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Acta Cryst. (2007). E63, m1747    [ doi:10.1107/S1600536807023707 ]

Bis{3-[(E)-2-(aminocarbonyl)hydrazonomethyl]pyridine}diaquadiisothiocyanatomanganese(II)

D.-C. Zhong, G.-Q. Guo and J.-H. Deng

Abstract top

In the title complex, [Mn(SCN)2(H-Pysc)2(H2O)2] {H-Pysc = 3-[2-(aminocarbonyl)hydrazonomethyl]pyridine, C7H8N4O}, MnII, located at an inversion centre, is coordinated by two thiocyanate anions, two water molecules and two molecules of the neutral Schiff base ligand H-Pysc, forming an octahedral configuration. The Schiff base acts as a monodentate ligand, coordinating to the metal through the pyridyl N atom, whereas the amide O and imine N atoms remain uncoordinated. The complex molecules are held together by intermolecular hydrogen bonds into a three-dimensional supramolecular network.

Comment top

Structurally characterized metal-organic complexes based on the Schiff base ligands derived from semicarbazone have been reported due to their antimicrobial, cytotoxic and antioxidant activities (Chen, Zhou, Liang et al., 2004; Chen, Zhou, Li et al., 2004; Beraldo et al., 2001). We report here the crystal structure of the title compound (I).

The Mn atom in compound (I) is six-coordinated by two O atoms of water molecules and four N atoms, two of which come from two thiocyanate anions and the rest from H-Pysc ligands (Fig. 1). The bond lengths and three trans angles at Mn1 suggests a slightly distorted octahedral geometry (Table 1).

The molecules are held together by intermolecular hydrogen bonding forming three-dimensional supramolecular network. The coordinated water molecules (O1W) donate H atoms to the terminal O1 atom and thiocyanate S atoms to form O—H···Oi and O—H···Sii hydrogen bonds, respectively (Table 2, Fig. 2) The O1 atoms also accept H atom from N3 to form N—H···Oiii hydrogen bonds (Table 2, Fig. 2).

Related literature top

For related literature, see: Beraldo et al. (2001); Chen, Zhou, Li et al. (2004); Chen, Zhou, Liang et al. (2004); Sheldrick (1997).

Experimental top

1.0 mmol H-Pysc, 0.5 mmol Mn(Ac)2.4H2O and 1.0 mmol of (NH4)SCN were dissolved in a water-ethanol mixture (1:2 v/v; 20 ml), and the mixture was stirred for ca 2 h at 343 K. The mixture was further stirred for another 1 h at 333 K and filtered. The resultant filtrate was left to stand for slow evaporation at room temperature. Colourless single crystals of (I) suitable for X-ray structure analysis were obtained after a period of 15 days (yield 72%).

Refinement top

Hydrogen atoms attached to carbon atoms and nitrogen atoms were positioned geometrically and treated as riding, with C—H = 0.93 Å, N—H = 0.86 Å, and Uiso(H) = 1.2Ueq(C or N)]. Water H atoms were located in difference maps and constrained to ride at O—H distances (0.85 Å) with Uiso(H) = 1.5Ueq(O).

