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Acta Cryst. (2007). E63, m2434-m2435    [ doi:10.1107/S1600536807041487 ]

(Acetato-[kappa]2O,O')(aqua-[kappa]O)[1-(2-pyridylmethylidene-[kappa]N)semicarbazide-[kappa]2N1,O](thiocyanato-[kappa]S)cadmium(II) monohydrate

L.-F. Deng, G.-Q. Guo, D.-C. Zhong, J.-H. Deng and M.-P. Guo

Abstract top

The Cd atom in the title complex, [Cd(C2H3O2)(NCS)(C7H8N4O)(H2O)]·H2O, is coordinated by one neutral Schiff base ligand, one acetate anion, one thiocyanate anion and one water molecule, forming a distorted pentagonal-bipyramidal geometry. The thiocyanate S atom and the coordinated water ligand occupy the apical positions of the coordination polyhedron. The acetate acts as a bidentate ligand through the carboxylate O atoms. The Schiff base, derived from the condensation of pyridine-2-carbaldehyde and semicarbazone, acts as a tridentate ligand, coordinating the metal through the amide, imine and pyridyl N atoms in a meridional fashion. The crystal packing is stabilized by [pi]-[pi] stacking interactions between the neighboring pyridine rings and hydrogen bonds involving the Schiff base, thiocyanate, water molecules and uncoordinated solvent water molecules.

Comment top

Crystal structures and properties of metal complexes based on pyridine-2-carbaldehyde semicarbazone (H-Pysc), owing to their antimicrobial, cytotoxic and antioxidant activities, have been reported in numerous papers (Zhou et al., 2004; Kaur et al., 2002; Carcelli et al., 1999; Zhong et al., 2007) in last several years. Herein, we report the synthesis and crystal structure of the title compound, (I).

Compound (I) is composed of one [Cd(HPysc)(SCN)(Ac)(H2O)] unit and one lattice water. The Cd atom in compound (I) is seven-coordinated (Fig. 1) by one S atom (from thiocyanate), two N atoms (from H-Pysc ligand) and four O atoms (one from the coordinated water molecule, one from H-Pysc ligand, and two from the acetate anion), forming a slightly distorted pentagonal bipyramidal geometry (Table 1). S1 and O1W occupy the apical positions of the coordination polyhedron. Similar to the corresponding nickel(II) complex (Zhou et al., 2004), the H-Pysc ligand is planar and utilizes its pyridyl N atom, amide O atom and imine N atom for metal coordination. This is in contrast to the highly related ligand pyridine-3-carbaldehyde-semicarbazone in it's cobalt(II) (Chen, Zhou, Liang et al., 2004) and nickel(II) (Chen, Zhou, Li et al., 2004) complexes, in which only the pyridyl N atoms bind to the metal ions. The acetate anion acts as a bidentate chelating ligand leading to two short C—O distances (O(2)—C(8) 1.261 (3) Å, O(3)—C(8) 1.260 (3) Å).

The molecules are connected by intermolecular hydrogen bonding interactions and π - π stacking interactions to form a three-dimensional supramolecular network. The coordinated water molecules (O1W) act as hydrogen bond donor sites towards the thiocyanate S1 atoms and acetate O3 atoms to form O—H···Si and O—H···Oii hydrogen bonds, respectively [symmetry codes i=x, 1/2 − y, 1/2 + z; ii = 1 − x, −y, 1 − z]. The uncoordinated water molecules (O2W) also act as a H atom donors, the accepters being the thiocyanate N5 atoms and acetate O2 atoms, respectively, forming O—H···Niii and O—H···Oi hydrogen bonds [symmetry codes iii=x, 3/2 − y, 1/2 + z]. In addition, the O1W atoms and semicarbazone O1 atoms accept H atoms from N4 to form N—H···Ov and N—H···Oiv hydrogen bonds [symmetry codes iv = 1 − x, 1 − y, 1 − z; v = x, 1 + y, z] (Table 2, Fig. 2).

Related literature top

For related literature, see: Carcelli et al. (1999); Chen, Zhou, Liang et al. (2004); Chen, Zhou, Li et al. (2004); Kaur et al. (2002); Zhong et al. (2007); Zhou et al. (2004).

Experimental top

H-Pysc (1.0 mmol) and Cd(Ac)2 × 4H2O (0.5 mmol) were dissolved in a water-ethanol mixture (1:1 v/v; 16 ml) at 353 K. After stirring for ca 2 hrs, 10 ml of a solution containing 1.0 mmol (NH4)SCN was added, then the mixture was further stirred for another 2 hrs. The resulting solution was filtered and the filtrate allowed to standing at room temperature. Well shaped colorless crystals suitable for X-rays diffraction were obtained in 58% yield after two weeks.

