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The title complex, {[Cd(C2O4)(C2H3N3S)(H2O)]·H2O}n, has a two-dimensional metal-organic framework, with the CdII cation coordinated by three oxalate ligands, a 1H-1,2,4-tri­az­ole-5(4H)-thione (H2trzS) ligand and a water mol­ecule. The CdO6S and oxalate units form an extended two-dimen­sional layered structure, with the terminal H2trzS ligands bonded to the CdII sites through the thione S atoms. Hydrogen-bond inter­actions exist between adjacent layers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614000102/wq3053sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614000102/wq3053Isup2.hkl
Contains datablock I

CCDC reference: 979478

Introduction top

In recent decades, the study of metal coordination polymers has witnessed tremendous growth as an attractive inter­face between synthetic chemistry and materials science. These studies have significantly boosted the understanding of the relationship between molecular structure and material function (Zhang et al., 2009, Wang, Zhang et al., 2010). Polyaza heterocyclic compounds have attracted considerable attention as ligands for producing coordination polymers with useful functional properties, such as gas storage (Zhang & Chen, 2008; Cha et al., 2010), magnetism (Ma et al., 2010; Wang, Liu et al., 2010) and catalysis (Wu et al., 2005; Jurss et al., 2010). As a ligand with multiple coordination sites, 1H-1,2,4-triazole-5(4H)-thione (H2trzS) has gained much attention, since it can bridge different metal centres to afford coordination polymers that exhibit extraordinary structural diversity (Cheng et al., 2009). Oxalate is unique due to its function as a bis-bidentate ligand, and a number of its coordination complexes have been obtained with rigid framework structures (García-Terán et al., 2004; Prasad et al., 2002). In some metal–organic frameworks (MOFs), more than one type of ligand has been used to expand their structural diversity, as well as to enhance their physical properties (García-Couceiro et al., 2005; Yang et al., 2013). In this work, we use both 1H-1,2,4-triazole-5(4H)-thione (H2trzS) and oxalate (ox) as mixed ligands to construct a new framework and report the structure of the title two-dimensional coordination polymer {[Cd(ox)(H2trzS)(H2O)].H2O}n, (I). To the best of our knowledge, (I) is the first example adopting the oxalate ligand as the second ligand among the H2trzS-based coordination polymers.

Experimental top

Synthesis and crystallization top

The title compound was prepared under mild hydro­thermal conditions. 3CdSO4.8H2O (0.133 mmol, 0.103 g), 1H-1,2,4-triazole-3-thiol (0.4 mmol, 0.0404 g), H2C2O4.2H2O (0.4 mmol, 0.0504 g) and water (5 ml) were placed in a Teflon-lined autoclave (23 ml) and the pH of the mixture was adjusted to 5.0 by slow addition of an NaOH (1.0 M) solution. The mixture was heated to 403 K for 4 [Time unit missing], and then cooled to room temperature at a rate of 5 K h-1. Colourless crystals of (I) suitable for X-ray analysis were obtained.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C and N atoms were refined in idealized positions using the riding-model approximation, with C—H = 0.93 Å, N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C,N). H atoms bonded to water O atoms were located in difference maps and treated as riding atoms [refined freely according to CIF data tables - please clarify], with a restraint of O—H = 0.840 (2) Å.

Comment top

Complex (I) is a two-dimensional coordination polymer. There is one CdII cation, one 1H-1,2,4-triazole-5(4H)-thione (H2trzS) group, two half-oxalate groups and two water molecules in the asymmetric unit (Fig. 1). Atom Cd1 is coordinated by six O atoms and a thione S atom from the monodentate H2trzS ligand. Water atom O5 is a terminal linkage. The Cd—O bond lengths are in the range 2.296 (2)–2.440 (2) Å and the Cd—S bond distance is 2.5637 (10) Å (Table 2). The C—O and C—N bond lengths are as expected.

