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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039177/bt2467sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039177/bt2467Isup2.hkl
Contains datablock I

CCDC reference: 660089

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.037
  • wR factor = 0.091
  • Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for S1 - C13 .. 7.81 su
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.96 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.74 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Fe1 - N1 .. 6.08 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Fe1 - N5_a .. 6.15 su
Alert level G PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe1 (2) 2.05
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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.

Structure description 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.

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).

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-\k4N1,N5:N2,N3]bis[(methanol-\kO)(thiocyanato-κN)iron(II)] top
Crystal data top
[Fe2(C12H8N5)2(NCS)2(CH4O)2]F(000) = 752
Mr = 736.41Dx = 1.560 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3100 reflections
a = 11.5051 (8) Åθ = 2.3–27.0°
b = 14.291 (1) ŵ = 1.11 mm1
c = 9.7794 (7) ÅT = 295 K
β = 102.885 (1)°Block, 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)
Graphite monochromatorRint = 0.032
φ and ω scansθmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1413
Tmin = 0.698, Tmax = 0.826k = 1718
8319 measured reflectionsl = 912
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0535P)2P]
where P = (Fo2 + 2Fc2)/3
3302 reflections(Δ/σ)max = 0.001
213 parametersΔρmax = 0.75 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
[Fe2(C12H8N5)2(NCS)2(CH4O)2]V = 1567.4 (2) Å3
Mr = 736.41Z = 2
Monoclinic, P21/cMo Kα radiation
a = 11.5051 (8) ŵ = 1.11 mm1
b = 14.291 (1) ÅT = 295 K
c = 9.7794 (7) Å0.35 × 0.20 × 0.18 mm
β = 102.885 (1)°
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)] = 0.0370 restraints
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.75 e Å3
3302 reflectionsΔρmin = 0.27 e Å3
213 parameters
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, º) 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—C6179.54 (18)
N3i—Fe1—O1—C1490.68 (18)Fe1—N1—C5—C62.0 (2)
N2—Fe1—O1—C142.91 (18)C3—C4—C5—N11.0 (3)
N1—Fe1—O1—C1475.52 (17)C3—C4—C5—C6179.54 (19)
N5i—Fe1—O1—C14163.64 (18)N3—N2—C6—N40.3 (2)
N6—Fe1—N1—C182.18 (18)Fe1—N2—C6—N4172.72 (12)
N3i—Fe1—N1—C1156.0 (2)N3—N2—C6—C5179.34 (17)
N2—Fe1—N1—C1177.91 (19)Fe1—N2—C6—C56.3 (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—C525.7 (3)C4—C5—C6—N2177.98 (19)
N2—Fe1—N1—C53.79 (14)N1—C5—C6—N4176.37 (19)
O1—Fe1—N1—C596.12 (15)C4—C5—C6—N43.2 (3)
N5i—Fe1—N1—C5172.96 (13)N2—N3—C7—N40.5 (2)
N6—Fe1—N2—C681.62 (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—C86.4 (2)
N1—Fe1—N2—C65.39 (15)C6—N4—C7—N30.3 (2)
N5i—Fe1—N2—C6148.1 (2)C6—N4—C7—C8176.7 (2)
N6—Fe1—N2—N389.26 (18)C12—N5—C8—C90.4 (3)
N3i—Fe1—N2—N39.1 (2)Fe1i—N5—C8—C9175.95 (16)
O1—Fe1—N2—N399.28 (18)C12—N5—C8—C7178.85 (17)
N1—Fe1—N2—N3176.27 (19)Fe1i—N5—C8—C72.5 (2)
N5i—Fe1—N2—N341.0 (3)N3—C7—C8—N55.7 (3)
C6—N2—N3—C70.5 (2)N4—C7—C8—N5177.49 (19)
Fe1—N2—N3—C7171.37 (14)N3—C7—C8—C9172.74 (19)
C6—N2—N3—Fe1i175.62 (14)N4—C7—C8—C94.1 (3)
Fe1—N2—N3—Fe1i12.5 (3)N5—C8—C9—C101.3 (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—C30.9 (3)C9—C10—C11—C120.1 (3)
C1—C2—C3—C40.9 (3)C8—N5—C12—C112.0 (3)
C2—C3—C4—C50.0 (3)Fe1i—N5—C12—C11173.83 (16)
C1—N1—C5—C40.9 (3)C10—C11—C12—N51.8 (3)
Fe1—N1—C5—C4177.56 (16)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1o···N4ii0.82 (3)1.89 (3)2.698 (2)169 (3)
Symmetry code: (ii) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Fe2(C12H8N5)2(NCS)2(CH4O)2]
Mr736.41
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)11.5051 (8), 14.291 (1), 9.7794 (7)
β (°) 102.885 (1)
V3)1567.4 (2)
Z2
Radiation typeMo Kα
µ (mm1)1.11
Crystal size (mm)0.35 × 0.20 × 0.18
Data collection
DiffractometerBruker APEX area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.698, 0.826
No. of measured, independent and
observed [I > 2σ(I)] reflections
8319, 3302, 2827
Rint0.032
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.092, 1.02
No. of reflections3302
No. of parameters213
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.75, 0.27

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1o···N4i0.82 (3)1.89 (3)2.698 (2)169 (3)
Symmetry code: (i) x+1, y+1/2, z+1/2.
 

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