Crystal structure of (1,3-thia­zole-2-carboxyl­ato-κN)(1,3-thia­zole-2-carb­oxy­lic acid-κN)silver(I)

Meundaeng, N.; Rujiwatra, A.; Prior, T.J.

doi:10.1107/S2056989019000124

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 2| February 2019| Pages 185-188

https://doi.org/10.1107/S2056989019000124

Open

access

Crystal structure of (1,3-thiazole-2-carboxylato-κN)(1,3-thiazole-2-carboxylic acid-κN)silver(I)

Natthaya Meundaeng,^a Apinpus Rujiwatra ^b and Timothy J. Prior ^c ^*

^aDepartment of Chemistry, Faculty of Science, King Mongkut's Institute of Technology Ladkrabang, Bangkok, 10520, Thailand, ^bDepartment of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand, and ^cChemistry, University of Hull, Kingston upon Hull, HU6 7RX, UK
^*Correspondence e-mail: t.prior@hull.ac.uk

Edited by G. S. Nichol, University of Edinburgh, Scotland (Received 15 October 2018; accepted 3 January 2019; online 11 January 2019)

The linear two-coordinate silver (I) complex [Ag(C₄H₂NO₂S)(C₄H₃NO₂S)] or [Ag(2-Htza)(2-tza)] is reported (2-Htza = 1,3-thiazole-2-carboxylic acid). The Ag^I ion is coordinated by two heterocyclic N atoms from two ligands in a linear configuration, forming a discrete coordination complex. There is an O—H⋯O hydrogen bond between 2-tza⁻ and 2tzaH of adjacent complexes. The hydrogen atom is shared between the two oxygen atoms. This interaction produces a hydrogen-bonded tape parallel to the [110] direction, which is augmented through intermolecular C—H⋯O hydrogen-bonding interactions between the bound thiazole groups. There is a further rather long Ag⋯O interaction [2.8401 (13) Å, compared with a mean of 2.54 (11) Å for 23 structures in the CSD] that assembles these tapes into columns, between which there are C—H⋯π interactions, leading to the formation of a three-dimensional supramolecular architecture.

Keywords: silver; 2-thiazolecarboxylic acid; hydrogen bonding; crystal structure.

CCDC reference: 1888609

1. Chemical context

1,3-Thiazoles have been known for over a century and many of their derivatives exhibit potential applications, particularly in drug design and biological activity (Ayati et al., 2015 ; Kashyap et al., 2012 ). The thiazolecarboxylic acids have also received attention as ligands in complexes of the first-row transition metals. This is due to the co-presence of the heterocyclic ring and the carboxyl group providing various coordination modes (Frija et al., 2016 ). They also favour the assembly of supramolecular architectures by establishing a variety of non-covalent interactions e.g. hydrogen bonding and π–π stacking interactions (Desiraju, 2002 ; Sherrington & Taskinen, 2001 ; Blake et al., 1999 ). Recently, we reported the syntheses and structural features of Co^II, Ni^II, and Cu^II complexes with thiazole-4-carboxylate (Meundaeng et al., 2016 ) and thiazole-5-carboxylate (Meundaeng et al., 2017 ). Herein we report the synthesis and crystal structure of the Ag^I complex with thiazole-2-carboxylic acid (2-tza).

2. Structural commentary

The monomeric complex of the title compound crystallizes in the monoclinic space group P2₁/c. The asymmetric unit contains one Ag^I ion and one 2-tza ligand which is formally 2-tza(H)_1/2. The whole molecular structure can be generated by an inversion centre; the Ag^I atom is located at the 2a Wyckoff position ( $[\overline{1}]$ ) (Fig. 1). The Ag^I centre shows a linear coordination with two 2-tza ligands coordinating through the heterocyclic N atoms with an Ag—N bond length of 2.1463 (14) Å. Statistically one of these ligands has an appended carboxylic acid and the other a carboxylate. A rather long Ag⋯O2 interaction is also observed with the distance of 2.8401 (13) Å. This is significantly larger than the mean value [2.54 (11) Å] of the Ag⋯O=C distances in the Cambridge Database (version 5.37 up to October 2018; Groom et al., 2016 ; 23 hits, silver bound by two nitrogen atoms, Ag⋯O=C distance recorded) and suggests that the interaction between the carbonyl and the silver atom is very weak. No interactions between the Ag centres are observed.

Figure 1
Molecular structure of [Ag(2-Htza)(2-tza)] with 50% probability ellipsoids showing the atom-labelling scheme. Symmetry code: (i) –x, 1 − y, 1 − z.

