Download citation
Download citation
link to html
One half of the mol­ecule of the title complex, [Mn(C14H13N4S)2], is related to the other half by a twofold axis passing through the Mn atom. This high-spin Mn atom is six-coordinated, in an octahedral geometry, by the azomethine N, the pyridyl N and the thiol­ate S atom of two planar 1-­(pyridin-2-yl)­ethanone N(4)-phenyl­thio­semicarbazone lig­ands. In the crystal, the mol­ecules are interconnected by N-­H...S and C-H...N interactions, forming a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102011976/sk1569sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102011976/sk1569Isup2.hkl
Contains datablock I

CCDC reference: 195600

Comment top

The formation of complexes with transition metal ions have been proposed as a step in the biological activity of certain thiosemicarbazones (West et al., 1993). Metal complexes of thiosemicarbazones assume interesting structural geometries which may be crucial in deciding their biological activities. Recently, we have reported some biologically active heterocyclic base adducts of CuII (Bindu et al., 1999), NiII (Bindu & Kurup, 1997) and FeIII (Bindu & Kurup, 1999) complexes of salicylaldehyde thiosemicarbazones. 2-Acetylpyridine thiosemicarbazones are the first thiosemicarbazones in which antimalarial activity was detected. The highest activity is reported when the N4 position is either disubstituted or part of a ring system (Klayman et al., 1979). Transition metal complexes of these thiosemicarbazones have also been screened for their medicinal properties (Scovill et al., 1982) and were found to be more active than the ligands. Manganese complexes are of considerable interest because they can mimic the active sites of manganese containing enzymes (Limburg et al., 1999). Spectral studies of MnII complexes of N(4)-substituted 2-acetylpyridine thiosemicarbazone has been reported (Garg et al., 1988), but their crystal structures have not been established so far. We have synthesized and crystallized MnII complexes of 2-acetylpyridine thiosemicarbazone in order to study systematically the relation between the structural and biological activities. An X-ray crystal structure analysis of the title compound, bis(1-pyridin-2-ylethanone 4-phenylthiosemicarbazonato)manganese(II), (I), was undertaken, and the results are reported here.

The title complex is an MnII complex of 2-acetylpyridine N(4)-phenylthiosemicarbazone and the ligands coordinate as NNS-donors through the azomethine N, the pyridyl N and the thiolate S atom.

The bond lengths and angles (Table 1) of the title complex (Fig. 1) are normal (Allen et al., 1987). The asymmetric unit contains one half of the molecule, and the another half is generated by a twofold axis passing through atom Mn1, which is coordinated octahedrally by NNS donors of the two deprotonated ligands. This structure is identical to the closely related FeIII (West et al., 1985) and CoIII (West et al., 1986) complexes, where the two coordinating azomethine N atoms are trans to each other and the other two sets of identical donor atoms are cis to each other.

The apical positions of the octahedron are occupied by the azomethine N2 atoms, with N2—Mn1—N2A being 170.4 (1)°. Average angles of the apical N2 atom to the basal plane [N1/N1i/S1/S1i; symmetry code: (i) -x, y, -z + 3/2] subtended at Mn1 is 89.9°, while the angles N1—Mn1—S1 and N1—Mn1—S1i are 147.8 (1) and 91.4 (1)°, respectively.

As a resuylt of the coordination, the thiosemicarbazone C8—S1 bond distance increases from 1.699 Å (Ferrari et al., 1992) to 1.740 (3) Å in (I), and the C8—N3 bond distance decreases from 1.358 Å (Ferrari et al., 1992) to 1.315 (3) Å. These bond distances are consistent with the C8—S1 having partial single-bond and C8—N3 partial double-bond character. The comparatively longer bond lengths of Mn1—N1, Mn1—N2 and Mn1—S1 indicate weak coordination to the MnII atom.

The whole molecule of the ligand is nearly planar excepting the phenyl C9—C14 ring which is twisted by an angle of 6.9 (1)° from the pyridyl ring. The planarity is mainly due to the double bond character of the C6—N2 and C8—N3 of the thiosemicarbazone joining the phenyl and pyridyl rings. The phenyl ring is intermolecularly hydrogen bonded to the thiosemicarbazone via C14—H14···N3 forming a six-membered ring of N3—C8—N4—C9—C14—H14 (Fig. 1).

