Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048908/im2038sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048908/im2038Isup2.hkl |
CCDC reference: 667138
1.0 mmol H-Pysc and 0.5 mmol Zn(Ac)2 × 4H2O were dissolved in a water-methanol mixture (1:1 v/v; 10 ml) at room temperature. After stirring for ca 1 h, 10 ml of the same mixture solvent containing 1.0 mmol of (NH4)SCN was added, then the mixture was further stirred for another 1 h. The resulting filtrate was left to stand for slow evaporation at room temperature. Colorless single crystals of (I) suitable for X-ray structure analysis were obtained after two weeks (yield 85%).
Hydrogen atoms attached to carbon atoms and nitrogen atoms were positioned geometrically refined using a riding model, with C—H = 0.95 Å, N—H = 0.88 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 (0.85 Å), with Uiso(H) = 1.5Ueq(O).
Metal complexes based on Schiff base ligands being synthesized by condensation of pyridine-3-carbaldehydehyde and thiosemicarbazone, semicarbazone and other amines (Mendes et al., 2001; Li et al., 2006) have attracted numerous chemists and biologists due to their antimicrobial, cytotoxic and antioxidant activities. Structurally characterized metal-organic complexes of Schiff bases derived from the condensation of pyridine- 3-carbaldehydehyde and semicarbazone have been reported during the last several years. (Chen, Zhou, Liang et al., 2004; Chen, Zhou, Li et al., 2004; Beraldo et al. 2001). As a consecutive work of our studies, we report herein the synthesis and crystal structure of the title compound, (I).
The title compound, (I) (Fig. 1), is isostructural with the manganese derivative of the same ligand (Zhong et al., 2007). The central Zn atom is situated at an crystallographic center of inversion and is hexa-coordinated by two O atoms of water molecules and four N atoms, two of which come from two thiocyanate anions and the others from H-Pysc ligands (Fig. 1), forming a slightly distorted octahedral geometry. The molecules are held together by intermolecular hydrogen bonding interactions forming a three- dimensional supramolecular network. The coordinated water molecules (O2) donate H atoms to the terminal O1 atom and thiocyanate S atoms to form O—H···Oii and O—H···Siii hydrogen bonds, respectively [symmetry codes ii = -1 + x, y, -1 + z; iii = 1 + x, y, z]. The O1 atoms also accept H atom from N to form N—H···Oiv hydrogen bonds [symmetry codes iv = 3 - x, 1 - y, 2 - z] (Table 1, Fig. 2).
For related literature, see: Beraldo et al. (2001); Chen, Zhou, Liang et al. (2004); Chen, Zhou, Li et al. (2004); Li et al. (2006); Mendes et al. (2001); Zhong et al. (2007).
Data collection: SMART (Bruker, 2004); cell refinement: SMART (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).
[Zn(NCS)2(C7H8N4O)2(H2O)2] | V = 559.4 (2) Å3 |
Mr = 545.91 | Z = 1 |
Triclinic, P1 | F(000) = 280 |
Hall symbol: -P 1 | Dx = 1.621 Mg m−3 |