3. Supramolecular features

In order to balance charge in this structure, the 2-tza ligand must be half protonated but we see no evidence for crystallographic ordering of the hydrogen position. In late stages of refinement, a maximum of electron density in the difference-Fourier map was present located 0.897 Å from the atom O2. This was modelled as a half occupied hydrogen atom. Thus, the overall composition is Ag⁺(2-Htza)(2-tza⁻). The carboxylate is located close to a second symmetry-equivalent carboxylate generated by the symmetry operation 1 − x, −y, 1 − z. Statistically, one of these two groups is protonated. The close approach facilitates the formation of a linear hydrogen bond between them (Table 1) and the O⋯O distance of 2.470 (3) Å strongly suggests that there is a hydrogen bond. Strangely, it is not the case that the O2—H2 distance is half the O2⋯O2ⁱ distance as is sometimes observed in similar systems (Leiva et al., 1999 ; Deloume et al., 1977 ). The partially occupied H2 atom is clearly identified from a Fourier map at the closer distance to the atom O2. Furthermore, the carboxyl O1 atom serves as a hydrogen-bonding acceptor with the heterocyclic H3 atom (Csp²—H⋯C=O) of an adjacent discrete molecule (Table 1). The occurrence of these hydrogen-bonding interactions results in the formation of a one-dimensional tape along the [110] direction (Fig. 2a). This tape is inclined at an angle of 55.278 (19)° with the (001) plane. Each tape is connected through an Ag⋯O1 interaction [d(Ag⋯O1) = 2.9606 (14) Å], generating columns of complex molecules along the [100] direction (Fig. 2b). These columns are further linked via C—H⋯π interactions between the thiazole rings (Table 1), leading to the formation of a three-dimensional supramolecular architecture (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the S1/N1/C2–C4 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O2ⁱ	0.84	1.65	2.470 (3)	165
C3—H3⋯O1ⁱⁱ	0.92	2.37	3.280 (2)	170
C4—H4⋯Cgⁱⁱⁱ	0.91 (3)	2.90 (2)	3.688 (2)	146 (1)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x-1, y+1, z; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
View of (a) hydrogen-bonding interactions (red dashed lines) leading to the formation of a one-dimensional tape along the [110] direction [symmetry codes: (i) −x + 1, −y, −z + 1, (ii) x − 1, y + 1, z] and (b) the weak Ag⋯O interactions (black dashed lines) holding each tape into a column.

Figure 3
View of supramolecular interactions; hydrogen bonds between the discrete units (red dashed lines), Ag⋯O interactions between adjacent one-dimensional tapes (black dashed lines) and C—H⋯π interactions between adjacent columns (purple dashed lines).

4. Database survey

A search of the Cambridge Structural Database (CSD version 5.37 up to October 2018; Groom et al., 2016) revealed a rather small number of previous reports of metal-containing compounds with thiazolecarboxylic acids: (i) there are three reports of thiazole-2-carboxylic acid (2-tza) structures, i.e. two tin^IV complexes (Yin & Wang, 2004 ; Yin et al., 2005 ) and a Zn^II complex (Rossin et al., 2011 ); (ii) three reports of structures with thiazole-4-carboxylic acid (4-tza) i.e. Cu^II and Zn^II complexes (Rossin et al., 2011) and Co^II, Ni^II, Cu^II complexes (Meundaeng et al., 2016) and one with Sn^IV (Gao et al., 2016 ); and two reports of thiazole-5-carboxylic acid (5-tza) complexes each with Cu^II (Rossin et al., 2014 ; Meundaeng et al., 2017). While the 4-tza ligand provides a predictable [N,O]-chelating mode of coordination and the 5-tza ligand exhibits bridging ability through its aromatic N atom and carboxyl O atom, the coordination of the 2-tza ligand to the metal occurs through O-monodentate, [N,O]- and [O,O]-chelating modes. So far, the S atom on the thiazole ring has been entirely innocent in the chemistry described. Compared to those first-row transition metals, the softer Ag^I ion could be a good candidate for the exploration of the coordination chemistry of these ligands, particularly the 2-tza ligand, as it can possibly bind to the metal ion in various modes of coordination: N- and O-monodentate, [N,O]-, [O,O]- and [S,O]-chelating modes.

