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In the title compound, [FeII(NCS)2(CH6N4S)2], the FeII cation is surrounded by two S atoms and two N atoms from thio­carbohydrazide groups and by two N atoms from thio­cyanate groups. The geometry around the FeII cation, which is located on a center of inversion, is distorted octa­hedral. The thio­carbohydrazide mol­ecule assumes a cistrans conformation, which is reinforced by an N—H...N hydrogen bond. Mol­ecules of the title compound are connected via inter­molecular N—H...S and N—H...N hydrogen bonds to form a three-dimensional network structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105009881/av1233sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105009881/av1233Isup2.hkl
Contains datablock I

CCDC reference: 275510

Comment top

Previously, bis[4-amino-3-methyl-1H-1,2,4-triazole-5(4H) -thione]dichlorocopper(II) dihydrate has been synthesized in our laboratory (Cai et al., 2004). In a similar tentative synthetic procedure, FeCl3 was used instead of CuCl2 to prepare iron compounds of the ligand. Unexpectedly, the title compound, (I), was synthesized, where the thiocarbohydrazide (TCH) ligand and thiocyanate anion maybe result from reaction of 4-amino-1,2,4-triazole-5-thione (ATT). From the search of the Cambridge Structural Database (CSD), it is known that only five crystal structures of TCH compounds (Braibanti et al., 1969, 1971, 1972; Bigoli et al., 1971, 1972) have been reported so far. In this paper, we make a careful study of the structure of (I) (Table 1).

In (I) (Fig. 1 and Table 1), owing to the obvious differences of bond lengths and bond angles around the FeII ion, which is located at an inversion center, the coordination is distorted octahedral. The equatorial plane consists of two amine N atoms and two S atoms from two TCH ligands, and the axial positions are filled by two N atoms from thiocyanate anions. The bond lengthd in the thiocyanate anion agrees with the data reported previously (Petrucenko et al., 1997; Wharf & Simard, 1998). The FeII ion is located in the C1/N1/N2/S1 plane, which has an a r.m.s. deviation of 0.057 (2) Å [or is this the deviation of Fe from the plane?]. The structure is similar to that of the bis(TCH)–dichloro–cadmium compound, except for the fact that in the latter the Cd atom lies out of the equivalent plane (Bigoli et al., 1971).

TCH molecules may assume cis--trans or ciscis conformations (see scheme below). In the title compound, TCH assumes a cistrans conformation, which has also been found in neutral TCH (Braibanti et al., 1969), bis(TCH)–dichloro–cadmium (Bigoli et al., 1971) and TCH hemihydrochloride (Braibanti et al., 1972). Conversely, the cis--cis conformation has been observed in TCH dihydrochloride dihydrate (Braibanti et al., 1971) and TCH sulfate (Bigoli et al., 1972). Interestingly, the cistrans comformation is reinforced by an N1—H1···N4 hydrogen bond [2.590 (3) Å; Fig. 1 and Table 2).

There are six kinds of intramolecular N—H···S hydrogen bonds with H···S distances shorter than 2.9 Å, the sum of the van der Waals radii of H and S atoms (Allen et al., 1997). As shown in Fig. 2, (I) is connected by N4—H4B···S1iii and N4—H4A···S2iv hydrogen bonds to form one-dimensional chains along the [001] direction (Fig. 2 and Table 2). Neighboring chains are associated with one another by an N1—H1···S2i hydrogen bond and are interrelated by translation to result in a supramolecular layer parallel to (100). There are various hydrogen-bonded rings embedded in the layer (Fig. 2), which can be described in graph-set notation (Etter, 1990; Grell et al., 2000) as R11(5), R22(8), R22(10), R22(14) and R44(8). The layers are associated to form the whole structure by N2—H2A···S2ii, N2—H2B···S1ii and N3—H3···S1v hydrogen bonds.

Experimental top

The title compound was synthesized by a hydrothermal method from a mixture of ATT (4 mmol, 0.76 g), FeCl3 (1 mmol, 0.16 g) and water (20 ml) in a 30 ml Tefon-lined stainless steel reactor. The solution was heated to 415 K for three days. After the reaction system was slowly cooled to room temperature, pale-blue block-shaped crystals were collected and washed with distilled water.

