Download citation
Download citation
link to html
The title complex, [CdCl2(C10H8N4S)2(CH4O)2], a neutral mononuclear mol­ecule, consists of a CdII ion, two 6-methyl-3-phenyl-1,2,4-triazolo[3,4-b][1,3,4]thia­diazole ligands, two chloride ligands and two coordinated methanol mol­ecules. The CdII ion, located on a center of symmetry, displays a distorted octa­hedral coordination geometry. A supra­molecular network structure is formed by inter­molecular O—H...Cl hydrogen bonds and π–π contacts [centroid–centroid distance 3.613 (7) Å].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038524/zl2054sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038524/zl2054Isup2.hkl
Contains datablock I

CCDC reference: 660071

Key indicators

  • Single-crystal X-ray study
  • T = 291 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.019
  • wR factor = 0.051
  • Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1 (2) 2.02
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 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 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 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

The molecular structure of 6-methyl-3-phenyl-[1,2,4]triazolo(3,4 - b)-1,3,4-thiadiazole (Fornies-Marquina et al., 1974) and its substituted derivatives (Molina et al., 1989; Huang et al., 2005; Naveen et al., 2006) have been reported, however, no metal complexes of these ligands have so far been reported. In this paper, we report the crystal structure of the title compound, (I), a Cd complex obtained by the reaction of 6-methyl-3-phenyl-[1,2,4]triazolo(3,4 - b)-1,3,4-thiadiazole with cadmium chloride in methanol solution.

As illustrated in Fig. 1, the CdII atom, which is a neutral mononuclear molecule, lies on a centre of symmetry and has a distorted octahedral geometry with six coordinating atoms: two N atoms from two 6-methyl-3-phenyl-[1,2,4]triazolo(3,4 - b)-1,3,4-thiadiazole, two O from two methanol molecules and two chlorine atoms (Table 1). The structural components are connected through O—H···Cl hydrogen bonding involving the coordinating methanol molecules as donors and the Cl atoms as acceptors and π-π stacking interactions between the phenyl and triazolo rings, thus forming a supramolecular network structure (Fig. 2; Table 2). The centroid-centroid distance of adjacent phenyl and triazolo rings (at 1 - x,-y,1 - z) is 3.613 (7) Å, indicating a normal π-π interaction.

Related literature top

For related literature, see: Fornies-Marquina et al. (1974); Molina et al. (1989); Naveen et al. (2006).

For related literature, see: Huang et al. (2005).

Experimental top

The title complex was prepared by the addition of a stoichiometric amount of cadmium chloride (1 mmol) to a hot methanol solution (10 ml) of 2-methyl-5-phenyl-s-triazolo(3,4 - b)-1,3,4-thiadiazole (1 mmol). The resulting solution was filtered, and yellow blocky crystals were obtained on slow evaporation of the solvent over several days at room temperature.

Refinement top

Carbon-bound and hydroxyl H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93–0.97 or O—H = 0.82 Å, and with Uiso(H) = 1.2 or 1.5 Ueq(C, O). The terminal methyl and hydroxyl groups were also allowed free rotation.

Structure description top

The molecular structure of 6-methyl-3-phenyl-[1,2,4]triazolo(3,4 - b)-1,3,4-thiadiazole (Fornies-Marquina et al., 1974) and its substituted derivatives (Molina et al., 1989; Huang et al., 2005; Naveen et al., 2006) have been reported, however, no metal complexes of these ligands have so far been reported. In this paper, we report the crystal structure of the title compound, (I), a Cd complex obtained by the reaction of 6-methyl-3-phenyl-[1,2,4]triazolo(3,4 - b)-1,3,4-thiadiazole with cadmium chloride in methanol solution.

As illustrated in Fig. 1, the CdII atom, which is a neutral mononuclear molecule, lies on a centre of symmetry and has a distorted octahedral geometry with six coordinating atoms: two N atoms from two 6-methyl-3-phenyl-[1,2,4]triazolo(3,4 - b)-1,3,4-thiadiazole, two O from two methanol molecules and two chlorine atoms (Table 1). The structural components are connected through O—H···Cl hydrogen bonding involving the coordinating methanol molecules as donors and the Cl atoms as acceptors and π-π stacking interactions between the phenyl and triazolo rings, thus forming a supramolecular network structure (Fig. 2; Table 2). The centroid-centroid distance of adjacent phenyl and triazolo rings (at 1 - x,-y,1 - z) is 3.613 (7) Å, indicating a normal π-π interaction.