In this structure, the CdO6S and oxalate units form an extended two-dimensional layered structure, with the η1-H2trzS ligands directly bonded to the CdII sites through the thione S atoms. The connectivity between the CdII cations and the oxalate units forms a unique layered architecture along the ab plane, with eight-membered re­cta­ngular apertures (four CdII cations and four oxalate ligands) within the layers, as shown in Fig. 2. The oxalate ligands link to the Cd1 sites of an adjacent aperture, forming the layered structure. It is noted that both µ2- and µ4-oxalate ligands are incorporated in this compound. In addition, the structure contains solvent water molecules, which extend the layers into a three-dimensional supra­molecular structure via hydrogen-bonding inter­actions (Fig. 3). Geometric details are given in Table 3.

Compared with the previously reported Cd analogue [CdCl2(H2trzS)2] (Zhang et al., 2008), the differences in the ancillary ligand and the diverse coordination modes of the H2trzS group lead to a different network. In (I), the µ2- and µ4-oxalate ligands connect the CdII sites into a layered structure. H2trzS in (I) adopts a monodentate η1-H2trzS coordination mode. By contrast, in [CdCl2(H2trzS)2], the CdII sites are linked through µ2-H2trzS and µ2-chloride ligands, affording a one-dimensional chain. Both monodentate η1-H2trzS and bidentate µ2-H2trzS are incorporated in this compound [Not clear - (I) or [CdCl2(H2trzS)2]?].

Powder X-ray diffraction (PXRD) experiments were carried out on (I) in order to establish the crystalline phase purity. As shown in Fig. 4, the major peak positions of the PXRD pattern of the bulk solid of (I) match well with those of the simulated pattern obtained from the single-crystal data, indicating the presence of mainly one crystalline phase in the coordination polymer.

The IR spectrum of complex (I) (Fig. 5) shows a medium–strong intensity band at 3469 cm-1, which can be assigned to the ν(OH) characteristic stretching frequency of the water molecules. The bands in the range of 2650–3000 cm-1 may be attributable to the ν(NH) and ν(CH) stretching frequency of the H2trzS ring. The band at 1316 cm-1 may be attributable to the symmetric vibration of the carboxyl­ate groups and that at 1597 cm-1 may be attributable to the asymmetric vibration of the carboxyl­ate groups. In the range 788–960 cm-1, many deformation vibrations and combinations of the H2trzS ring can be found (Liu et al., 2009).

In summary, a new cadmium coordination polymer has been prepared using the mixed ligands 1H-1,2,4-triazole-5(4H)-thione and oxalate under hydro­thermal conditions. This result reveals that the mixed-ligand synthetic approach is viable for obtaining unusual MOFs in H2trzS-based systems.

Related literature top

For related literature, see: Cha et al. (2010); Cheng et al. (2009); García-Couceiro, Olea, Castillo, Luque, Román, de Pablo, Gómez-Herrero, Zamora & l (2005); García-Terán, Castillo, Luque, García-Couceiro, Román & Lezama (2004); Jurss et al. (2010); Liu et al. (2009); Ma et al. (2010); Prasad et al. (2002); Wang, Liu, Huang, Sui, Huang, Chen & You (2010); Wang, Zhang, Liu, Shan, Cao, Wang, Luo & Yang (2010); Wu et al. (2005); Yang et al. (2013); Zhang & Chen (2008); Zhang et al. (2009); Zhang, Li, Cheng, Qin, Zhang & Yao (2008).

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
Fig. 1. The structure of (I), showing the atom-numbering scheme and 30% probability displacement ellipsoids. H atoms have been omitted for clarity. [Symmetry codes: (i) -x, -y + 2, -z + 1; (ii) -x - 1, -y + 1, -z + 1; (iii) ?, ?, ? [Please provide missing details]]

Fig. 2. A view of the two-dimensional layer in (I). All H atoms have been omitted for clarity.