Refinement top

All H atoms were located in a difference Fourier map and were refined with fixed positions and Uiso(H) set to 0.08.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The formula unit of (I), with atom labels, showing 40% probability displacement ellipsoids. Hydrogen bonds are illustrated as dashed lines.
[Figure 2] Fig. 2. Part of the crystal structure, showing a supramolecular layer of N—H···S hydrogen bonds, which is built up from hydrogen-bonded N—H···S chains. Hydrogen bonds are shown as dashed lines. Atoms labeled with a hash (#), an asterisk (*) or two asterisks (**) are at the symmetry positions (x, y, z − 1), (−x, −y + 1, −z − 1) and (−x, −y, −z), respectively.
Bis(thiocarbohydrazide)thiocyanatoiron(II) top
Crystal data top
[Fe(NCS)2(CH6N4S)2]Z = 1
Mr = 384.37F(000) = 196.0
Triclinic, P1Dx = 1.786 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.2176 (6) ÅCell parameters from 856 reflections
b = 8.0061 (9) Åθ = 2.6–24.3°
c = 8.7683 (10) ŵ = 1.64 mm1
α = 78.662 (2)°T = 273 K
β = 84.150 (2)°Block, pale blue
γ = 88.891 (2)°0.37 × 0.16 × 0.12 mm
V = 357.26 (7) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
1299 independent reflections
Radiation source: fine-focus sealed tube1240 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.009
ϕ and ω scansθmax = 25.3°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 65
Tmin = 0.729, Tmax = 0.824k = 99
1926 measured reflectionsl = 109
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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0396P)2 + 0.3522P]
where P = (Fo2 + 2Fc2)/3
1276 reflections(Δ/σ)max < 0.001
88 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
[Fe(NCS)2(CH6N4S)2]γ = 88.891 (2)°
Mr = 384.37V = 357.26 (7) Å3
Triclinic, P1Z = 1
a = 5.2176 (6) ÅMo Kα radiation
b = 8.0061 (9) ŵ = 1.64 mm1
c = 8.7683 (10) ÅT = 273 K
α = 78.662 (2)°0.37 × 0.16 × 0.12 mm
β = 84.150 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
1299 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1240 reflections with I > 2σ(I)
Tmin = 0.729, Tmax = 0.824Rint = 0.009
1926 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.080H-atom parameters constrained
S = 1.07Δρmax = 0.29 e Å3
1276 reflectionsΔρmin = 0.48 e Å3
88 parameters
Special details top

