catena-Poly[bis­(sulfamethoxazolium) [[trichloridocadmate(II)]-μ-chlorido] monohydrate]

Annamalai Subashini; Packianathan Thomas Muthiah; Gabriele Bocelli; Andrea Cantoni

doi:10.1107/S1600536807067190

. 2007 Dec 21;64(Pt 1):m250–m251. doi: 10.1107/S1600536807067190

catena-Poly[bis(sulfamethoxazolium) [[trichloridocadmate(II)]-μ-chlorido] monohydrate]

Annamalai Subashini ^a, Packianathan Thomas Muthiah ^a,^*, Gabriele Bocelli ^b, Andrea Cantoni ^b

PMCID: PMC2915166 PMID: 21200590

Abstract

In the title compound, {(C₁₀H₁₂N₃O₃S)₂[CdCl₄]·H₂O}_n, the Cd^II atom is five-coordinate with a distorted trigonal–bipyramidal geometry formed by chloride ions. The Cd atom and two of the Cl atoms lie on a mirror plane. The cation is protonated on the amino group N atom; it is not coordinated to cadmium, but is hydrogen bonded to the chlorido ligands. Each water molecule bridges two chlorido ligands, generating ring motifs along the –Cd—Cl—Cd– chains. The isoxazole unit and the amide groups are linked through a pair of N—H⋯N hydrogen bonds. The crystal structure is stabilized by N—H⋯O, O—H⋯Cl, C—H⋯N, N—H⋯Cl and C—H⋯O hydrogen bonds.

Related literature

For related literature, see: Abramenko & Sergienko (2002 ▶); Bettinetti et al. (1982 ▶); Dai et al. (2002 ▶); Fawcett et al. (1978 ▶); Haridas et al. (1984 ▶); Kagi & Vallee (1960 ▶); Kálmán et al. (1981 ▶); Kendi et al. (2000 ▶); Schaffers & Keszler (1993 ▶); Singh et al. (1984 ▶); Subashini et al. (2007 ▶); Subha Nandhini et al. (2002 ▶); Takasuka & Nakai (2001 ▶); Tao et al. (2003 ▶); Yukawa et al. (1982 ▶).

Experimental

Crystal data

(C₁₀H₁₂N₃O₃S)₂[CdCl₄]·H₂O
M _r = 780.82
Orthorhombic,
a = 15.088 (2) Å
b = 35.028 (3) Å
c = 5.562 (3) Å
V = 2939.5 (17) Å³
Z = 4
Cu Kα radiation
μ = 11.07 mm⁻¹
T = 293 K
0.19 × 0.16 × 0.14 mm

Data collection

Siemens AED single-crystal diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.227, T _max = 0.306 (expected range = 0.157–0.212)
2834 measured reflections
2834 independent reflections
2470 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.111
S = 1.05
2834 reflections
203 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.04 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: local program (Belletti et al., 1993 ▶); cell refinement: local program; data reduction: local program; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807067190/fi2052sup1.cif

e-64-0m250-sup1.cif^{(23.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067190/fi2052Isup2.hkl

e-64-0m250-Isup2.hkl^{(136.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Cd1—Cl2	2.4828 (17)
Cd1—Cl3	2.469 (2)
Cd1—Cl1ⁱ	2.902 (2)
Cd1—Cl2ⁱⁱ	2.4828 (17)
Cd1—Cl1	2.6688 (19)

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Cl1—Cd1—Cl2ⁱⁱ	92.51 (3)
Cl2—Cd1—Cl3	113.69 (3)
Cl1ⁱ—Cd1—Cl2	84.90 (3)
Cl2—Cd1—Cl2ⁱⁱ	131.63 (4)
Cl1—Cd1—Cl2	92.51 (3)
Cl1—Cd1—Cl3	95.12 (5)
Cl1—Cd1—Cl1ⁱ	173.60 (5)
Cl1ⁱ—Cd1—Cl2ⁱⁱ	84.90 (3)
Cl1ⁱ—Cd1—Cl3	91.27 (5)
Cl2ⁱⁱ—Cd1—Cl3	113.69 (3)
Cd1—Cl1—Cd1ⁱⁱⁱ	173.60 (7)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯Cl3ⁱ	0.96	2.11	3.035 (5)	161
O1W—H2W⋯Cl3	0.95	2.11	3.036 (5)	164
N4—H4A⋯Cl2^iv	0.94 (5)	2.26 (5)	3.184 (4)	171 (4)
N4—H4B⋯O1W^v	0.91 (5)	1.86 (5)	2.758 (4)	169 (4)
N4—H4B⋯O1Wⁱⁱⁱ	0.91 (5)	1.86 (5)	2.758 (4)	169 (4)
N4—H4C⋯Cl2^vi	0.85 (4)	2.49 (4)	3.196 (4)	141 (4)
N4—H4C⋯O1^vi	0.85 (4)	2.33 (5)	2.871 (4)	122 (4)
N7—H7⋯N8^vii	0.86	2.58	3.188 (5)	129
C2—H2⋯O2	0.93	2.55	2.911 (4)	103
C9—H9⋯O2	0.93	2.50	2.991 (4)	113
C9—H9⋯N8ⁱ	0.93	2.58	3.354 (5)	141