a = 6.661 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.251 (2) Å | θ = 2.2–26.0° |
c = 10.328 (2) Å | µ = 1.33 mm−1 |
α = 65.765 (2)° | T = 173 K |
β = 82.438 (2)° | Block, white |
γ = 74.637 (2)° | 0.36 × 0.30 × 0.22 mm |
Bruker SMART CCD area-detector diffractometer | 2169 independent reflections |
Radiation source: fine-focus sealed tube | 2028 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
φ and ω scans | θmax = 26.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.626, Tmax = 0.742 | k = −11→11 |
4371 measured reflections | l = −10→12 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0572P)2 + 0.0984P] where P = (Fo2 + 2Fc2)/3 |
2169 reflections | (Δ/σ)max < 0.001 |
159 parameters | Δρmax = 0.74 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
[Zn(NCS)2(C7H8N4O)2(H2O)2] | γ = 74.637 (2)° |
Mr = 545.91 | V = 559.4 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.661 (1) Å | Mo Kα radiation |
b = 9.251 (2) Å | µ = 1.33 mm−1 |
c = 10.328 (2) Å | T = 173 K |
α = 65.765 (2)° | 0.36 × 0.30 × 0.22 mm |
β = 82.438 (2)° |
Bruker SMART CCD area-detector diffractometer | 2169 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2028 reflections with I > 2σ(I) |
Tmin = 0.626, Tmax = 0.742 | Rint = 0.073 |
4371 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.74 e Å−3 |
2169 reflections | Δρmin = −0.58 e Å−3 |
159 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.5000 | 0.5000 | 0.5000 | 0.01975 (16) | |
C1 | 0.9145 (3) | 0.3158 (3) | 0.8704 (2) | 0.0194 (4) | |
C2 | 0.8475 (3) | 0.1800 (3) | 0.9697 (2) | 0.0230 (5) | |
H2 | 0.9054 | 0.1234 | 1.0614 | 0.028* | |
C3 | 0.6960 (4) | 0.1300 (3) | 0.9317 (2) | 0.0280 (5) | |
H3 | 0.6530 | 0.0346 | 0.9956 | 0.034* | |
C4 | 0.6054 (4) | 0.2192 (3) | 0.7997 (2) | 0.0248 (5) | |
H4 | 0.4991 | 0.1837 | 0.7761 | 0.030* | |
C5 | 0.8161 (3) | 0.3982 (3) | 0.7395 (2) | 0.0215 (4) | |
H5 | 0.8609 | 0.4910 | 0.6719 | 0.026* | |
C6 | 1.0788 (4) | 0.3762 (3) | 0.8988 (2) | 0.0232 (5) | |
H6 | 1.1187 | 0.4698 | 0.8285 | 0.028* | |
C7 | 1.4282 (4) | 0.2913 (3) | 1.1602 (2) | 0.0231 (5) | |
N1 | 0.6620 (3) | 0.3537 (2) | 0.70405 (18) | 0.0191 (4) | |
N2 | 1.1687 (3) | 0.3027 (2) | 1.01843 (19) | 0.0222 (4) | |
N3 | 1.3182 (3) | 0.3681 (2) | 1.03825 (19) | 0.0245 (4) | |
H3A | 1.3433 | 0.4593 | 0.9726 | 0.029* | |
N4 | 1.3754 (4) | 0.1569 (3) | 1.2579 (2) | 0.0365 (5) | |
H4A | 1.4414 | 0.1037 | 1.3386 | 0.044* | |
H4B | 1.2748 | 0.1218 | 1.2414 | 0.044* | |
O1 | 1.5688 (3) | 0.3483 (2) | 1.17600 (17) | 0.0269 (4) | |
O2 | 0.7266 (3) | 0.3584 (2) | 0.40154 (18) | 0.0262 (4) | |
H2A | 0.672 (5) | 0.331 (4) | 0.355 (3) | 0.038 (8)* | |
H2B | 0.819 (5) | 0.276 (4) | 0.455 (3) | 0.034 (8)* | |
N5 | 0.3130 (3) | 0.3310 (3) | 0.5528 (2) | 0.0286 (4) | |
C8 | 0.2314 (3) | 0.2262 (3) | 0.5733 (2) | 0.0217 (5) | |
S1 | 0.11985 (9) | 0.07746 (7) | 0.60024 (7) | 0.02934 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0215 (2) | 0.0237 (2) | 0.0187 (2) | −0.00941 (15) | −0.00541 (14) | −0.00894 (17) |