In the crystal, the molecules are linked by intermolecular N4—H4A···S1, C7—H7C···N3 and C11—H11···N3 interactions (Table 2) into a three-dimensional network (Fig. 2).

Experimental top

The 2-acetylpyridine N(4)-phenylthiosemicarbazone ligand was prepared according to the procedure of Klayman et al. (1979). A hot ethanol solution of MnCl2·4H2O (0.198 g, 1 mmol) was added to a hot ethanol solution of 2-acetylpyridine N(4)-phenylthiosemicarbazone (2 mmol). The mixture was warmed gently for 1 h with stirring. The separated light-yellow compound was collected, washed with ethanol and ether, and finally dried over P4O10 in vacuo. Brown single crystals suitable for X-ray analysis were obtained from dimethylformamide solution after three weeks.

Refinement top

H atoms were fixed geometrically and treated as riding atoms on their parent C atoms, with C—H distances in the range 0.93–0.96 Å and Uiso(H) = 1.2 Ueq(C), except for atom H4A, which was located from a difference map and was refined isotropically.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. The structure of the title complex, showing 50% probability displacement ellipsoids and the atom-numbering scheme. The dashed lines denote the intramolecular hydrogen bonds. [Symmetry code: (i) -x, y, -z + 3/2.]
[Figure 2] Fig. 2. The packing structure of the title complex, viewed down the a axis, showing the three-dimensional network. The dashed lines denote the intermolecular hydrogen bonds.
Bis(1-pyridin-2-ylethanone-κN 4-phenylthiosemicarbazonato-κ2N4,S)manganese(II) top
Crystal data top
[Mn(C14H13N4S)2]F(000) = 1228
Mr = 593.63Dx = 1.416 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5869 reflections
a = 13.5897 (1) Åθ = 2.5–28.3°
b = 18.7968 (1) ŵ = 0.66 mm1
c = 10.9688 (1) ÅT = 183 K
β = 96.427 (1)°Block, brown
V = 2784.29 (4) Å30.24 × 0.20 × 0.16 mm
Z = 4
Data collection top
Siemens SMART CCD area-detector
diffractometer
3381 independent reflections
Radiation source: fine-focus sealed tube2456 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.090
Detector resolution: 8.33 pixels mm-1θmax = 28.3°, θmin = 2.5°
ω scansh = 1017
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 2424
Tmin = 0.858, Tmax = 0.902l = 1414
8419 measured reflections
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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145H atoms treated by a mixture of independent and constrained refinement
S = 0.98 w = 1/[σ2(Fo2) + (0.0641P)2]
where P = (Fo2 + 2Fc2)/3
3381 reflections(Δ/σ)max < 0.001
182 parametersΔρmax = 0.75 e Å3
0 restraintsΔρmin = 1.34 e Å3
Crystal data top
[Mn(C14H13N4S)2]V = 2784.29 (4) Å3
Mr = 593.63Z = 4
Monoclinic, C2/cMo Kα radiation
a = 13.5897 (1) ŵ = 0.66 mm1
b = 18.7968 (1) ÅT = 183 K
c = 10.9688 (1) Å0.24 × 0.20 × 0.16 mm
β = 96.427 (1)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
3381 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
2456 reflections with I > 2σ(I)
Tmin = 0.858, Tmax = 0.902Rint = 0.090
8419 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.145H atoms treated by a mixture of independent and constrained refinement
S = 0.98Δρmax = 0.75 e Å3
3381 reflectionsΔρmin = 1.34 e Å3
182 parameters
Special details top