Fig. 3. A packing diagram for (I), showing the hydrogen bonds (dashed lines). All H atoms, except for those involved in the weak interactions, have been omitted. All atoms are shown as wires or sticks.

Fig. 4. Simulated (bottom) and experimental (top) powder X-ray diffraction patterns of (I).

Fig. 5. The IR spectrum of (I).
Poly[[aqua(µ-oxalato)[1H-1,2,4-triazole-5(4H)-thione]cadmium(II)] monohydrate] top
Crystal data top
[Cd(C2O4)(C2H3N3S)(H2O)]·H2OZ = 2
Mr = 337.61F(000) = 328
Triclinic, P1Dx = 2.340 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.1241 (12) ÅCell parameters from 1807 reflections
b = 8.4939 (17) Åθ = 3.4–27.5°
c = 10.224 (2) ŵ = 2.51 mm1
α = 67.94 (3)°T = 298 K
β = 80.46 (3)°Parallelepiped, colourless
γ = 77.48 (3)°0.18 × 0.13 × 0.11 mm
V = 479.08 (16) Å3
Data collection top
Rigaku Saturn 724 CCD area-detector
diffractometer
2096 independent reflections
Radiation source: fine-focus sealed tube2063 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
scintillation counter scansθmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2002)
h = 77
Tmin = 0.566, Tmax = 0.655k = 811
3967 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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0243P)2 + 0.645P]
where P = (Fo2 + 2Fc2)/3
2096 reflections(Δ/σ)max = 0.008
152 parametersΔρmax = 0.50 e Å3
6 restraintsΔρmin = 0.58 e Å3
Crystal data top
[Cd(C2O4)(C2H3N3S)(H2O)]·H2Oγ = 77.48 (3)°
Mr = 337.61V = 479.08 (16) Å3
Triclinic, P1Z = 2
a = 6.1241 (12) ÅMo Kα radiation
b = 8.4939 (17) ŵ = 2.51 mm1
c = 10.224 (2) ÅT = 298 K
α = 67.94 (3)°0.18 × 0.13 × 0.11 mm
β = 80.46 (3)°
Data collection top
Rigaku Saturn 724 CCD area-detector
diffractometer
2096 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2002)
2063 reflections with I > 2σ(I)
Tmin = 0.566, Tmax = 0.655Rint = 0.029
3967 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0236 restraints
wR(F2) = 0.061H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.50 e Å3
2096 reflectionsΔρmin = 0.58 e Å3
152 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
Cd10.06101 (3)0.72697 (2)0.36944 (2)0.02138 (8)
S10.16890 (14)0.67263 (11)0.13487 (8)0.03012 (18)
O10.0964 (4)0.8018 (3)0.5624 (2)0.0281 (5)
O20.1294 (4)0.9938 (3)0.6672 (2)0.0287 (5)
O50.2415 (4)0.9201 (3)0.2340 (3)0.0376 (6)
OW10.2909 (6)0.1351 (4)0.0417 (3)0.0519 (7)
N10.6216 (4)0.5468 (3)0.1247 (3)0.0283 (5)
H10.66410.64150.06840.034*
N20.6448 (5)0.2761 (4)0.2602 (3)0.0333 (6)
N30.4260 (4)0.3591 (3)0.2547 (3)0.0285 (5)
H30.31300.30960.29890.034*
C10.4083 (5)0.5249 (4)0.1733 (3)0.0243 (6)
C20.7569 (6)0.3954 (5)0.1792 (4)0.0335 (7)
H20.91240.37850.16090.040*
C30.0652 (5)0.9420 (3)0.5665 (3)0.0205 (5)
O30.2238 (3)0.4587 (3)0.5331 (2)0.0244 (4)
C40.4311 (5)0.4276 (4)0.5450 (3)0.0203 (5)
O40.5387 (4)0.2902 (3)0.6223 (3)0.0324 (5)
H40.257 (7)1.023 (2)0.229 (6)0.082 (19)*
H50.364 (4)0.887 (5)0.273 (6)0.086 (19)*
HW20.237 (8)0.089 (6)0.1253 (18)0.072 (17)*
HW10.270 (12)0.076 (7)0.004 (5)0.13 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.01985 (12)0.01948 (14)0.02487 (12)0.00268 (8)0.00135 (8)0.00853 (9)
S10.0284 (4)0.0344 (4)0.0263 (4)0.0008 (3)0.0035 (3)0.0123 (3)
O10.0336 (12)0.0221 (11)0.0300 (11)0.0121 (9)0.0076 (9)0.0110 (9)