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I) showing the 50% probability displacement ellipsoids and the atom-labelling scheme [symmetry code: (i) - x + 1, - y, - z.].
[Figure 2] Fig. 2. Three-dimensional supramolecular network constructed by hydrogen bonds (dashed lines).
Bis{3-[(E)-2-(aminocarbonyl)hydrazonomethyl]pyridine}- diaquadiisothiocyanatomanganese(II) top
Crystal data top
[Mn(SCN)2(C7H8N4O)2(H2O)2]Z = 1
Mr = 535.48F(000) = 275
Triclinic, P1Dx = 1.551 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.6998 (19) ÅCell parameters from 2857 reflections
b = 9.329 (3) Åθ = 2.2–28.4°
c = 10.478 (3) ŵ = 0.80 mm−1
α = 64.770 (3)°T = 173 K
β = 82.711 (3)°Block, colourless
γ = 75.384 (3)°0.56 × 0.46 × 0.35 mm
V = 573.1 (3) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		2738 independent reflections
Radiation source: fine-focus sealed tube2010 reflections with I > 2σ(I)
graphiteRint = 0.068
phi and ω scansθmax = 28.4°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −8→8
Tmin = 0.647, Tmax = 0.753k = −12→12
5162 measured reflectionsl = −13→13
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0574P)2 + 0.0195P]
where P = (Fo2 + 2Fc2)/3
2738 reflections(Δ/σ)max < 0.001
151 parametersΔρmax = 0.61 e Å−3
0 restraintsΔρmin = −0.48 e Å−3
Crystal data top
[Mn(SCN)2(C7H8N4O)2(H2O)2]γ = 75.384 (3)°
Mr = 535.48V = 573.1 (3) Å3
Triclinic, P1Z = 1
a = 6.6998 (19) ÅMo Kα radiation
b = 9.329 (3) ŵ = 0.80 mm−1
c = 10.478 (3) ÅT = 173 K
α = 64.770 (3)°0.56 × 0.46 × 0.35 mm
β = 82.711 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2738 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		2010 reflections with I > 2σ(I)
Tmin = 0.647, Tmax = 0.753Rint = 0.068
5162 measured reflectionsθmax = 28.4°
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.116Δρmax = 0.61 e Å−3
S = 1.06Δρmin = −0.48 e Å−3
2738 reflectionsAbsolute structure: ?
151 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Mn10.50000.00000.00000.03568 (17)
S10.11296 (10)−0.42537 (8)0.10273 (8)0.0535 (2)
O1−0.5650 (3)0.1500 (2)−0.67672 (18)0.0485 (4)
N2−0.1690 (3)0.1982 (2)−0.5220 (2)0.0377 (4)
O1W0.2788 (3)0.1500 (2)0.09562 (18)0.0509 (5)
H1B0.18220.23160.05420.076*
H1A0.31690.16960.15920.076*
N10.3320 (3)0.1506 (2)−0.21142 (19)0.0347 (4)
C10.1792 (3)0.1049 (3)−0.2461 (2)0.0347 (5)
H10.13380.0120−0.17810.042*
C20.0843 (3)0.1862 (3)−0.3759 (2)0.0327 (5)
N3−0.3197 (3)0.1331 (2)−0.5403 (2)0.0413 (5)
H3A−0.34780.0434−0.47330.050*
C80.2205 (3)−0.2772 (3)0.0791 (2)0.0394 (5)
C30.1501 (3)0.3210 (3)−0.4753 (2)0.0391 (5)
H30.09170.3774−0.56630.047*
C6−0.0808 (3)0.1251 (3)−0.4029 (2)0.0377 (5)
H6−0.12160.0317−0.33210.045*
C50.3886 (3)0.2840 (3)−0.3076 (2)0.0410 (5)
H50.49330.3205−0.28420.049*
N50.2998 (3)−0.1731 (3)0.0611 (2)0.0514 (5)
C7−0.4251 (3)0.2080 (3)−0.6625 (3)0.0410 (5)
C40.3025 (4)0.3718 (3)−0.4394 (3)0.0481 (6)
H40.34790.4661−0.50460.058*
N4−0.3730 (4)0.3407 (3)−0.7595 (2)0.0654 (7)
H4B−0.43840.3936−0.83980.078*
H4A−0.27280.3762−0.74380.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0336 (3)0.0431 (3)0.0360 (3)−0.0139 (2)−0.01144 (19)−0.0156 (2)
S10.0500 (4)0.0465 (4)0.0689 (5)−0.0199 (3)−0.0100 (3)−0.0207 (3)
O10.0491 (9)0.0577 (11)0.0472 (10)−0.0107 (8)−0.0229 (8)−0.0242 (9)
N20.0311 (9)0.0479 (11)0.0422 (11)−0.0095 (8)−0.0094 (8)−0.0232 (9)
O1W0.0520 (10)0.0606 (11)0.0473 (10)−0.0018 (8)−0.0200 (8)−0.0298 (9)
N10.0306 (8)0.0422 (10)0.0369 (10)−0.0084 (7)−0.0099 (7)−0.0188 (8)
C10.0311 (10)0.0422 (12)0.0344 (11)−0.0119 (9)−0.0062 (9)−0.0156 (10)