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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
Mn10.00000.18600 (3)0.75000.01431 (17)
N10.09372 (16)0.26856 (11)0.8594 (2)0.0169 (5)
N20.14513 (16)0.19602 (11)0.6694 (2)0.0136 (4)
N30.17098 (16)0.15613 (11)0.57195 (19)0.0150 (5)
C10.0645 (2)0.30444 (15)0.9536 (3)0.0232 (6)
H10.00120.29630.97520.028*
C20.1242 (2)0.35322 (16)1.0207 (3)0.0270 (7)
H20.10080.37811.08480.032*
C30.2191 (2)0.36450 (16)0.9912 (3)0.0274 (7)
H30.26050.39731.03480.033*
C40.2518 (2)0.32612 (15)0.8956 (3)0.0219 (6)
H40.31600.33200.87560.026*
C50.18743 (19)0.27872 (13)0.8299 (2)0.0147 (5)
C60.21475 (19)0.23553 (13)0.7240 (2)0.0145 (5)
C70.3175 (2)0.23835 (16)0.6859 (3)0.0240 (6)
H7A0.33760.19140.66480.036*
H7B0.36250.25640.75240.036*
H7C0.31800.26910.61610.036*
S10.01753 (5)0.10103 (4)0.57191 (7)0.02047 (19)
C80.09992 (19)0.11305 (13)0.5263 (2)0.0147 (5)
N40.11774 (18)0.07022 (13)0.4299 (2)0.0199 (5)
C90.2038 (2)0.05697 (14)0.3732 (2)0.0160 (5)
C100.1929 (2)0.00808 (15)0.2760 (3)0.0224 (6)
H100.13120.01230.25320.027*
C110.2721 (2)0.01038 (15)0.2134 (3)0.0257 (7)
H110.26340.04230.14840.031*
C120.3641 (2)0.01885 (16)0.2480 (3)0.0266 (7)
H120.41790.00620.20710.032*
C130.3761 (2)0.06757 (15)0.3446 (3)0.0249 (6)
H130.43830.08690.36820.030*
C140.2963 (2)0.08753 (15)0.4061 (3)0.0203 (6)
H140.30470.12110.46870.024*
H4A0.074 (2)0.0387 (16)0.421 (3)0.019 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0118 (3)0.0110 (3)0.0201 (3)0.0000.0019 (2)0.000
N10.0194 (11)0.0112 (10)0.0196 (12)0.0004 (9)0.0004 (9)0.0002 (9)
N20.0142 (11)0.0100 (10)0.0164 (11)0.0014 (8)0.0010 (8)0.0007 (8)
N30.0183 (11)0.0131 (11)0.0137 (11)0.0015 (9)0.0020 (9)0.0023 (8)
C10.0269 (16)0.0200 (14)0.0223 (15)0.0039 (12)0.0015 (12)0.0007 (11)
C20.0344 (17)0.0226 (15)0.0227 (16)0.0054 (13)0.0023 (12)0.0064 (12)
C30.0343 (17)0.0181 (14)0.0268 (16)0.0024 (13)0.0099 (13)0.0054 (12)
C40.0232 (15)0.0180 (14)0.0231 (15)0.0036 (11)0.0036 (11)0.0016 (11)
C50.0160 (13)0.0111 (12)0.0160 (13)0.0000 (10)0.0023 (10)0.0030 (10)
C60.0158 (12)0.0102 (12)0.0173 (13)0.0009 (10)0.0004 (10)0.0031 (10)
C70.0176 (14)0.0254 (15)0.0290 (16)0.0072 (12)0.0029 (11)0.0020 (12)
S10.0132 (3)0.0194 (4)0.0293 (4)0.0043 (3)0.0043 (3)0.0087 (3)
C80.0152 (12)0.0134 (12)0.0155 (13)0.0002 (10)0.0015 (10)0.0016 (9)
N40.0179 (12)0.0203 (12)0.0221 (13)0.0086 (10)0.0046 (9)0.0079 (10)
C90.0195 (13)0.0140 (13)0.0145 (13)0.0021 (10)0.0019 (10)0.0002 (10)
C100.0225 (15)0.0205 (14)0.0245 (15)0.0090 (11)0.0041 (11)0.0063 (11)
C110.0279 (16)0.0223 (15)0.0279 (16)0.0055 (13)0.0072 (12)0.0085 (12)
C120.0220 (15)0.0272 (16)0.0321 (17)0.0012 (12)0.0096 (12)0.0068 (13)
C130.0170 (14)0.0265 (16)0.0310 (16)0.0051 (12)0.0019 (12)0.0061 (13)
C140.0210 (14)0.0187 (14)0.0210 (14)0.0030 (11)0.0007 (11)0.0064 (11)
Geometric parameters (Å, º) top
Mn1—N22.258 (2)C7—H7A0.9600
Mn1—N12.264 (2)C7—H7B0.9600
Mn1—S12.5137 (8)C7—H7C0.9600
N1—C11.332 (3)S1—C81.740 (3)
N1—C51.362 (3)C8—N41.372 (3)
N2—C61.296 (3)N4—C91.406 (3)
N2—N31.383 (3)N4—H4A0.83 (3)
N3—C81.315 (3)C9—C141.393 (4)
C1—C21.381 (4)C9—C101.403 (4)
