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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023707/kp2108sup1.cif
Contains datablocks Mn, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023707/kp2108Isup2.hkl
Contains datablock I

CCDC reference: 651361

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.040
  • wR factor = 0.116
  • Data-to-parameter ratio = 18.1

checkCIF/PLATON results

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Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 300 Deg. PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C8 .. 5.06 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.36 PLAT420_ALERT_2_C D-H Without Acceptor N4 - H4B ... ?
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 1.99
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 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

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.

Structure description 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).

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

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 m3
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 mm1
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)
Graphite monochromatorRint = 0.068
phi and ω scansθmax = 28.4°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 88
Tmin = 0.647, Tmax = 0.753k = 1212
5162 measured reflectionsl = 1313
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 Å3
0 restraintsΔρmin = 0.48 e Å3
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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.06Δρmax = 0.61 e Å3
2738 reflectionsΔρmin = 0.48 e Å3
151 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
Mn10.50000.00000.00000.03568 (17)
S10.11296 (10)0.42537 (8)0.10273 (8)0.0535 (2)
O10.5650 (3)0.1500 (2)0.67672 (18)0.0485 (4)
N20.1690 (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)
H10.13380.01200.17810.042*
C20.0843 (3)0.1862 (3)0.3759 (2)0.0327 (5)
N30.3197 (3)0.1331 (2)0.5403 (2)0.0413 (5)
H3A0.34780.04340.47330.050*
C80.2205 (3)0.2772 (3)0.0791 (2)0.0394 (5)
C30.1501 (3)0.3210 (3)0.4753 (2)0.0391 (5)
H30.09170.37740.56630.047*
C60.0808 (3)0.1251 (3)0.4029 (2)0.0377 (5)
H60.12160.03170.33210.045*
C50.3886 (3)0.2840 (3)0.3076 (2)0.0410 (5)
H50.49330.32050.28420.049*
N50.2998 (3)0.1731 (3)0.0611 (2)0.0514 (5)
C70.4251 (3)0.2080 (3)0.6625 (3)0.0410 (5)
C40.3025 (4)0.3718 (3)0.4394 (3)0.0481 (6)
H40.34790.46610.50460.058*
N40.3730 (4)0.3407 (3)0.7595 (2)0.0654 (7)
H4B0.43840.39360.83980.078*
H4A0.27280.37620.74380.078*
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, º) 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 code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) 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) x1, y, z1.

Experimental details

Crystal data
Chemical formula[Mn(SCN)2(C7H8N4O)2(H2O)2]
Mr535.48
Crystal system, space groupTriclinic, P1
Temperature (K)173
a, b, c (Å)6.6998 (19), 9.329 (3), 10.478 (3)
α, β, γ (°)64.770 (3), 82.711 (3), 75.384 (3)
V3)573.1 (3)
Z1
Radiation typeMo Kα
µ (mm1)0.80
Crystal size (mm)0.56 × 0.46 × 0.35
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.647, 0.753
No. of measured, independent and
observed [I > 2σ(I)] reflections
5162, 2738, 2010
Rint0.068
(sin θ/λ)max1)0.669
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.116, 1.06
No. of reflections2738
No. of parameters151
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.61, 0.48

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Selected geometric parameters (Å, º) 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 code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) 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) x1, y, z1.
 

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