5. Synthesis and crystallization

AgNO₃ (0.0170 g, 0.100 mmol) and 2-Htza (0.0129 g, 0.100 mmol) were dissolved in 5.0 mL of deionized water in a small vial (ca 16 mm in diameter). The vial was left undisturbed at ambient temperature for three days during which colourless block-shaped crystals of the title compound crystallized and were isolated for X-ray data collection.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydroxy H atom was positioned geometrically (O—H = 0.84) and refined as riding, with U_iso(H) = 1.5U_eq(O). The C-bound H atoms were refined isotropically, with U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[Ag(C₄H₂NO₂S)(C₄H₃NO₂S)]
M_r	365.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	5.8613 (9), 5.0180 (6), 18.278 (3)
β (°)	98.303 (13)
V (Å³)	531.94 (14)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.29
Crystal size (mm)	0.25 × 0.18 × 0.10

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Multi-scan (SORTAV; Blessing, 1995 )
T_min, T_max	0.868, 0.927
No. of measured, independent and observed [I > 2σ(I)] reflections	3482, 1691, 1354
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.725

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.044, 0.90
No. of reflections	1691
No. of parameters	82
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.34
Computer programs: X-AREA (Stoe & Cie, 2002 ), SORTAV (Blessing, 1995), SHELXT (Sheldrick, 2015a ), SHELXL2014/7 (Sheldrick, 2015b ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and CrystalMaker (Palmer, 2014 ).

Supporting information

CCDC reference: 1888609

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019000124/nk2248sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019000124/nk2248Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019000124/nk2248Isup3.mol

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and CrystalMaker (Palmer, 2014); software used to prepare material for publication: WinGX (Farrugia, 2012).

(1,3-Thiazole-2-carboxylato-κN)(1,3-thiazole-2-carboxylic acid-κN)silver(I) top

Crystal data top

[Ag(C₄H₂NO₂S)(C₄H₃NO₂S)]	F(000) = 356
M_r = 365.13	D_x = 2.280 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.8613 (9) Å	Cell parameters from 3235 reflections
b = 5.0180 (6) Å	θ = 3.5–34.2°
c = 18.278 (3) Å	µ = 2.29 mm⁻¹
β = 98.303 (13)°	T = 150 K
V = 531.94 (14) Å³	Block, colourless
Z = 2	0.25 × 0.18 × 0.10 mm

Data collection top

Stoe IPDS2 diffractometer	1354 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.026
ω–scans	θ_max = 31.0°, θ_min = 3.5°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −8→8
T_min = 0.868, T_max = 0.927	k = −7→6
3482 measured reflections	l = −21→26
1691 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.020	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.044	w = 1/[σ²(F_o²) + (0.0208P)²] where P = (F_o² + 2F_c²)/3
S = 0.90	(Δ/σ)_max < 0.001
1691 reflections	Δρ_max = 0.45 e Å⁻³
82 parameters	Δρ_min = −0.33 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ag1	0.0000	0.5000	0.5000	0.02294 (6)
S1	0.39928 (7)	0.66825 (9)	0.30440 (3)	0.01892 (9)
O2	0.3909 (2)	0.1980 (3)	0.47470 (7)	0.0195 (3)
H2	0.4842	0.0819	0.4938	0.029*	0.5
O1	0.6413 (2)	0.2412 (3)	0.39263 (8)	0.0245 (3)
N1	0.1394 (2)	0.6325 (3)	0.40394 (8)	0.0153 (3)
C4	0.1715 (3)	0.8824 (4)	0.30037 (11)	0.0192 (3)
H4	0.1351 (11)	1.009 (4)	0.2649 (10)	0.023*
C3	0.0518 (3)	0.8370 (4)	0.35772 (10)	0.0169 (3)
H3	−0.076 (3)	0.934 (2)	0.3650 (2)	0.020*
C2	0.3237 (2)	0.5272 (3)	0.38216 (9)	0.0140 (3)
C1	0.4673 (3)	0.3028 (3)	0.41895 (10)	0.0160 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.01955 (8)	0.03224 (11)	0.01899 (10)	0.00117 (9)	0.00935 (6)	0.00427 (10)
S1	0.01923 (17)	0.0192 (2)	0.0203 (2)	0.00206 (15)	0.00930 (15)	0.00304 (17)
O2	0.0197 (5)	0.0164 (6)	0.0221 (7)	0.0033 (4)	0.0023 (5)	0.0040 (5)
O1	0.0193 (5)	0.0224 (6)	0.0331 (8)	0.0073 (5)	0.0078 (5)	0.0006 (6)
N1	0.0140 (5)	0.0158 (7)	0.0162 (7)	0.0018 (5)	0.0028 (5)	−0.0001 (6)
C4	0.0205 (7)	0.0149 (8)	0.0216 (9)	0.0025 (6)	0.0015 (7)	0.0040 (7)
C3	0.0161 (6)	0.0153 (7)	0.0189 (8)	0.0028 (6)	0.0012 (6)	−0.0005 (7)
C2	0.0133 (6)	0.0137 (7)	0.0152 (7)	0.0005 (5)	0.0031 (5)	0.0007 (7)
C1	0.0149 (6)	0.0128 (7)	0.0195 (8)	0.0011 (5)	0.0000 (6)	−0.0023 (7)