For related literature, see: Fornies-Marquina et al. (1974); Molina et al. (1989); Naveen et al. (2006).

For related literature, see: Huang et al. (2005).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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, 2004); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related to the labelled atoms by the symmetry operator (-x, 2 - y, -z).
[Figure 2] Fig. 2. A packing view of (I), showing the intermolecular hydrogen bonding interactions as broken lines.
Dichloridobis(methanol-κO)bis(6-methyl-3-phenyl-1,2,4-τriazolo[3,4-b][1,3,4]thiadiazole-κN1)cadmium(II) top
Crystal data top
[CdCl2(C10H8N4S)2(CH4O)2]Z = 1
Mr = 679.91F(000) = 342
Triclinic, P1Dx = 1.714 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7576 (9) ÅCell parameters from 2400 reflections
b = 8.6138 (11) Åθ = 1.4–28.0°
c = 12.1019 (15) ŵ = 1.23 mm1
α = 95.588 (1)°T = 291 K
β = 104.037 (1)°Block, yellow
γ = 102.496 (1)°0.44 × 0.31 × 0.22 mm
V = 658.81 (15) Å3
Data collection top
Bruker APEX II area-detector
diffractometer
2386 independent reflections
Radiation source: fine-focus sealed tube2327 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.011
φ and ω scansθmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.633, Tmax = 0.764k = 1010
4509 measured reflectionsl = 1414
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)] = 0.019Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.051H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0249P)2 + 0.3405P]
where P = (Fo2 + 2Fc2)/3
2386 reflections(Δ/σ)max < 0.001
171 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.45 e Å3
Crystal data top
[CdCl2(C10H8N4S)2(CH4O)2]γ = 102.496 (1)°
Mr = 679.91V = 658.81 (15) Å3
Triclinic, P1Z = 1
a = 6.7576 (9) ÅMo Kα radiation
b = 8.6138 (11) ŵ = 1.23 mm1
c = 12.1019 (15) ÅT = 291 K
α = 95.588 (1)°0.44 × 0.31 × 0.22 mm
β = 104.037 (1)°
Data collection top
Bruker APEX II area-detector
diffractometer
2386 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2327 reflections with I > 2σ(I)
Tmin = 0.633, Tmax = 0.764Rint = 0.011
4509 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.051H-atom parameters constrained
S = 1.12Δρmax = 0.46 e Å3
2386 reflectionsΔρmin = 0.45 e Å3
171 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
Cd10.00001.00000.00000.02382 (7)
Cl10.21045 (8)0.79569 (6)0.04065 (4)0.03678 (13)
S10.03252 (8)0.61793 (6)0.16761 (4)0.03174 (12)
O10.3105 (2)1.20734 (17)0.02416 (13)0.0378 (3)
H1A0.39611.19710.02450.057*
N10.0945 (3)0.9611 (2)0.19295 (13)0.0293 (4)
N20.1805 (3)1.0753 (2)0.29327 (14)0.0287 (3)
C70.1962 (3)0.9992 (2)0.38328 (16)0.0257 (4)
N30.1205 (2)0.83616 (18)0.34395 (13)0.0249 (3)
N40.0906 (3)0.69736 (19)0.39330 (14)0.0280 (3)
C10.3662 (3)1.2428 (3)0.52946 (18)0.0343 (4)
H10.36961.30280.46980.041*
C20.4460 (4)1.3187 (3)0.6438 (2)0.0411 (5)
H20.50061.42980.66000.049*
C30.4446 (3)1.2307 (3)0.73328 (18)0.0410 (5)
H30.49881.28220.80930.049*
C40.3625 (4)1.0656 (3)0.70944 (18)0.0400 (5)
H40.36221.00610.76960.048*
C50.2802 (3)0.9882 (3)0.59548 (17)0.0336 (4)
H50.22440.87730.57970.040*
C60.2815 (3)1.0772 (2)0.50492 (16)0.0266 (4)
C100.0617 (3)0.8198 (2)0.22672 (15)0.0265 (4)
C80.0103 (3)0.5756 (2)0.31026 (16)0.0292 (4)
C90.0456 (4)0.4066 (3)0.33259 (19)0.0425 (5)
H9A0.00250.40460.41380.064*
H9B0.02030.34150.29150.064*
