiation source: fine-focus sealed tube1225 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.054
T = 293(2) Kθmax = 26.0º
[var phi] and ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 2000)h = −23→18
Tmin = 0.867, Tmax = 0.944k = −23→23
14412 measured reflectionsl = −18→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.121  w = 1/[σ2(Fo2) + (0.0491P)2 + 25.4234P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
1346 reflectionsΔρmax = 0.39 e Å3
97 parametersΔρmin = −0.37 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Mn10.69057 (3)−0.05943 (3)0.12500.0215 (2)
C10.56957 (19)−0.11100 (19)−0.0239 (2)0.0318 (8)
H1A0.6082−0.1244−0.05760.038*
C20.5042 (2)−0.1237 (2)−0.0580 (2)0.0402 (10)
H2A0.4989−0.1454−0.11340.048*
C30.4464 (2)−0.1038 (2)−0.0088 (3)0.0431 (10)
H3A0.4015−0.1118−0.03050.052*
C40.45662 (19)−0.0717 (2)0.0735 (2)0.0358 (9)
H4A0.4187−0.05790.10820.043*
C50.52424 (17)−0.06066 (18)0.1029 (2)0.0259 (7)
C60.54152 (16)−0.02572 (17)0.1886 (2)0.0214 (7)
C70.75000.0594 (3)0.00000.0300 (11)
H7A0.75000.10800.00000.036*
N10.58042 (15)−0.08037 (14)0.05536 (18)0.0250 (6)
N20.60816 (13)−0.01663 (13)0.20974 (16)0.0196 (6)
N30.4964 (2)0.00000.25000.0272 (9)
O10.70537 (14)0.03180 (15)0.0481 (2)0.0501 (8)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mn10.0221 (3)0.0221 (3)0.0203 (4)0.0017 (3)0.00432 (19)−0.00432 (19)
C10.0325 (19)0.041 (2)0.0219 (17)0.0094 (16)−0.0010 (15)−0.0133 (15)
C20.041 (2)0.051 (2)0.0280 (18)0.0110 (19)−0.0106 (17)−0.0199 (18)
C30.033 (2)0.060 (3)0.037 (2)0.0061 (18)−0.0149 (17)−0.019 (2)
C40.0266 (19)0.048 (2)0.0325 (19)0.0032 (16)−0.0025 (16)−0.0150 (17)
C50.0272 (18)0.0303 (18)0.0202 (16)0.0008 (14)−0.0028 (13)−0.0057 (14)
C60.0210 (16)0.0264 (17)0.0167 (14)0.0000 (13)−0.0021 (12)−0.0049 (13)
C70.032 (3)0.023 (2)0.035 (3)0.0000.001 (2)0.000
N10.0279 (15)0.0275 (15)0.0197 (14)0.0018 (12)−0.0009 (11)−0.0086 (11)
N20.0225 (14)0.0210 (14)0.0154 (12)−0.0015 (10)−0.0012 (11)−0.0058 (10)
N30.0205 (19)0.039 (2)0.0217 (18)0.0000.000−0.0090 (17)
O10.0370 (16)0.0438 (16)0.069 (2)0.0047 (13)0.0165 (15)0.0253 (15)

Geometric parameters (Å, °)

Mn1—O12.107 (3)C3—H3A0.9300
Mn1—O1i2.107 (3)C4—C51.382 (5)
Mn1—N2i2.180 (3)C4—H4A0.9300
Mn1—N22.180 (3)C5—N11.341 (4)
Mn1—N12.382 (3)C5—C61.480 (4)
Mn1—N1i2.382 (3)C6—N21.324 (4)
C1—N11.335 (4)C6—N31.350 (4)
C1—C21.372 (5)C7—O11.234 (3)
C1—H1A0.9300C7—O1ii1.234 (3)
C2—C31.379 (5)C7—H7A0.9300
C2—H2A0.9300N2—N2iii1.359 (5)
C3—C41.386 (5)N3—C6iii1.350 (4)
O1—Mn1—O1i94.23 (17)C2—C3—H3A120.6
O1—Mn1—N2i103.46 (11)C4—C3—H3A120.6
O1i—Mn1—N2i95.84 (10)C5—C4—C3118.7 (3)
O1—Mn1—N295.84 (10)C5—C4—H4A120.6
O1i—Mn1—N2103.46 (11)C3—C4—H4A120.6
N2i—Mn1—N2151.55 (13)N1—C5—C4122.6 (3)
O1—Mn1—N191.19 (11)N1—C5—C6113.9 (3)
O1i—Mn1—N1172.74 (12)C4—C5—C6123.5 (3)
N2i—Mn1—N187.58 (9)N2—C6—N3114.0 (3)
N2—Mn1—N171.13 (9)N2—C6—C5118.6 (3)
O1—Mn1—N1i172.74 (12)N3—C6—C5127.4 (3)
O1i—Mn1—N1i91.19 (11)O1—C7—O1ii129.3 (5)
N2i—Mn1—N1i71.13 (9)O1—C7—H7A115.3
N2—Mn1—N1i87.58 (9)O1ii—C7—H7A115.3
N1—Mn1—N1i83.84 (14)C1—N1—C5117.8 (3)
N1—C1—C2123.2 (3)C1—N1—Mn1126.6 (2)
N1—C1—H1A118.4C5—N1—Mn1115.5 (2)
C2—C1—H1A118.4C6—N2—N2iii105.75 (17)
C1—C2—C3119.0 (3)C6—N2—Mn1120.59 (19)
C1—C2—H2A120.5N2iii—N2—Mn1133.48 (7)
C3—C2—H2A120.5C6—N3—C6iii100.6 (4)
C2—C3—C4118.7 (4)C7—O1—Mn1139.8 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2099).

References

  • Bruker (2000). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, X.-M. & Tong, M.-L. (2007). Acc. Chem. Res.40, 162–170. [PubMed]
  • Cheng, L., Zhang, W.-X., Ye, B.-H., Lin, J.-B. & Chen, X.-M. (2007a). Inorg. Chem.46, 1135–1143. [PubMed]
  • Cheng, L., Zhang, W.-X., Ye, B.-H., Lin, J.-B. & Chen, X.-M. (2007b). Eur. J. Inorg. Chem. pp. 2668–2676.
  • Sheldrick, G. M. (2000). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhang, X.-M. (2005). Coord. Chem. Rev.249, 1201–1219.

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