O20.0361 (12)0.0230 (11)0.0267 (10)0.0103 (9)0.0074 (9)0.0098 (9)
O50.0302 (13)0.0231 (13)0.0542 (16)0.0053 (10)0.0046 (11)0.0071 (11)
OW10.068 (2)0.0374 (16)0.0416 (15)0.0230 (14)0.0027 (14)0.0008 (13)
N10.0274 (13)0.0267 (14)0.0303 (13)0.0090 (11)0.0038 (10)0.0098 (11)
N20.0287 (14)0.0284 (15)0.0386 (15)0.0002 (11)0.0011 (11)0.0105 (12)
N30.0262 (13)0.0237 (13)0.0332 (13)0.0071 (10)0.0028 (10)0.0081 (11)
C10.0286 (15)0.0253 (15)0.0216 (13)0.0066 (12)0.0019 (11)0.0119 (12)
C20.0258 (16)0.042 (2)0.0345 (16)0.0056 (14)0.0025 (13)0.0173 (15)
C30.0205 (13)0.0159 (14)0.0225 (13)0.0045 (10)0.0010 (10)0.0035 (11)
O30.0170 (9)0.0214 (10)0.0323 (11)0.0053 (8)0.0028 (8)0.0052 (9)
C40.0207 (13)0.0187 (14)0.0223 (13)0.0043 (11)0.0013 (10)0.0080 (11)
O40.0217 (11)0.0267 (12)0.0420 (13)0.0027 (9)0.0099 (9)0.0024 (10)
Geometric parameters (Å, º) top
Cd1—O12.296 (2)N1—C21.343 (5)
Cd1—O2i2.377 (2)N1—C11.345 (4)
Cd1—O32.386 (2)N1—H10.8600
Cd1—O52.422 (3)N2—C21.290 (4)
Cd1—O4ii2.438 (2)N2—N31.371 (4)
Cd1—O3iii2.441 (2)N3—C11.331 (4)
Cd1—S12.5643 (10)N3—H30.8600
S1—C11.704 (3)C2—H20.9300
O1—C31.263 (3)C3—C3i1.559 (5)
O2—C31.241 (3)O3—C41.256 (3)
O2—Cd1i2.377 (2)O3—Cd1iii2.441 (2)
O5—H40.840 (2)C4—O41.252 (4)
O5—H50.840 (2)C4—C4ii1.553 (5)
OW1—HW20.840 (2)O4—Cd1ii2.438 (2)
OW1—HW10.840 (2)
O1—Cd1—O2i70.83 (8)H4—O5—H5105.8 (5)
O1—Cd1—O387.12 (8)HW2—OW1—HW1105.9 (5)
O2i—Cd1—O3127.38 (8)C2—N1—C1108.3 (3)
O1—Cd1—O590.01 (9)C2—N1—H1125.9
O2i—Cd1—O576.08 (9)C1—N1—H1125.9
O3—Cd1—O5153.24 (8)C2—N2—N3103.5 (3)
O1—Cd1—O4ii102.59 (9)C1—N3—N2112.4 (3)
O2i—Cd1—O4ii71.42 (8)C1—N3—H3123.8
O3—Cd1—O4ii67.73 (8)N2—N3—H3123.8
O5—Cd1—O4ii138.57 (8)N3—C1—N1104.1 (3)
O1—Cd1—O3iii78.97 (8)N3—C1—S1127.7 (2)
O2i—Cd1—O3iii142.39 (8)N1—C1—S1128.2 (2)
O3—Cd1—O3iii71.16 (8)N2—C2—N1111.8 (3)
O5—Cd1—O3iii82.17 (8)N2—C2—H2124.1
O4ii—Cd1—O3iii138.69 (8)N1—C2—H2124.1
O1—Cd1—S1169.54 (6)O2—C3—O1125.3 (3)
O2i—Cd1—S1108.16 (6)O2—C3—C3i118.0 (3)
O3—Cd1—S1101.12 (6)O1—C3—C3i116.7 (3)
O5—Cd1—S179.73 (7)C4—O3—Cd1119.76 (18)
O4ii—Cd1—S186.61 (7)C4—O3—Cd1iii130.91 (19)
O3iii—Cd1—S197.48 (6)Cd1—O3—Cd1iii108.84 (8)
C1—S1—Cd1100.58 (10)O4—C4—O3126.2 (3)
C3—O1—Cd1118.45 (18)O4—C4—C4ii116.4 (3)
C3—O2—Cd1i115.75 (18)O3—C4—C4ii117.4 (3)
Cd1—O5—H4115 (4)C4—O4—Cd1ii118.60 (19)
Cd1—O5—H5109 (4)
Symmetry codes: (i) x, y+2, z+1; (ii) x+1, y+1, z+1; (iii) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···OW1iv0.861.862.712 (4)170
OW1—HW2···O2iii0.84 (1)2.01 (1)2.842 (4)170 (5)
N3—H3···O1iii0.861.892.733 (3)165
O5—H5···O4iii0.84 (1)1.92 (2)2.686 (3)152 (4)
Symmetry codes: (iii) x, y+1, z+1; (iv) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[Cd(C2O4)(C2H3N3S)(H2O)]·H2O
Mr337.61
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)6.1241 (12), 8.4939 (17), 10.224 (2)
α, β, γ (°)67.94 (3), 80.46 (3), 77.48 (3)
V3)479.08 (16)
Z2
Radiation typeMo Kα
µ (mm1)2.51
Crystal size (mm)0.18 × 0.13 × 0.11
Data collection
DiffractometerRigaku Saturn 724 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2002)
Tmin, Tmax0.566, 0.655
No. of measured, independent and
observed [I > 2σ(I)] reflections
3967, 2096, 2063
Rint0.029
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.061, 1.08
No. of reflections2096
No. of parameters152
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.50, 0.58