C1 | 0.0178 (10) | 0.0241 (11) | 0.0205 (10) | −0.0042 (8) | −0.0029 (8) | −0.0126 (9) |
C2 | 0.0232 (11) | 0.0272 (11) | 0.0198 (10) | −0.0048 (9) | −0.0049 (8) | −0.0098 (9) |
C3 | 0.0296 (12) | 0.0293 (12) | 0.0245 (11) | −0.0137 (9) | −0.0049 (9) | −0.0046 (9) |
C4 | 0.0254 (11) | 0.0275 (12) | 0.0258 (11) | −0.0105 (9) | −0.0050 (9) | −0.0108 (10) |
C5 | 0.0238 (11) | 0.0234 (11) | 0.0200 (10) | −0.0076 (8) | −0.0038 (8) | −0.0090 (9) |
C6 | 0.0255 (11) | 0.0254 (11) | 0.0217 (10) | −0.0084 (9) | −0.0061 (9) | −0.0090 (9) |
C7 | 0.0261 (11) | 0.0275 (11) | 0.0195 (10) | −0.0021 (9) | −0.0064 (9) | −0.0137 (9) |
N1 | 0.0178 (8) | 0.0243 (9) | 0.0194 (8) | −0.0053 (7) | −0.0031 (7) | −0.0117 (7) |
N2 | 0.0219 (9) | 0.0266 (9) | 0.0237 (9) | −0.0060 (7) | −0.0063 (7) | −0.0136 (8) |
N3 | 0.0262 (10) | 0.0268 (10) | 0.0243 (9) | −0.0087 (8) | −0.0106 (8) | −0.0095 (8) |
N4 | 0.0436 (13) | 0.0440 (13) | 0.0234 (10) | −0.0202 (10) | −0.0125 (9) | −0.0051 (9) |
O1 | 0.0285 (9) | 0.0323 (9) | 0.0265 (8) | −0.0067 (7) | −0.0114 (7) | −0.0152 (7) |
O2 | 0.0291 (9) | 0.0309 (9) | 0.0235 (8) | −0.0049 (7) | −0.0093 (7) | −0.0144 (7) |
N5 | 0.0314 (11) | 0.0318 (10) | 0.0262 (10) | −0.0125 (8) | −0.0105 (8) | −0.0087 (8) |
C8 | 0.0229 (11) | 0.0254 (11) | 0.0179 (10) | −0.0060 (9) | −0.0079 (8) | −0.0073 (8) |
S1 | 0.0290 (3) | 0.0257 (3) | 0.0373 (4) | −0.0123 (3) | −0.0048 (3) | −0.0115 (3) |
Zn1—N5 | 2.109 (2) | C5—N1 | 1.343 (3) |
Zn1—N5i | 2.109 (2) | C5—H5 | 0.9500 |
Zn1—O2i | 2.1611 (16) | C6—N2 | 1.280 (3) |
Zn1—O2 | 2.1611 (16) | C6—H6 | 0.9500 |
Zn1—N1 | 2.2182 (18) | C7—O1 | 1.247 (3) |
Zn1—N1i | 2.2182 (18) | C7—N4 | 1.340 (3) |
C1—C2 | 1.396 (3) | C7—N3 | 1.364 (3) |
C1—C5 | 1.400 (3) | N2—N3 | 1.369 (3) |
C1—C6 | 1.463 (3) | N3—H3A | 0.8800 |
C2—C3 | 1.373 (3) | N4—H4A | 0.8800 |
C2—H2 | 0.9500 | N4—H4B | 0.8800 |
C3—C4 | 1.391 (3) | O2—H2A | 0.79 (4) |
C3—H3 | 0.9500 | O2—H2B | 0.87 (3) |
C4—N1 | 1.344 (3) | N5—C8 | 1.167 (3) |
C4—H4 | 0.9500 | C8—S1 | 1.641 (2) |
N5—Zn1—N5i | 180.0 | C3—C4—H4 | 118.7 |
N5—Zn1—O2i | 90.68 (8) | N1—C5—C1 | 123.8 (2) |
N5i—Zn1—O2i | 89.32 (8) | N1—C5—H5 | 118.1 |
N5—Zn1—O2 | 89.32 (8) | C1—C5—H5 | 118.1 |
N5i—Zn1—O2 | 90.68 (8) | N2—C6—C1 | 119.9 (2) |
O2i—Zn1—O2 | 180.000 (1) | N2—C6—H6 | 120.1 |
N5—Zn1—N1 | 90.02 (7) | C1—C6—H6 | 120.1 |
N5i—Zn1—N1 | 89.98 (7) | O1—C7—N4 | 123.7 (2) |
O2i—Zn1—N1 | 90.58 (6) | O1—C7—N3 | 119.6 (2) |
O2—Zn1—N1 | 89.42 (6) | N4—C7—N3 | 116.8 (2) |
N5—Zn1—N1i | 89.98 (7) | C5—N1—C4 | 117.08 (18) |
N5i—Zn1—N1i | 90.02 (7) | C5—N1—Zn1 | 121.60 (14) |
O2i—Zn1—N1i | 89.42 (6) | C4—N1—Zn1 | 121.28 (15) |
O2—Zn1—N1i | 90.58 (6) | C6—N2—N3 | 116.5 (2) |
N1—Zn1—N1i | 180.0 | C7—N3—N2 | 119.70 (19) |
C2—C1—C5 | 117.9 (2) | C7—N3—H3A | 120.1 |
C2—C1—C6 | 122.8 (2) | N2—N3—H3A | 120.1 |
C5—C1—C6 | 119.3 (2) | C7—N4—H4A | 120.0 |
C3—C2—C1 | 118.5 (2) | C7—N4—H4B | 120.0 |
C3—C2—H2 | 120.8 | H4A—N4—H4B | 120.0 |
C1—C2—H2 | 120.8 | Zn1—O2—H2A | 111 (2) |
C2—C3—C4 | 120.0 (2) | Zn1—O2—H2B | 118.7 (19) |