Refinement top

Hydrogen atoms bound to carbon atoms and nitrogen atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å, N—H = 0.86 Å, and Uiso(H) = 1.2Ueq(C or N). Water Hydrogen atoms were located in difference maps and constrained to ride at the as-found O—H distances (0.89 Å), with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-labeling scheme.
[Figure 2] Fig. 2. Three-dimensional supramolecular network constructed by hydrogen bonding interactions (dashed lines) and p\-p\ stacking interaction.
(Acetato-κ2O,O')(aqua-κO)[1-(2-pyridylmethylidene-κN)semicarbazide-\ κ2N1,O](thiocyanato-κS)cadmium(II) monohydrate top
Crystal data top
[Cd(C2H3O2)(NCS)(C7H8N4O)(H2O)]·H2OZ = 4
Mr = 429.73F000 = 856
Monoclinic, P21/cDx = 1.814 Mg m−3
Hall symbol: -P 2ybcMo Kα radiation
λ = 0.71073 Å
a = 14.767 (1) Åθ = 2.8–28.4º
b = 7.7345 (7) ŵ = 1.55 mm−1
c = 13.964 (1) ÅT = 173 (2) K
β = 99.340 (1)ºBlock, colourless
V = 1573.7 (3) Å30.35 × 0.28 × 0.22 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer		3919 independent reflections
Radiation source: fine-focus sealed tube2921 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.072
T = 173(2) Kθmax = 28.4º
ω scansθmin = 2.8º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −19→19
Tmin = 0.601, Tmax = 0.718k = −9→10
14208 measured reflectionsl = −18→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.056  w = 1/[σ2(Fo2) + (0.0183P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.93(Δ/σ)max = 0.001
3919 reflectionsΔρmax = 0.48 e Å−3
199 parametersΔρmin = −0.63 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cd(C2H3O2)(NCS)(C7H8N4O)(H2O)]·H2OV = 1573.7 (3) Å3
Mr = 429.73Z = 4
Monoclinic, P21/cMo Kα
a = 14.767 (1) ŵ = 1.55 mm−1
b = 7.7345 (7) ÅT = 173 (2) K
c = 13.964 (1) Å0.35 × 0.28 × 0.22 mm
β = 99.340 (1)º
Data collection top
Bruker SMART APEXII CCD
diffractometer		3919 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2921 reflections with I > 2σ(I)
Tmin = 0.601, Tmax = 0.718Rint = 0.072
14208 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028199 parameters
wR(F2) = 0.056H-atom parameters constrained
S = 0.93Δρmax = 0.48 e Å−3
3919 reflectionsΔρmin = −0.63 e Å−3
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
Cd10.688818 (11)0.12412 (2)0.472629 (12)0.02909 (6)
S10.72697 (6)0.26945 (11)0.30933 (5)0.0539 (2)
O10.59934 (11)0.3712 (2)0.50308 (13)0.0371 (4)
N10.83695 (13)0.0190 (3)0.54372 (14)0.0336 (5)
O30.54727 (11)−0.0111 (2)0.39860 (11)0.0369 (4)
O1W0.63610 (11)0.0075 (2)0.61140 (11)0.0330 (4)
O20.67697 (12)−0.1351 (2)0.38194 (14)0.0451 (5)
C80.59050 (17)−0.1326 (3)0.36624 (17)0.0331 (5)
N30.73204 (13)0.4873 (3)0.58458 (14)0.0341 (5)
H3A0.76170.57450.61210.041*
N20.77331 (13)0.3339 (3)0.57216 (14)0.0303 (5)