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) top
xyzUiso*/Ueq
Fe0.00000.50000.00000.02507 (17)
S10.27457 (11)0.51899 (8)0.26337 (7)0.02761 (18)
S20.53874 (14)0.02470 (9)0.22669 (9)0.0404 (2)
N10.0853 (4)0.2790 (3)0.2442 (2)0.0284 (5)
N20.1998 (4)0.3175 (3)0.1019 (2)0.0270 (4)
N50.2314 (4)0.2958 (3)0.1009 (2)0.0333 (5)
N40.0759 (5)0.1786 (3)0.5005 (3)0.0354 (5)
N30.2054 (4)0.3123 (3)0.4562 (2)0.0305 (5)
C10.1197 (4)0.3603 (3)0.3228 (3)0.0224 (5)
C20.3557 (5)0.1816 (3)0.1526 (3)0.0287 (5)
H10.16810.19890.28310.080*
H2A0.21550.21540.02450.080*
H2B0.36690.35300.11900.080*
H4B0.01790.22640.59490.080*
H30.33900.36860.51690.080*
H4A0.20100.10550.51530.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe0.0247 (3)0.0286 (3)0.0232 (3)0.00152 (19)0.00230 (19)0.0085 (2)
S10.0252 (3)0.0315 (3)0.0274 (3)0.0061 (2)0.0007 (2)0.0100 (2)
S20.0388 (4)0.0338 (4)0.0457 (4)0.0068 (3)0.0077 (3)0.0004 (3)
N10.0289 (11)0.0327 (11)0.0260 (11)0.0078 (9)0.0047 (8)0.0145 (9)
N20.0250 (11)0.0339 (11)0.0230 (10)0.0013 (8)0.0029 (8)0.0101 (8)
N50.0328 (12)0.0365 (12)0.0289 (11)0.0079 (10)0.0030 (9)0.0033 (9)
N40.0486 (14)0.0321 (11)0.0279 (11)0.0022 (10)0.0013 (9)0.0129 (9)
N30.0344 (12)0.0321 (11)0.0255 (11)0.0036 (9)0.0047 (9)0.0104 (9)
C10.0215 (11)0.0231 (11)0.0225 (11)0.0033 (9)0.0025 (9)0.0042 (9)
C20.0265 (13)0.0338 (13)0.0253 (12)0.0042 (11)0.0029 (10)0.0070 (10)
Geometric parameters (Å, º) top
Fe—N5i2.118 (2)N1—H10.917
Fe—N52.118 (2)N2—H2A0.953
Fe—N2i2.187 (2)N2—H2B0.929
Fe—N22.187 (2)N5—C21.156 (3)
Fe—S12.5699 (6)N4—N31.414 (3)
Fe—S1i2.5699 (6)N4—H4B0.919
S1—C11.710 (2)N4—H4A0.885
S2—C21.634 (3)N3—C11.333 (3)
N1—C11.320 (3)N3—H30.903
N1—N21.414 (3)
N5i—Fe—N5180.00 (11)N2—N1—H1116.2
N5i—Fe—N2i87.93 (8)N1—N2—Fe117.36 (14)
N5—Fe—N2i92.07 (8)N1—N2—H2A109.12
N5i—Fe—N292.07 (8)Fe—N2—H2A106.08
N5—Fe—N287.93 (8)N1—N2—H2B106.40
N2i—Fe—N2180.00 (9)Fe—N2—H2B111.20
N5i—Fe—S190.09 (6)H2A—N2—H2B106.2
N5—Fe—S189.91 (6)C2—N5—Fe177.9 (2)
N2i—Fe—S1100.82 (5)N3—N4—H4B104.8
N2—Fe—S179.18 (5)N3—N4—H4A103.2
N5i—Fe—S1i89.91 (6)H4B—N4—H4A109.5
N5—Fe—S1i90.09 (6)C1—N3—N4118.4 (2)
N2i—Fe—S1i79.18 (5)C1—N3—H3119.3
N2—Fe—S1i100.82 (5)N4—N3—H3122.2
S1—Fe—S1i180.00 (3)N1—C1—N3116.2 (2)
C1—S1—Fe96.41 (8)N1—C1—S1123.98 (18)
C1—N1—N2122.55 (19)N3—C1—S1119.85 (18)
C1—N1—H1121.1N5—C2—S2178.0 (2)
N5i—Fe—S1—C197.09 (10)N2i—Fe—N5—C2159 (6)
N5—Fe—S1—C182.91 (10)N2—Fe—N5—C221 (6)
N2i—Fe—S1—C1175.00 (9)S1—Fe—N5—C258 (6)
N2—Fe—S1—C15.00 (9)S1i—Fe—N5—C2122 (6)
S1i—Fe—S1—C1175 (100)N2—N1—C1—N3179.2 (2)
C1—N1—N2—Fe6.6 (3)N2—N1—C1—S10.7 (3)
N5i—Fe—N2—N196.30 (17)N4—N3—C1—N11.2 (3)
N5—Fe—N2—N183.70 (17)N4—N3—C1—S1178.82 (17)
N2i—Fe—N2—N1125 (100)Fe—S1—C1—N14.1 (2)
S1—Fe—N2—N16.60 (15)Fe—S1—C1—N3175.93 (18)
S1i—Fe—N2—N1173.40 (15)Fe—N5—C2—S2142 (5)
N5i—Fe—N5—C20 (100)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N40.922.212.590 (3)104
N1—H1···S2ii0.922.603.397 (2)145
N2—H2A···S2iii0.952.653.510 (2)151
N2—H2B···S1iii0.932.573.443 (2)157
N4—H4B···S1iv0.922.703.482 (2)143
N4—H4A···S2v0.892.893.597 (2)138
N3—H3···S1vi0.902.683.565 (2)167
Symmetry codes: (ii) x, y, z; (iii) x1, y, z; (iv) x, y+1, z1; (v) x, y, z1; (vi) x+1, y+1, z1.

Experimental details

Crystal data
Chemical formula[Fe(NCS)2(CH6N4S)2]
Mr384.37
Crystal system, space groupTriclinic, P1
Temperature (K)273
a, b, c (Å)5.2176 (6), 8.0061 (9), 8.7683 (10)
α, β, γ (°)78.662 (2), 84.150 (2), 88.891 (2)
V3)357.26 (7)
Z1
Radiation typeMo Kα
µ (mm1)1.64
Crystal size (mm)0.37 × 0.16 × 0.12
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.729, 0.824
No. of measured, independent and
observed [I > 2σ(I)] reflections
1926, 1299, 1240
Rint0.009
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.080, 1.07
No. of reflections1276
No. of parameters88
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.48

Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXL97 (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
Fe—N52.118 (2)N1—C11.320 (3)
Fe—N22.187 (2)N1—N21.414 (3)
Fe—S12.5699 (6)N5—C21.156 (3)
S1—C11.710 (2)N4—N31.414 (3)
S2—C21.634 (3)N3—C11.333 (3)
N5—Fe—N287.93 (8)N2—Fe—S179.18 (5)
N5—Fe—S189.91 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N40.922.212.590 (3)104
N1—H1···S2i0.922.603.397 (2)145
N2—H2A···S2ii0.952.653.510 (2)151
N2—H2B···S1ii0.932.573.443 (2)157
N4—H4B···S1iii0.922.703.482 (2)143
N4—H4A···S2iv0.892.893.597 (2)138
N3—H3···S1v0.902.683.565 (2)167
Symmetry codes: (i) x, y, z; (ii) x1, y, z; (iii) x, y+1, z1; (iv) x, y, z1; (v) x+1, y+1, z1.
 

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