C2—C3—H3 | 120.0 | H2A—O2—H2B | 110 (3) |
C4—C3—H3 | 120.0 | C8—N5—Zn1 | 170.6 (2) |
N1—C4—C3 | 122.7 (2) | N5—C8—S1 | 178.9 (2) |
N1—C4—H4 | 118.7 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1ii | 0.79 (3) | 1.99 (3) | 2.723 (3) | 155 (3) |
O2—H2B···S1iii | 0.87 (3) | 2.49 (3) | 3.355 (2) | 170 (3) |
N3—H3A···O1iv | 0.88 | 1.98 | 2.862 (3) | 174 |
Symmetry codes: (ii) x−1, y, z−1; (iii) x+1, y, z; (iv) −x+3, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(NCS)2(C7H8N4O)2(H2O)2] |
Mr | 545.91 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 6.661 (1), 9.251 (2), 10.328 (2) |
α, β, γ (°) | 65.765 (2), 82.438 (2), 74.637 (2) |
V (Å3) | 559.4 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.33 |
Crystal size (mm) | 0.36 × 0.30 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.626, 0.742 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4371, 2169, 2028 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.107, 1.01 |
No. of reflections | 2169 |
No. of parameters | 159 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.74, −0.58 |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1i | 0.79 (3) | 1.99 (3) | 2.723 (3) | 155 (3) |
O2—H2B···S1ii | 0.87 (3) | 2.49 (3) | 3.355 (2) | 170 (3) |
N3—H3A···O1iii | 0.88 | 1.98 | 2.862 (3) | 174 |
Symmetry codes: (i) x−1, y, z−1; (ii) x+1, y, z; (iii) −x+3, −y+1, −z+2. |
Metal complexes based on Schiff base ligands being synthesized by condensation of pyridine-3-carbaldehydehyde and thiosemicarbazone, semicarbazone and other amines (Mendes et al., 2001; Li et al., 2006) have attracted numerous chemists and biologists due to their antimicrobial, cytotoxic and antioxidant activities. Structurally characterized metal-organic complexes of Schiff bases derived from the condensation of pyridine- 3-carbaldehydehyde and semicarbazone have been reported during the last several years. (Chen, Zhou, Liang et al., 2004; Chen, Zhou, Li et al., 2004; Beraldo et al. 2001). As a consecutive work of our studies, we report herein the synthesis and crystal structure of the title compound, (I).
The title compound, (I) (Fig. 1), is isostructural with the manganese derivative of the same ligand (Zhong et al., 2007). The central Zn atom is situated at an crystallographic center of inversion and is hexa-coordinated by two O atoms of water molecules and four N atoms, two of which come from two thiocyanate anions and the others from H-Pysc ligands (Fig. 1), forming a slightly distorted octahedral geometry. The molecules are held together by intermolecular hydrogen bonding interactions forming a three- dimensional supramolecular network. The coordinated water molecules (O2) donate H atoms to the terminal O1 atom and thiocyanate S atoms to form O—H···Oii and O—H···Siii hydrogen bonds, respectively [symmetry codes ii = -1 + x, y, -1 + z; iii = 1 + x, y, z]. The O1 atoms also accept H atom from N to form N—H···Oiv hydrogen bonds [symmetry codes iv = 3 - x, 1 - y, 2 - z] (Table 1, Fig. 2).