N40.59726 (15)0.6374 (3)0.56943 (16)0.0416 (5)
H4A0.53940.64960.54940.050*
H4B0.62780.71860.60210.050*
C70.63933 (17)0.4936 (3)0.54996 (17)0.0313 (5)
C60.85542 (17)0.3042 (3)0.61182 (18)0.0359 (6)
H60.89050.38890.64770.043*
C10.86846 (18)−0.1400 (4)0.5326 (2)0.0422 (7)
H10.8304−0.21830.49480.051*
C50.89292 (16)0.1320 (3)0.59916 (17)0.0347 (6)
N50.8725 (2)0.5003 (4)0.3657 (2)0.0673 (8)
C90.5393 (2)−0.2757 (4)0.3088 (2)0.0486 (7)
C20.95532 (19)−0.1941 (4)0.5746 (2)0.0495 (8)
H20.9748−0.30640.56570.059*
C40.98095 (18)0.0857 (4)0.6424 (2)0.0468 (7)
H41.01850.16540.67970.056*
C100.8116 (2)0.4066 (4)0.3455 (2)0.0478 (7)
C31.0120 (2)−0.0781 (4)0.6296 (2)0.0521 (8)
H31.0709−0.11050.65800.062*
O2W0.79164 (14)0.6935 (3)0.74484 (15)0.0604 (6)
H9C0.4875−0.31890.33480.091*
H9B0.5195−0.25230.23960.091*
H9A0.5857−0.36530.31350.091*
H2B0.75350.66090.78480.091*
H1B0.57450.01230.60700.091*
H1A0.66170.05400.66790.091*
H2A0.82070.79260.76170.091*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02724 (9)0.02820 (10)0.03121 (10)0.00117 (8)0.00290 (6)−0.00288 (8)
S10.0649 (5)0.0621 (5)0.0335 (4)−0.0032 (4)0.0041 (3)0.0104 (4)
O10.0324 (9)0.0285 (9)0.0484 (11)0.0034 (8)0.0007 (8)−0.0104 (9)
N10.0293 (11)0.0400 (13)0.0316 (12)0.0045 (10)0.0054 (9)0.0037 (10)
O30.0344 (10)0.0398 (11)0.0361 (10)−0.0003 (8)0.0043 (8)−0.0082 (8)
O1W0.0320 (9)0.0350 (10)0.0318 (9)−0.0012 (8)0.0047 (7)−0.0025 (8)
O20.0356 (10)0.0459 (12)0.0537 (12)−0.0028 (9)0.0068 (8)−0.0107 (10)
C80.0378 (13)0.0347 (14)0.0269 (12)−0.0052 (12)0.0058 (10)0.0005 (12)
N30.0334 (11)0.0265 (12)0.0410 (13)−0.0023 (9)0.0020 (9)−0.0086 (9)
N20.0315 (11)0.0307 (12)0.0292 (11)0.0011 (9)0.0065 (9)−0.0010 (9)
N40.0398 (12)0.0303 (12)0.0532 (14)0.0053 (10)0.0030 (10)−0.0113 (11)
C70.0357 (13)0.0293 (14)0.0291 (13)0.0011 (11)0.0056 (10)0.0021 (11)
C60.0330 (13)0.0428 (16)0.0304 (14)−0.0021 (12)0.0007 (11)−0.0068 (12)
C10.0393 (14)0.0395 (17)0.0490 (17)0.0081 (13)0.0108 (12)0.0035 (13)
C50.0289 (12)0.0450 (16)0.0304 (13)0.0022 (12)0.0054 (10)0.0037 (12)
N50.0597 (17)0.0463 (17)0.096 (2)0.0005 (15)0.0134 (16)0.0116 (16)
C90.0502 (17)0.0477 (18)0.0483 (18)−0.0103 (15)0.0092 (14)−0.0194 (14)
C20.0474 (17)0.0512 (18)0.0519 (18)0.0213 (15)0.0141 (15)0.0142 (15)
C40.0337 (14)0.067 (2)0.0368 (16)0.0091 (14)−0.0014 (12)0.0015 (14)
C100.0564 (19)0.0404 (18)0.0489 (18)0.0171 (15)0.0150 (15)0.0139 (14)
C30.0358 (15)0.074 (2)0.0447 (17)0.0203 (15)0.0013 (13)0.0126 (16)
O2W0.0694 (14)0.0664 (15)0.0482 (12)−0.0270 (12)0.0179 (11)−0.0203 (11)
Geometric parameters (Å, °) top
Cd1—N22.357 (2)N2—C61.269 (3)
Cd1—O22.3629 (18)N4—C71.323 (3)
Cd1—O1W2.3800 (15)N4—H4A0.8600
Cd1—N12.393 (2)N4—H4B0.8600
Cd1—O12.4000 (16)C6—C51.464 (4)
