supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2319    [ doi:10.1107/S1600536807039177 ]

Bis([mu]-3,5-di-2-pyridyl-1,2,4-triazolato-[kappa]4N1,N5:N2,N3)bis[(methanol-[kappa]O)(thiocyanato-[kappa]N)iron(II)]

G.-B. Jiang, X.-N. Zeng, Y.-S. Fang, M.-H. Zeng and S. W. Ng

Abstract top

In the title centrosymmetric dinuclear iron(II) compound, [Fe2(C12H8N5)2(NCS)2(CH4O)2], the deprotonated 3,5-di-2-pyridyl-1,2,4-triazole ligand uses a pair of Npyridyl/Ntriazolyl atoms to chelate one metal atom and the other pair of Npyridyl/Ntriazolyl atoms to chelate the other metal atom. Each Fe atom is octahedrally coordinated by four N atoms surrounding the metal center in a square-planar environment. Above and below this plane are located the N atom of the thiocyanate anion and the O atom of the methanol molecule. Intermolecular O-H...N hydrogen bonding gives rise to a layer motif.

Comment top

The coordination chemistry of the class of 3,5-di-2-pyridyl-1,2,4-triazole N-heterocycles has been reviewed (Klingele & Brooker, 2003). The deprotonated 3,5-di-2-pyridyl-1,2,4-triazole monoanion is capable of using the pyridyl as well as the triazolyl nitrogen atoms to coordinate to more than one metal center, as noted in the trichloridodicopper(I)copper(II) (Chen, Zhou et al., 2006) and tetrachloridodiiron(III) and dichloridodiron(II) (Chen, Hu et al., 2006) complexes. Centrosymmetric dinuclear (C12H8N5)2(CH4O)2(NCS)2Fe2 has the deprotonated ligand using a pair of N'pyridyl/N1 atoms to chelate to one metal atom and its other pair of N"pyridyl/N2 atoms to chelate to the other metal atom, the four nitrogen atoms approximating a square. The six-coordinate environment has the nitrogen atom of the thiocyanate anion and the oxygen atom of the methanol molecule in the other two sites of the octahedron. Intermolecular hydrogen bonding between the hydroxy group and the 4-nitrogen atom of the ligand gives rise to a layer motif.

Related literature top

For a review of the coordination chemistry of 3,5-di-2-pyridyl-1,2,4-triazoles and related N-heterocycles, see Klingele & Brooker (2003). For the crystal structure of dinuclear derivatives of the deprotonated ligand, see Chen, Hu et al. (2006) and Chen, Zhou et al. (2006).

Experimental top

4-Amino-3,5-di-2-pyridyl-1,2,4-triazole was purchased from Aldrich Chemical Company. 3,5-di-2-pyridyl-1,2,4-triazole was synthesized by the deammoniation of the compound. Sulfuric acid (2M, 20 ml) was added to a mixture of the compound (11.9 g, 0.05 mol) and sodium nitrite (3.45 g, 0.05 mol) at 273 K. Hypophosphorus acid (0.05 mol) when added gave an immediate precipitate, which was then purified by recrystallization from ethanol (80% yield). 3,5-di-2-pyridyl-1,2,4-triazole, ferrous sulfate and potassium thiocyanate (0.1 mmol each) were suspended in methanol (8 ml). The suspension was heated in a 23-ml, Teflon-lined Parr bomb at 383 K for 96 h. The bomb was then cooled at 5 K h−1 to room temperature. Block-shaped crystals were picked by hand (40% yield).