Geometric parameters (Å, º) top

Ag1—N1ⁱ	2.1463 (14)	N1—C2	1.3151 (19)
Ag1—N1	2.1463 (14)	N1—C3	1.380 (2)
S1—C2	1.7026 (17)	C4—C3	1.362 (2)
S1—C4	1.7071 (18)	C4—H4	0.91 (3)
O2—C1	1.283 (2)	C3—H3	0.92 (2)
O2—H2	0.8400	C2—C1	1.505 (2)
O1—C1	1.2280 (19)

N1ⁱ—Ag1—N1	180.00 (8)	C4—C3—N1	114.09 (14)
C2—S1—C4	90.10 (8)	C4—C3—H3	123.0
C1—O2—H2	109.5	N1—C3—H3	123.0
C2—N1—C3	111.27 (14)	N1—C2—C1	126.61 (14)
C2—N1—Ag1	123.33 (12)	N1—C2—S1	114.18 (13)
C3—N1—Ag1	125.39 (10)	C1—C2—S1	119.21 (11)
C3—C4—S1	110.35 (14)	O1—C1—O2	127.78 (16)
C3—C4—H4	124.8	O1—C1—C2	117.10 (15)
S1—C4—H4	124.8	O2—C1—C2	115.12 (13)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the S1/N1/C2–C4 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O2ⁱⁱ	0.84	1.65	2.470 (3)	165
C3—H3···O1ⁱⁱⁱ	0.92	2.37	3.280 (2)	170
C4—H4···Cg^iv	0.91 (3)	2.90 (2)	3.688 (2)	146 (1)

Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x−1, y+1, z; (iv) −x, y+1/2, −z+1/2.

Funding information

This work was funded by the Thailand Research Fund and the National Research University Project. NM thanks the Science Achievement Scholarship of Thailand and the Graduate School, Chiang Mai University for the PhD scholarship.

References

Ayati, A., Emami, S., Asadipour, A., Shafiee, A. & Foroumadi, A. (2015). Eur. J. Med. Chem. 97, 699–718. CrossRef CAS Google Scholar
Blake, A. J., Champness, N. R., Hubberstey, P., Li, W.-S., Withersby, M. A. & Schröder, M. (1999). Coord. Chem. Rev. 183, 117–138. Web of Science CrossRef CAS Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Deloume, J.-P., Faure, R. & Loiseleur, H. (1977). Acta Cryst. B33, 2709–2712. CrossRef CAS IUCr Journals Google Scholar
Desiraju, G. R. (2002). Acc. Chem. Res. 35, 565–573. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Frija, L. M. T., Pombeiro, A. J. L. & Kopylovich, M. N. (2016). Coord. Chem. Rev. 308, 32–55. CrossRef CAS Google Scholar
Gao, J., Yuan, Y., Cui, A.-J., Tian, F., He, M.-Y. & Chen, Q. (2016). Z. Naturforsch. B: Chem. Sci. 71, 843–848. Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Kashyap, S. J., Garg, V. K., Sharma, P. K., Kumar, N., Dudhe, R. & Gupta, J. K. (2012). Med. Chem. Res. 21, 2123–2132. CrossRef CAS Google Scholar
Leiva, À., Clegg, W., Cucurull-Sánchez, L., González-Duarte, P. & Pons, J. (1999). J. Chem. Crystallogr. 29, 1097–1101. CrossRef CAS Google Scholar
Meundaeng, N., Rujiwatra, A. & Prior, T. J. (2016). Transition Met. Chem. 41, 7, 783–793. Google Scholar
Meundaeng, N., Rujiwatra, A. & Prior, T. J. (2017). J. Solid State Chem. 245, 138–145. CrossRef CAS Google Scholar
Palmer, D. C. (2014). CrystalMaker. CrystalMaker Software Ltd, Oxfordshire, England. Google Scholar
Rossin, A., Di Credico, B., Giambastiani, G., Gonsalvi, L., Peruzzini, M. & Reginato, G. (2011). Eur. J. Inorg. Chem. pp. 539–548. CrossRef Google Scholar
Rossin, A., Tuci, G., Giambastiani, G. & Peruzzini, M. (2014). ChemPlusChem 79, 406-412. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sherrington, D. C. & Taskinen, K. A. (2001). Chem. Soc. Rev. 30, 83–93. Web of Science CrossRef CAS Google Scholar
Stoe & Cie (2002). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar
Yin, H.-D., Gao, Z. J. & Wang, C.-H. (2005). Chin. J. Chem. 23, 928–932. CAS Google Scholar
Yin, H.-D. & Wang, C.-H. (2004). Appl. Organomet. Chem. 18, 411–412. Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.