H9C0.19570.36490.30690.064*
C110.3701 (4)1.3467 (3)0.1099 (2)0.0519 (6)
H10A0.25101.39140.10770.078*
H10B0.48141.42500.09530.078*
H10C0.41791.31760.18460.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02905 (11)0.02292 (11)0.01872 (10)0.00580 (8)0.00528 (7)0.00425 (7)
Cl10.0386 (3)0.0388 (3)0.0361 (3)0.0168 (2)0.0112 (2)0.0022 (2)
S10.0461 (3)0.0253 (2)0.0220 (2)0.0082 (2)0.0065 (2)0.00352 (19)
O10.0324 (8)0.0315 (8)0.0454 (9)0.0019 (6)0.0123 (7)0.0034 (6)
N10.0398 (9)0.0263 (8)0.0215 (8)0.0093 (7)0.0066 (7)0.0040 (6)
N20.0361 (9)0.0262 (8)0.0229 (8)0.0077 (7)0.0067 (7)0.0024 (6)
C70.0270 (9)0.0270 (9)0.0240 (9)0.0083 (8)0.0077 (7)0.0036 (7)
N30.0309 (8)0.0254 (8)0.0193 (7)0.0085 (7)0.0066 (6)0.0058 (6)
N40.0349 (9)0.0270 (8)0.0247 (8)0.0095 (7)0.0094 (7)0.0091 (7)
C10.0363 (11)0.0329 (11)0.0320 (10)0.0079 (9)0.0070 (9)0.0042 (9)
C20.0391 (12)0.0353 (11)0.0410 (12)0.0058 (9)0.0046 (9)0.0075 (10)
C30.0365 (11)0.0537 (14)0.0268 (10)0.0108 (10)0.0036 (9)0.0089 (10)
C40.0432 (12)0.0532 (14)0.0242 (10)0.0129 (11)0.0091 (9)0.0072 (9)
C50.0380 (11)0.0349 (11)0.0267 (10)0.0073 (9)0.0081 (8)0.0042 (8)
C60.0240 (9)0.0323 (10)0.0230 (9)0.0089 (8)0.0055 (7)0.0006 (8)
C100.0328 (10)0.0279 (10)0.0200 (9)0.0097 (8)0.0068 (7)0.0049 (7)
C80.0353 (10)0.0297 (10)0.0247 (9)0.0105 (8)0.0082 (8)0.0084 (8)
C90.0642 (15)0.0284 (11)0.0323 (11)0.0081 (10)0.0096 (10)0.0089 (9)
C110.0438 (13)0.0419 (14)0.0585 (16)0.0012 (11)0.0091 (11)0.0136 (11)
Geometric parameters (Å, º) top
Cd1—N1i2.3438 (16)C1—C61.390 (3)
Cd1—N12.3438 (16)C1—C21.394 (3)
Cd1—O1i2.3785 (14)C1—H10.9300
Cd1—O12.3785 (14)C2—C31.382 (3)
Cd1—Cl12.5721 (5)C2—H20.9300
Cd1—Cl1i2.5721 (5)C3—C41.383 (3)
S1—C101.731 (2)C3—H30.9300
S1—C81.7672 (19)C4—C51.394 (3)
O1—C111.423 (3)C4—H40.9300
O1—H1A0.9300C5—C61.398 (3)
N1—C101.313 (3)C5—H50.9300
N1—N21.399 (2)C8—C91.491 (3)
N2—C71.319 (3)C9—H9A0.9600
C7—N31.379 (2)C9—H9B0.9600
C7—C61.476 (2)C9—H9C0.9600
N3—C101.362 (2)C11—H10A0.9600
N3—N41.386 (2)C11—H10B0.9600
N4—C81.299 (3)C11—H10C0.9600
N1i—Cd1—N1180.00 (8)C3—C2—C1120.7 (2)
N1i—Cd1—O1i93.09 (6)C3—C2—H2119.7
N1—Cd1—O1i86.91 (6)C1—C2—H2119.7
N1i—Cd1—O186.91 (6)C2—C3—C4119.8 (2)
N1—Cd1—O193.09 (6)C2—C3—H3120.1
O1i—Cd1—O1180.0C4—C3—H3120.1
N1i—Cd1—Cl193.32 (4)C3—C4—C5120.1 (2)
N1—Cd1—Cl186.68 (4)C3—C4—H4119.9
O1i—Cd1—Cl192.17 (4)C5—C4—H4119.9
O1—Cd1—Cl187.83 (4)C4—C5—C6120.1 (2)
N1i—Cd1—Cl1i86.68 (4)C4—C5—H5120.0
N1—Cd1—Cl1i93.32 (4)C6—C5—H5120.0
O1i—Cd1—Cl1i87.83 (4)C1—C6—C5119.51 (18)
O1—Cd1—Cl1i92.17 (4)C1—C6—C7118.98 (18)
Cl1—Cd1—Cl1i180.00 (2)C5—C6—C7121.51 (18)
C10—S1—C887.32 (9)N1—C10—N3110.67 (16)
C11—O1—Cd1122.51 (14)N1—C10—S1139.33 (15)
C11—O1—H1A118.8N3—C10—S1110.00 (14)
Cd1—O1—H1A118.7N4—C8—C9122.19 (18)
C10—N1—N2106.37 (15)N4—C8—S1117.17 (15)
C10—N1—Cd1124.10 (12)C9—C8—S1120.63 (15)
N2—N1—Cd1129.41 (12)C8—C9—H9A109.5
C7—N2—N1108.57 (15)C8—C9—H9B109.5
N2—C7—N3108.37 (16)H9A—C9—H9B109.5
N2—C7—C6125.23 (17)C8—C9—H9C109.5
N3—C7—C6126.40 (17)H9A—C9—H9C109.5
C10—N3—C7106.01 (15)H9B—C9—H9C109.5
C10—N3—N4117.68 (15)O1—C11—H10A109.5
C7—N3—N4136.30 (15)O1—C11—H10B109.5
C8—N4—N3107.80 (15)H10A—C11—H10B109.5
C6—C1—C2119.8 (2)O1—C11—H10C109.5
C6—C1—H1120.1H10A—C11—H10C109.5
C2—C1—H1120.1H10B—C11—H10C109.5
Symmetry code: (i) x, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Cl1ii0.932.573.2005 (16)126
Symmetry code: (ii) x+1, y+2, z.