Refinement top

Carbon-bound H atoms were placed at calculated positions (C–H 0.93 – 0.96 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 – 1.5 times Ueq(C). The hydroxy H atom was located in a difference Fourier map, and its positional and displacement parameters were refined.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of (C12H8N5)2(CH4O)2(NCS)2Fe2. Displacement ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radii.
Bis[µ-3,5-di-2-pyridyl-1,2,4-triazolato-\ κ4N1,N5:N2,N3]bis[(methanol-\ κO)(thiocyanato-κN)iron(II)] top
Crystal data top
[Fe2(C12H8N5)2(NCS)2(CH4O)2]F000 = 752
Mr = 736.41Dx = 1.560 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3100 reflections
a = 11.5051 (8) Åθ = 2.3–27.0º
b = 14.291 (1) ŵ = 1.11 mm−1
c = 9.7794 (7) ÅT = 295 (2) K
β = 102.885 (1)ºBlock, black
V = 1567.4 (2) Å30.35 × 0.20 × 0.18 mm
Z = 2
Data collection top
Bruker APEX area-detector
diffractometer		3302 independent reflections
Radiation source: fine-focus sealed tube2827 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.032
T = 293(2) Kθmax = 27.0º
φ and ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→13
Tmin = 0.698, Tmax = 0.826k = −17→18
8319 measured reflectionsl = −9→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.092  w = 1/[σ2(Fo2) + (0.0535P)2P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
3302 reflectionsΔρmax = 0.75 e Å−3
213 parametersΔρmin = −0.27 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Fe2(C12H8N5)2(NCS)2(CH4O)2]V = 1567.4 (2) Å3
Mr = 736.41Z = 2
Monoclinic, P21/cMo Kα
a = 11.5051 (8) ŵ = 1.11 mm−1
b = 14.291 (1) ÅT = 295 (2) K
c = 9.7794 (7) Å0.35 × 0.20 × 0.18 mm
β = 102.885 (1)º
Data collection top
Bruker APEX area-detector
diffractometer		3302 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2827 reflections with I > 2σ(I)
Tmin = 0.698, Tmax = 0.826Rint = 0.032
8319 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037213 parameters
wR(F2) = 0.092H atoms treated by a mixture of
independent and constrained refinement
S = 1.02Δρmax = 0.75 e Å−3
3302 reflectionsΔρmin = −0.27 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.64986 (2)0.524340 (19)0.41164 (3)0.01615 (11)
S10.95226 (5)0.42521 (5)0.81308 (6)0.02961 (16)
O10.54102 (13)0.57952 (11)0.21963 (16)0.0211 (3)
H1o0.541 (2)0.636 (2)0.207 (3)0.038 (8)*
N10.70485 (15)0.41319 (12)0.26974 (19)0.0207 (4)
N20.53238 (15)0.40957 (12)0.40463 (18)0.0178 (4)