C1—H10.9300C10—C111.385 (4)
C2—C31.381 (4)C10—H100.9300
C2—H20.9300C11—C121.379 (4)
C3—C41.386 (4)C11—H110.9300
C3—H30.9300C12—C131.397 (4)
C4—C51.392 (4)C12—H120.9300
C4—H40.9300C13—C141.391 (4)
C5—C61.498 (3)C13—H130.9300
C6—C71.503 (3)C14—H140.9300
N2i—Mn1—N2170.43 (10)C4—C5—C6123.5 (2)
N2i—Mn1—N1101.51 (8)N2—C6—C5116.0 (2)
N2—Mn1—N171.70 (8)N2—C6—C7123.0 (2)
N2i—Mn1—N1i71.70 (8)C5—C6—C7121.0 (2)
N2—Mn1—N1i101.51 (8)C6—C7—H7A109.5
N1—Mn1—N1i93.47 (11)C6—C7—H7B109.5
N2i—Mn1—S1110.27 (6)H7A—C7—H7B109.5
N2—Mn1—S176.09 (6)C6—C7—H7C109.5
N1—Mn1—S1147.76 (6)H7A—C7—H7C109.5
N1i—Mn1—S191.44 (6)H7B—C7—H7C109.5
N2i—Mn1—S1i76.09 (6)C8—S1—Mn197.50 (9)
N2—Mn1—S1i110.27 (6)N3—C8—N4118.0 (2)
N1—Mn1—S1i91.44 (6)N3—C8—S1129.0 (2)
N1i—Mn1—S1i147.76 (6)N4—C8—S1113.07 (19)
S1—Mn1—S1i101.11 (4)C8—N4—C9132.2 (2)
C1—N1—C5118.8 (2)C8—N4—H4A109 (2)
C1—N1—Mn1124.00 (19)C9—N4—H4A116 (2)
C5—N1—Mn1117.13 (17)C14—C9—C10118.8 (2)
C6—N2—N3115.6 (2)C14—C9—N4125.7 (2)
C6—N2—Mn1119.44 (17)C10—C9—N4115.5 (2)
N3—N2—Mn1124.48 (15)C11—C10—C9121.3 (3)
C8—N3—N2112.9 (2)C11—C10—H10119.4
N1—C1—C2122.7 (3)C9—C10—H10119.4
N1—C1—H1118.6C12—C11—C10119.7 (3)
C2—C1—H1118.6C12—C11—H11120.2
C3—C2—C1119.1 (3)C10—C11—H11120.2
C3—C2—H2120.4C11—C12—C13119.7 (3)
C1—C2—H2120.4C11—C12—H12120.2
C2—C3—C4118.9 (3)C13—C12—H12120.2
C2—C3—H3120.5C14—C13—C12120.9 (3)
C4—C3—H3120.5C14—C13—H13119.5
C3—C4—C5119.3 (3)C12—C13—H13119.5
C3—C4—H4120.4C13—C14—C9119.6 (3)
C5—C4—H4120.4C13—C14—H14120.2
N1—C5—C4121.1 (2)C9—C14—H14120.2
N1—C5—C6115.3 (2)
N2i—Mn1—N1—C16.2 (2)C3—C4—C5—C6179.1 (3)
N2—Mn1—N1—C1179.2 (2)N3—N2—C6—C5179.8 (2)
N1i—Mn1—N1—C178.2 (2)Mn1—N2—C6—C57.1 (3)
S1—Mn1—N1—C1176.46 (17)N3—N2—C6—C70.3 (4)
S1i—Mn1—N1—C169.9 (2)Mn1—N2—C6—C7172.36 (19)
N2i—Mn1—N1—C5177.44 (18)N1—C5—C6—N22.9 (3)
N2—Mn1—N1—C54.43 (17)C4—C5—C6—N2177.3 (2)
N1i—Mn1—N1—C5105.42 (19)N1—C5—C6—C7176.6 (2)
S1—Mn1—N1—C57.2 (3)C4—C5—C6—C73.2 (4)
S1i—Mn1—N1—C5106.46 (18)N2i—Mn1—S1—C8174.73 (10)
N1—Mn1—N2—C66.34 (18)N2—Mn1—S1—C82.22 (10)
N1i—Mn1—N2—C696.21 (19)N1—Mn1—S1—C84.92 (15)
S1—Mn1—N2—C6175.17 (19)N1i—Mn1—S1—C8103.73 (10)
S1i—Mn1—N2—C678.27 (19)S1i—Mn1—S1—C8106.14 (9)
N1—Mn1—N2—N3178.3 (2)N2—N3—C8—N4179.3 (2)
N1i—Mn1—N2—N391.82 (19)N2—N3—C8—S10.1 (3)
S1—Mn1—N2—N33.20 (17)Mn1—S1—C8—N32.3 (3)
S1i—Mn1—N2—N393.70 (18)Mn1—S1—C8—N4177.22 (18)
C6—N2—N3—C8175.0 (2)N3—C8—N4—C97.2 (4)
Mn1—N2—N3—C82.8 (3)S1—C8—N4—C9172.3 (2)
C5—N1—C1—C22.0 (4)C8—N4—C9—C140.3 (5)
Mn1—N1—C1—C2178.3 (2)C8—N4—C9—C10179.3 (3)
N1—C1—C2—C31.5 (4)C14—C9—C10—C110.4 (4)
C1—C2—C3—C40.4 (4)N4—C9—C10—C11179.2 (3)
C2—C3—C4—C51.7 (4)C9—C10—C11—C121.0 (5)
C1—N1—C5—C40.7 (4)C10—C11—C12—C130.9 (5)
Mn1—N1—C5—C4177.20 (19)C11—C12—C13—C140.5 (5)
C1—N1—C5—C6179.1 (2)C12—C13—C14—C91.9 (4)
Mn1—N1—C5—C62.6 (3)C10—C9—C14—C131.8 (4)
C3—C4—C5—N11.2 (4)N4—C9—C14—C13177.7 (3)
Symmetry code: (i) x, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···S1ii0.84 (3)2.74 (3)3.494 (3)151 (3)
C7—H7C···N3iii0.962.513.472 (4)176
C11—H11···N3iv0.932.573.365 (4)143
C14—H14···N30.932.342.927 (4)121
Symmetry codes: (ii) x, y, z+1; (iii) x+1/2, y+1/2, z+1; (iv) x, y, z1/2.