Cd1—O32.4146 (16)C6—H60.9300
Cd1—S12.6829 (8)C1—C21.386 (4)
Cd1—C82.749 (3)C1—H10.9300
S1—C101.655 (4)C5—C41.388 (4)
O1—C71.244 (3)N5—C101.154 (4)
N1—C11.332 (3)C9—H9C0.9582
N1—C51.356 (3)C9—H9B0.9803
O3—C81.260 (3)C9—H9A0.9695
O1W—H1B0.9021C2—C31.374 (4)
O1W—H1A0.8926C2—H20.9300
O2—C81.260 (3)C4—C31.369 (4)
C8—C91.497 (4)C4—H40.9300
N3—N21.358 (3)C3—H30.9300
N3—C71.377 (3)O2W—H2B0.8910
N3—H3A0.8600O2W—H2A0.8910
N2—Cd1—O2152.38 (7)O2—C8—Cd159.06 (13)
N2—Cd1—O1W89.57 (6)O3—C8—Cd161.41 (12)
O2—Cd1—O1W96.27 (6)C9—C8—Cd1178.4 (2)
N2—Cd1—N168.20 (7)N2—N3—C7115.3 (2)
O2—Cd1—N185.24 (7)N2—N3—H3A122.4
O1W—Cd1—N186.06 (6)C7—N3—H3A122.4
N2—Cd1—O166.52 (6)C6—N2—N3121.3 (2)
O2—Cd1—O1140.86 (6)C6—N2—Cd1120.63 (17)
O1W—Cd1—O183.98 (6)N3—N2—Cd1118.12 (14)
N1—Cd1—O1133.60 (7)C7—N4—H4A120.0
N2—Cd1—O3152.75 (6)C7—N4—H4B120.0
O2—Cd1—O354.50 (6)H4A—N4—H4B120.0
O1W—Cd1—O379.02 (5)O1—C7—N4123.3 (2)
N1—Cd1—O3134.41 (7)O1—C7—N3121.2 (2)
O1—Cd1—O387.56 (6)N4—C7—N3115.5 (2)
N2—Cd1—S192.79 (5)N2—C6—C5117.7 (2)
O2—Cd1—S184.69 (5)N2—C6—H6121.1
O1W—Cd1—S1172.92 (4)C5—C6—H6121.1
N1—Cd1—S1101.01 (5)N1—C1—C2123.1 (3)
O1—Cd1—S190.84 (5)N1—C1—H1118.5
O3—Cd1—S195.98 (4)C2—C1—H1118.5
N2—Cd1—C8176.58 (7)N1—C5—C4121.5 (3)
O2—Cd1—C827.22 (7)N1—C5—C6116.6 (2)
O1W—Cd1—C887.27 (6)C4—C5—C6121.9 (3)
N1—Cd1—C8110.22 (8)C8—C9—H9C114.8
O1—Cd1—C8114.40 (7)C8—C9—H9B115.8
O3—Cd1—C827.28 (6)H9C—C9—H9B108.0
S1—Cd1—C890.50 (5)C8—C9—H9A101.7
C10—S1—Cd1105.18 (10)H9C—C9—H9A108.9
C7—O1—Cd1118.10 (15)H9B—C9—H9A107.1
C1—N1—C5118.0 (2)C3—C2—C1118.5 (3)
C1—N1—Cd1125.32 (18)C3—C2—H2120.7
C5—N1—Cd1116.69 (16)C1—C2—H2120.7
C8—O3—Cd191.31 (14)C3—C4—C5119.5 (3)
Cd1—O1W—H1B112.9C3—C4—H4120.3
Cd1—O1W—H1A114.8C5—C4—H4120.3
H1B—O1W—H1A108.8N5—C10—S1176.0 (3)
C8—O2—Cd193.72 (15)C4—C3—C2119.4 (3)
O2—C8—O3120.5 (2)C4—C3—H3120.3
O2—C8—C9119.4 (2)C2—C3—H3120.3
O3—C8—C9120.1 (2)H2B—O2W—H2A113.8
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···S1i0.892.463.348 (2)170
O1W—H1B···O3ii0.901.792.689 (2)177
O2W—H2A···N5iii0.892.213.038 (4)154
O2W—H2B···O2i0.891.912.791 (3)169
N3—H3A···O2W0.862.052.773 (3)141
N4—H4A···O1iv0.862.072.916 (3)169
N4—H4B···O1Wv0.862.242.959 (3)141
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) x, −y+3/2, z+1/2; (iv) −x+1, −y+1, −z+1; (v) x, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···S1i0.892.463.348 (2)170
O1W—H1B···O3ii0.901.792.689 (2)177
O2W—H2A···N5iii0.892.213.038 (4)154
O2W—H2B···O2i0.891.912.791 (3)169
N3—H3A···O2W0.862.052.773 (3)141
N4—H4A···O1iv0.862.072.916 (3)169
N4—H4B···O1Wv0.862.242.959 (3)141
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) x, −y+3/2, z+1/2; (iv) −x+1, −y+1, −z+1; (v) x, y+1, z.
references
References top

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