N30.44253 (14)0.39173 (11)0.47076 (18)0.0175 (4)
N40.47467 (15)0.26108 (11)0.35794 (18)0.0178 (4)
N50.26895 (15)0.32792 (12)0.58072 (18)0.0199 (4)
N60.78557 (18)0.48169 (13)0.5746 (2)0.0271 (4)
C10.79195 (19)0.42006 (16)0.2001 (2)0.0253 (5)
H10.83480.47570.20640.030*
C20.82160 (19)0.34804 (17)0.1186 (2)0.0264 (5)
H20.88220.35590.07060.032*
C30.7597 (2)0.26473 (16)0.1102 (2)0.0251 (5)
H30.77860.21520.05730.030*
C40.66880 (18)0.25605 (14)0.1818 (2)0.0214 (5)
H40.62580.20060.17780.026*
C50.64317 (18)0.33118 (14)0.2593 (2)0.0192 (4)
C60.54899 (17)0.33112 (14)0.3386 (2)0.0165 (4)
C70.41065 (17)0.30331 (14)0.4418 (2)0.0166 (4)
C80.31801 (17)0.26428 (14)0.5074 (2)0.0185 (4)
C90.28571 (18)0.17074 (15)0.4987 (2)0.0224 (5)
H90.31990.12910.44590.027*
C100.20137 (19)0.14047 (17)0.5702 (2)0.0256 (5)
H100.17950.07770.56800.031*
C110.1505 (2)0.20409 (17)0.6443 (2)0.0274 (5)
H110.09370.18520.69280.033*
C120.18556 (18)0.29756 (16)0.6456 (2)0.0247 (5)
H120.14920.34070.69370.030*
C130.85569 (19)0.45901 (15)0.6734 (2)0.0221 (5)
C140.4317 (2)0.53995 (17)0.1449 (3)0.0333 (6)
H14A0.40080.57660.06260.050*
H14B0.37520.53950.20390.050*
H14C0.44530.47700.11790.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.01877 (17)0.01035 (18)0.01979 (18)−0.00042 (11)0.00532 (12)−0.00032 (11)
S10.0239 (3)0.0385 (4)0.0252 (3)0.0026 (3)0.0028 (2)0.0052 (3)
O10.0241 (8)0.0122 (8)0.0251 (8)−0.0013 (6)0.0019 (6)0.0026 (6)
N10.0213 (9)0.0175 (9)0.0244 (10)0.0008 (7)0.0076 (7)0.0012 (7)
N20.0215 (8)0.0118 (8)0.0216 (9)−0.0015 (7)0.0079 (7)−0.0002 (7)
N30.0201 (8)0.0118 (9)0.0222 (9)−0.0008 (7)0.0083 (7)0.0008 (7)
N40.0206 (9)0.0121 (9)0.0205 (9)−0.0013 (7)0.0043 (7)−0.0006 (7)
N50.0192 (8)0.0178 (10)0.0219 (9)−0.0016 (7)0.0027 (7)0.0001 (7)
N60.0282 (10)0.0216 (11)0.0289 (11)0.0028 (8)0.0009 (9)−0.0004 (8)
C10.0232 (11)0.0216 (12)0.0317 (13)−0.0004 (9)0.0076 (9)0.0037 (10)
C20.0232 (11)0.0310 (13)0.0270 (12)0.0045 (10)0.0101 (9)0.0016 (10)
C30.0310 (12)0.0225 (12)0.0220 (12)0.0077 (10)0.0065 (9)−0.0023 (9)
C40.0244 (11)0.0161 (11)0.0231 (11)0.0013 (9)0.0042 (9)−0.0005 (9)
C50.0204 (10)0.0160 (11)0.0206 (11)0.0015 (8)0.0032 (8)0.0017 (8)
C60.0189 (10)0.0122 (10)0.0178 (10)−0.0002 (8)0.0028 (8)0.0012 (8)
C70.0184 (9)0.0122 (10)0.0190 (10)−0.0010 (8)0.0037 (8)0.0000 (8)
C80.0193 (10)0.0173 (11)0.0179 (11)0.0000 (8)0.0019 (8)0.0024 (8)
C90.0245 (11)0.0181 (11)0.0242 (11)−0.0022 (9)0.0045 (9)−0.0012 (9)
C100.0255 (11)0.0229 (12)0.0269 (12)−0.0083 (9)0.0023 (9)0.0017 (10)
C110.0229 (11)0.0317 (14)0.0285 (12)−0.0087 (10)0.0078 (9)0.0033 (10)
C120.0225 (11)0.0279 (13)0.0247 (11)−0.0014 (10)0.0071 (9)−0.0013 (10)
C130.0248 (11)0.0165 (11)0.0274 (12)−0.0013 (9)0.0107 (10)−0.0024 (9)
C140.0347 (13)0.0219 (13)0.0362 (14)−0.0059 (11)−0.0071 (11)0.0029 (11)
Geometric parameters (Å, °) top
Fe1—O12.160 (2)C2—C31.380 (3)
Fe1—N12.289 (2)C2—H20.9300
Fe1—N22.117 (2)C3—C41.388 (3)
Fe1—N3i2.106 (2)C3—H30.9300
Fe1—N5i2.303 (2)C4—C51.383 (3)
Fe1—N62.059 (2)C4—H40.9300
S1—C131.630 (2)C5—C61.467 (3)
O1—C141.423 (3)C7—C81.471 (3)
O1—H1o0.82 (3)C8—C91.385 (3)
N1—C11.335 (3)C9—C101.386 (3)
N1—C51.362 (3)C9—H90.9300
N2—C61.329 (3)C10—C111.372 (3)
N2—N31.360 (2)C10—H100.9300
N4—C61.357 (2)C11—C121.394 (3)
N4—C71.359 (3)C11—H110.9300
N5—C121.335 (3)C12—H120.9300
N5—C81.356 (3)C14—H14A0.9600
N6—C131.158 (3)C14—H14B0.9600
C1—C21.390 (3)C14—H14C0.9600
C1—H10.9300
N6—Fe1—N3i97.69 (7)C2—C3—C4118.9 (2)
N6—Fe1—N299.45 (7)C2—C3—H3120.5
N3i—Fe1—N293.59 (6)C4—C3—H3120.5
N6—Fe1—O1166.75 (7)C5—C4—C3118.93 (19)
N3i—Fe1—O190.08 (6)C5—C4—H4120.5
N2—Fe1—O190.71 (6)C3—C4—H4120.5
N6—Fe1—N189.98 (7)N1—C5—C4122.55 (19)
N3i—Fe1—N1165.34 (6)N1—C5—C6113.25 (18)
N2—Fe1—N172.75 (6)C4—C5—C6124.20 (19)
O1—Fe1—N184.91 (6)N2—C6—N4113.04 (17)
N6—Fe1—N5i90.82 (7)N2—C6—C5117.38 (17)
N3i—Fe1—N5i73.18 (6)N4—C6—C5129.58 (18)
N2—Fe1—N5i164.32 (6)N3—C7—N4112.96 (17)
O1—Fe1—N5i81.13 (6)N3—C7—C8117.37 (18)
N1—Fe1—N5i119.40 (6)N4—C7—C8129.61 (18)
C14—O1—Fe1125.15 (14)N5—C8—C9122.85 (19)
C14—O1—H1o109.9 (18)N5—C8—C7113.81 (18)
Fe1—O1—H1o118.5 (19)C9—C8—C7123.32 (19)
C1—N1—C5117.57 (18)C8—C9—C10118.6 (2)
C1—N1—Fe1126.76 (15)C8—C9—H9120.7
C5—N1—Fe1115.65 (13)C10—C9—H9120.7
C6—N2—N3106.25 (16)C11—C10—C9119.2 (2)
C6—N2—Fe1120.63 (13)C11—C10—H10120.4
N3—N2—Fe1132.64 (13)C9—C10—H10120.4
C7—N3—N2106.24 (16)C10—C11—C12118.9 (2)
C7—N3—Fe1i120.61 (13)C10—C11—H11120.6
N2—N3—Fe1i133.04 (13)C12—C11—H11120.6
C6—N4—C7101.51 (16)N5—C12—C11123.0 (2)
C12—N5—C8117.44 (19)N5—C12—H12118.5
C12—N5—Fe1i127.71 (15)C11—C12—H12118.5
C8—N5—Fe1i114.73 (13)N6—C13—S1178.7 (2)
C13—N6—Fe1174.49 (19)O1—C14—H14A109.5
N1—C1—C2123.1 (2)O1—C14—H14B109.5
N1—C1—H1118.4H14A—C14—H14B109.5
C2—C1—H1118.4O1—C14—H14C109.5
C3—C2—C1118.9 (2)H14A—C14—H14C109.5
C3—C2—H2120.5H14B—C14—H14C109.5
C1—C2—H2120.5
N6—Fe1—O1—C14143.2 (3)C1—N1—C5—C6−179.54 (18)
N3i—Fe1—O1—C14−90.68 (18)Fe1—N1—C5—C62.0 (2)
N2—Fe1—O1—C142.91 (18)C3—C4—C5—N1−1.0 (3)
N1—Fe1—O1—C1475.52 (17)C3—C4—C5—C6179.54 (19)
N5i—Fe1—O1—C14−163.64 (18)N3—N2—C6—N4−0.3 (2)
N6—Fe1—N1—C1−82.18 (18)Fe1—N2—C6—N4172.72 (12)
N3i—Fe1—N1—C1156.0 (2)N3—N2—C6—C5−179.34 (17)
N2—Fe1—N1—C1177.91 (19)Fe1—N2—C6—C5−6.3 (2)
O1—Fe1—N1—C185.58 (18)C7—N4—C6—N20.0 (2)
N5i—Fe1—N1—C18.7 (2)C7—N4—C6—C5178.9 (2)
N6—Fe1—N1—C596.12 (15)N1—C5—C6—N22.5 (3)
N3i—Fe1—N1—C5−25.7 (3)C4—C5—C6—N2−177.98 (19)
N2—Fe1—N1—C5−3.79 (14)N1—C5—C6—N4−176.37 (19)
O1—Fe1—N1—C5−96.12 (15)C4—C5—C6—N43.2 (3)
N5i—Fe1—N1—C5−172.96 (13)N2—N3—C7—N4−0.5 (2)
N6—Fe1—N2—C6−81.62 (16)Fe1i—N3—C7—N4176.19 (13)
N3i—Fe1—N2—C6179.96 (16)N2—N3—C7—C8176.88 (16)
O1—Fe1—N2—C689.84 (16)Fe1i—N3—C7—C8−6.4 (2)
N1—Fe1—N2—C65.39 (15)C6—N4—C7—N30.3 (2)
N5i—Fe1—N2—C6148.1 (2)C6—N4—C7—C8−176.7 (2)
N6—Fe1—N2—N389.26 (18)C12—N5—C8—C9−0.4 (3)
N3i—Fe1—N2—N3−9.1 (2)Fe1i—N5—C8—C9175.95 (16)
O1—Fe1—N2—N3−99.28 (18)C12—N5—C8—C7−178.85 (17)
N1—Fe1—N2—N3176.27 (19)Fe1i—N5—C8—C7−2.5 (2)
N5i—Fe1—N2—N3−41.0 (3)N3—C7—C8—N55.7 (3)
C6—N2—N3—C70.5 (2)N4—C7—C8—N5−177.49 (19)
Fe1—N2—N3—C7−171.37 (14)N3—C7—C8—C9−172.74 (19)
C6—N2—N3—Fe1i−175.62 (14)N4—C7—C8—C94.1 (3)
Fe1—N2—N3—Fe1i12.5 (3)N5—C8—C9—C10−1.3 (3)
C5—N1—C1—C20.1 (3)C7—C8—C9—C10176.91 (19)
Fe1—N1—C1—C2178.33 (16)C8—C9—C10—C111.6 (3)
N1—C1—C2—C3−0.9 (3)C9—C10—C11—C12−0.1 (3)
C1—C2—C3—C40.9 (3)C8—N5—C12—C112.0 (3)
C2—C3—C4—C50.0 (3)Fe1i—N5—C12—C11−173.83 (16)
C1—N1—C5—C40.9 (3)C10—C11—C12—N5−1.8 (3)
Fe1—N1—C5—C4−177.56 (16)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1o···N4ii0.82 (3)1.89 (3)2.698 (2)169 (3)
Symmetry codes: (ii) −x+1, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1o···N4i0.82 (3)1.89 (3)2.698 (2)169 (3)
Symmetry codes: (i) −x+1, y+1/2, −z+1/2.
Acknowledgements top

This work was supported by the Natural Science Foundation of Guangxi, Guangxi Normal University and the University of Malaya.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2002). SMART (Version 6.36A) and SAINT (Version 6.36A). Bruker AXS Inc., Madison, Wisconsin, USA.

Chen, J.-C., Hu, S.-H., Zhou, A.-J., Tong, M.-L. & Tong, Y.-X. (2006). Z. Anorg. Allg. Chem. 632, 475–481.

Chen, J.-C., Zhou, A.-J., Hu, S. H., Tong, M.-L. & Tong, Y.-X. (2006). J. Mol. Struct. 794, 225–229.

Klingele, M. H. & Brooker, S. (2003). Coord. Chem. Rev. 241, 119–132.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Westrip, S. P. (2007). publCIF. In preparation.