C20.0246 (9)0.0439 (12)0.0351 (11)−0.0067 (8)−0.0057 (8)−0.0205 (10)
N30.0385 (10)0.0475 (11)0.0434 (11)−0.0132 (8)−0.0183 (8)−0.0170 (9)
C80.0354 (11)0.0468 (13)0.0368 (12)−0.0107 (9)−0.0125 (9)−0.0139 (10)
C30.0329 (10)0.0501 (13)0.0353 (12)−0.0093 (10)−0.0095 (9)−0.0159 (10)
C60.0321 (10)0.0447 (12)0.0398 (13)−0.0101 (9)−0.0104 (9)−0.0172 (10)
C50.0347 (11)0.0498 (13)0.0443 (14)−0.0171 (10)−0.0101 (10)−0.0180 (11)
N50.0496 (12)0.0577 (13)0.0519 (13)−0.0251 (10)−0.0142 (10)−0.0165 (11)
C70.0404 (11)0.0497 (13)0.0396 (13)−0.0062 (10)−0.0142 (10)−0.0231 (11)
C40.0434 (12)0.0522 (15)0.0461 (15)−0.0229 (11)−0.0109 (11)−0.0083 (12)
N40.0730 (16)0.0786 (17)0.0439 (13)−0.0333 (14)−0.0224 (12)−0.0097 (12)
Geometric parameters (Å, °) top
Mn1—N52.193 (2)C1—H10.9500
Mn1—N5i2.193 (2)C2—C31.381 (3)
Mn1—O1Wi2.2203 (17)C2—C61.471 (3)
Mn1—O1W2.2203 (17)N3—C71.358 (3)
Mn1—N12.3085 (18)N3—H3A0.8800
Mn1—N1i2.3085 (18)C8—N51.158 (3)
S1—C81.630 (2)C3—C41.380 (3)
O1—C71.246 (3)C3—H30.9500
N2—C61.276 (3)C6—H60.9500
N2—N31.372 (2)C5—C41.383 (3)
O1W—H1B0.8533C5—H50.9500
O1W—H1A0.8447C7—N41.320 (3)
N1—C51.335 (3)C4—H40.9500
N1—C11.345 (2)N4—H4B0.8800
C1—C21.387 (3)N4—H4A0.8800
N5—Mn1—N5i180.00 (9)C3—C2—C6122.49 (19)
N5—Mn1—O1Wi88.84 (8)C1—C2—C6119.0 (2)
N5i—Mn1—O1Wi91.16 (8)C7—N3—N2119.6 (2)
N5—Mn1—O1W91.16 (8)C7—N3—H3A120.2
N5i—Mn1—O1W88.84 (8)N2—N3—H3A120.2
O1Wi—Mn1—O1W180.00 (13)N5—C8—S1178.8 (2)
N5—Mn1—N190.01 (7)C4—C3—C2118.5 (2)
N5i—Mn1—N189.99 (7)C4—C3—H3120.8
O1Wi—Mn1—N190.48 (6)C2—C3—H3120.8
O1W—Mn1—N189.52 (6)N2—C6—C2119.7 (2)
N5—Mn1—N1i89.99 (7)N2—C6—H6120.1
N5i—Mn1—N1i90.01 (7)C2—C6—H6120.1
O1Wi—Mn1—N1i89.52 (6)N1—C5—C4123.3 (2)
O1W—Mn1—N1i90.48 (6)N1—C5—H5118.4
N1—Mn1—N1i180.00 (6)C4—C5—H5118.4
C6—N2—N3116.5 (2)C8—N5—Mn1167.3 (2)
Mn1—O1W—H1B127.1O1—C7—N4123.9 (2)
Mn1—O1W—H1A120.4O1—C7—N3119.1 (2)
H1B—O1W—H1A104.6N4—C7—N3117.1 (2)
C5—N1—C1116.89 (18)C3—C4—C5119.3 (2)
C5—N1—Mn1121.13 (13)C3—C4—H4120.4
C1—N1—Mn1121.93 (15)C5—C4—H4120.4
N1—C1—C2123.5 (2)C7—N4—H4B120.0
N1—C1—H1118.2C7—N4—H4A120.0
C2—C1—H1118.2H4B—N4—H4A120.0
C3—C2—C1118.52 (19)
Symmetry codes: (i) −x+1, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···O1ii0.841.902.724 (3)164
O1W—H1B···S1iii0.852.523.352 (2)164
N3—H3A···O1iv0.881.992.865 (3)175
N4—H4A···N20.882.282.637 (3)104
Symmetry codes: (ii) x+1, y, z+1; (iii) −x, −y, −z; (iv) −x−1, −y, −z−1.
Table 1
Selected geometric parameters (Å, °) top
Mn1—N52.193 (2)Mn1—N12.3085 (18)
Mn1—O1W2.2203 (17)
N5—Mn1—N5i180.00 (9)O1W—Mn1—N189.52 (6)
N5—Mn1—O1Wi88.84 (8)N5—Mn1—N1i89.99 (7)
N5—Mn1—O1W91.16 (8)O1W—Mn1—N1i90.48 (6)
O1Wi—Mn1—O1W180.00 (13)N1—Mn1—N1i180.00 (6)
N5—Mn1—N190.01 (7)
Symmetry codes: (i) −x+1, −y, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···O1ii0.841.902.724 (3)164
O1W—H1B···S1iii0.852.523.352 (2)164
N3—H3A···O1iv0.881.992.865 (3)175
N4—H4A···N20.882.282.637 (3)104
Symmetry codes: (ii) x+1, y, z+1; (iii) −x, −y, −z; (iv) −x−1, −y, −z−1.
references
References top

Beraldo, H., Nacif, W.-F. & West, D.-X. (2001). Spectrochim. Acta Part A, 57, 1847–1854.

Bruker (1997). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. please check added reference.

Bruker (1998). SMART (Version 5.051), SAINT (Version 5.01) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Chen, Z.-F., Zhou, J., Liang, H., Tan, Y.-H. & Zhang, Y. (2004). Acta Cryst. E60, m802–m804.

Chen, Z.-F., Zhou, J., Li, D.-Q., Tan, M.-X., Liang, H. & Zhang, Y. (2004). Acta Cryst. E60, m861–m862.

Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473.

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