Computer programs: CrystalClear (Rigaku, 2002), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Cd1—O12.296 (2)Cd1—O4ii2.438 (2)
Cd1—O2i2.377 (2)Cd1—O3iii2.441 (2)
Cd1—O32.386 (2)Cd1—S12.5643 (10)
Cd1—O52.422 (3)
O1—Cd1—O2i70.83 (8)O3—Cd1—O3iii71.16 (8)
O1—Cd1—O387.12 (8)O5—Cd1—O3iii82.17 (8)
O1—Cd1—O590.01 (9)O1—Cd1—S1169.54 (6)
O3—Cd1—O5153.24 (8)O3—Cd1—S1101.12 (6)
O3—Cd1—O4ii67.73 (8)O3iii—Cd1—S197.48 (6)
O5—Cd1—O4ii138.57 (8)
Symmetry codes: (i) x, y+2, z+1; (ii) x+1, y+1, z+1; (iii) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···OW1iv0.861.862.712 (4)170
OW1—HW2···O2iii0.840 (2)2.011 (8)2.842 (4)170 (5)
N3—H3···O1iii0.861.892.733 (3)165
O5—H5···O4iii0.840 (2)1.92 (2)2.686 (3)152 (4)
Symmetry codes: (iii) x, y+1, z+1; (iv) x+1, y+1, z.
 

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