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Symmetry codes: (i) Inline graphic ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

AS thanks Bharathidasan University, Tiruchirappalli, Tamil Nadu, India, for the award of a Research Studentship (Ref. CCCD/ PhD-2/15504/2004).

supplementary crystallographic information

Comment

Polynuclear d¹⁰– metal complexes have been found to exhibit intriguing structural and photoluminescent properties (Dai et al., 2002; Tao et al., 2003). Chloride-bridged cadmium(II) polymeric complexes are of considerable interest, because they may act as photoactive materials. Cadmium is found to occur naturally in at least one protein, metallothionein (Kagi & Vallee, 1960). Sulfonamides constitute an important class of antimicrobial agents. The drug, 4-[5-methylisoxazol-3-yl)aminosulfonyl] aniline [Sulfamethoxazole (SMZ)] prevents the formation of dihydrofolic acid, a compound that bacteria must be able to make in order to survive. The two polymorphs of SMZ (Bettinetti et al., 1982) have already been reported in literature. Recently, the crystal structure of sulfamethoxazole hydrochloride (Subashini et al., 2007) has been reported from our laboratory. X-ray analysis reveals that (I) possesses a polynuclear structure with the Cd atom and two of the Cl atoms on a special positions(m). The Cd atom has trigonal bipyramidal coordination geometry formed by five chloride anions. The Cd1—Cl1, Cd1—Cl2, Cd1—Cl3, and Cd—Clⁱ bond lengths are 2.669 (2), 2.4828 (17), 2.469 (2) and 2.902 (2)Å respectively. The mean Cd—Cl distance, 2.630 (2) Å, is in agreement with the corresponding distances reported in the structures of complexes of CdCl₂ with 4-hydroxy-L-proline [2.620 (2) Å] (Yukawa et al., 1982), β-alanine [2.619 (5) Å] (Subha Nandhini et al., 2002) and L– alanine [2.61 (1) Å] (Schaffers & Keszler, 1993). The Cd—Cl distances reported for tetrameric cadmium(II) complex (Fawcett et al., 1978), viz. 2.946 (6) and 2.946 (5) Å, are longer compared to those in the present structure.

The atoms around the sulfonamide S atom in (I) are arranged in a slightly distorted tetrahedral configuration. The largest deviation is in the angle O1—S1—O2 [121.22 (17)°], but it confirms to the non-tetrahedral nature commonly observed in sulfonamides (Haridas et al., 1984; Kendi et al., 2000; Takasuka & Nakai, 2001). The S1—C1 distance of 1.760 (3)Å (I) is a normal single-bond value and matches well with those observed in other sulfonamides (Singh et al., 1984; Abramenko & Sergienko, 2002). In the present structure the dihedral angle between the isoxazole and amino phenyl plane is found to be 88.31 (18)°, whereas in neutral SMZ structures the dihedral angles are 73.1 (5)° for Form 1 and 79.6 (6)° for Form 2 (Bettinetti et al., 1982) respectively. The two torsion angles τ₁ (C—C—S—N) and τ₂ (C—S—N—C) defining the conformation of the sulfonamide group are reported to lie in the range 70–120° and 60–90°, respectively (Kálmán et al., 1981). The torsion angles τ₁ is -81.9 (3)° (C6—C1—S1—N7) and τ₂ is -73.6 (3)° (C1—S1—N7—C8). In neutral forms, the torsion angles τ₁ are -76.5 (9)° (Form 1) and -78.5 (5)° (Form 2). The torsion angles τ₂ are -56.1 (4)° in form 1 and -61.5 (8)° in form 2. In sulfamethoxazole hydrochloride the torsion angles are (τ₁) 73.2 (3)° and (τ₂) -71.2 (3)° (Subashini et al., 2007). The cation is protonated on the amine nitrogen (N4) atom. The drug is not coordinated to cadmium and the amino group (N4) of the drug is hydrogen bonded to the chloride ions. 4-ammonio group acts as a bridge between the sulfonamide oxygen atom and water molecules. Four smz cations and two water molecules are connected through N—H···O hydrogen bonds forming a 24 membered ring with graph-set R⁴₆(24) (Fig. 2). The isoxazole moiety and the amide groups are paired through a pair of N—H···N hydrogen bonds. A C—H···N hydrogen bond is observed between isoxazole carbon (C9) and nitrogen (N8). The water O1W atom does not participate in coordination with cadmium. Each water molecule bridges two chloride ions generating ring motifs along the –Cd—Cl—Cd- chains as shown in Fig 3.

Experimental

Hot ethanol solution of sulfamethoxazole (Qualigens, 63 mg) and an aqueous solution of cadmium chloride (CdCl₂.2H₂O, 98%) (SISCO CHEM, 54 mg) were mixed in a 1:1 stoichiometric ratio. On slow evaporation light brown prismatic crystals of the title complex were formed.