Experimental details

Crystal data
Chemical formula[CdCl2(C10H8N4S)2(CH4O)2]
Mr679.91
Crystal system, space groupTriclinic, P1
Temperature (K)291
a, b, c (Å)6.7576 (9), 8.6138 (11), 12.1019 (15)
α, β, γ (°)95.588 (1), 104.037 (1), 102.496 (1)
V3)658.81 (15)
Z1
Radiation typeMo Kα
µ (mm1)1.23
Crystal size (mm)0.44 × 0.31 × 0.22
Data collection
DiffractometerBruker APEX II area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.633, 0.764
No. of measured, independent and
observed [I > 2σ(I)] reflections
4509, 2386, 2327
Rint0.011
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.051, 1.12
No. of reflections2386
No. of parameters171
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.46, 0.45

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004), SHELXTL.

Selected geometric parameters (Å, º) top
Cd1—N12.3438 (16)Cd1—Cl12.5721 (5)
Cd1—O12.3785 (14)
N1i—Cd1—O1i93.09 (6)N1—Cd1—Cl186.68 (4)
N1i—Cd1—O186.91 (6)O1i—Cd1—Cl192.17 (4)
N1—Cd1—O193.09 (6)O1—Cd1—Cl187.83 (4)
N1i—Cd1—Cl193.32 (4)
Symmetry code: (i) x, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Cl1ii0.932.573.2005 (16)125.6
Symmetry code: (ii) x+1, y+2, z.
 

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