Experimental details

Crystal data
Chemical formula[Mn(C14H13N4S)2]
Mr593.63
Crystal system, space groupMonoclinic, C2/c
Temperature (K)183
a, b, c (Å)13.5897 (1), 18.7968 (1), 10.9688 (1)
β (°) 96.427 (1)
V3)2784.29 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.66
Crystal size (mm)0.24 × 0.20 × 0.16
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.858, 0.902
No. of measured, independent and
observed [I > 2σ(I)] reflections
8419, 3381, 2456
Rint0.090
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.145, 0.98
No. of reflections3381
No. of parameters182
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.75, 1.34

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
Mn1—N22.258 (2)Mn1—S12.5137 (8)
Mn1—N12.264 (2)
N2i—Mn1—N1101.51 (8)N2i—Mn1—S1110.27 (6)
N2—Mn1—N171.70 (8)N2—Mn1—S176.09 (6)
Symmetry code: (i) x, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···S1ii0.84 (3)2.74 (3)3.494 (3)151 (3)
C7—H7C···N3iii0.962.513.472 (4)176
C11—H11···N3iv0.932.573.365 (4)143
C14—H14···N30.932.342.927 (4)121
Symmetry codes: (ii) x, y, z+1; (iii) x+1/2, y+1/2, z+1; (iv) x, y, z1/2.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds