Bis[2-(thio­phen-2-yl)quinoxaline-κN4]silver(I) perchlorate

Crundwell, G.

doi:10.1107/S2414314623002468

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 3| March 2023| x230246

https://doi.org/10.1107/S2414314623002468

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Bis[2-(thiophen-2-yl)quinoxaline-κN⁴]silver(I) perchlorate

Guy Crundwell ^a ^*

^aDepartment of Chemistry & Biochemistry, Central Connecticut State University, 1619 Stanley Street, New Britain, CT 06053, USA
^*Correspondence e-mail: crundwellg@ccsu.edu

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 8 March 2023; accepted 13 March 2023; online 21 March 2023)

The crystal of the title salt, [Ag(C₁₂H₈N₂S)₂]ClO₄, has C2/c symmetry whereby the silver(I) atom sits on a twofold rotation axis, as does the perchlorate anion, which is disordered about this axis. The thienylquinoxaline ligand is nearly planar with the thienyl ring making a dihedral angle of 10.88 (8)° with respect to the quinoxaline moiety.

Keywords: crystal structure; silver(I); quinoxalines; thienyl rings.

CCDC reference: 2248354

Structure description

The silver(I) metal center sits on a twofold symmetry axis (Fig. 1). As a result of the position of the twofold axis, the two thienylquinoxaline ligands, which are bonding via their quinoxaline N atoms, adopt a configuration whereby both of the quinoxaline units are pointing to the same side of the molecule, as opposed to the tetrafluoridoborate complex with the same cation, which crystallizes with the two ligands pointing in opposite directions (Crundwell, 2013 ). The thienylquinoxaline ligand is nearly planar, with the thienyl ring making a dihedral angle of 10.88 (8)° with respect to the quinoxaline moiety. This is similar to the nearly planar ligand configuration in the tetrafluoridoborate salt (Crundwell, 2013).

Figure 1
A view of the title compound (Farrugia, 2012

). Displacement ellipsoids are drawn at the 50% probability level.

Synthesis and crystallization

Crystals were grown by combining warmed methanolic solutions of AgClO₄ and 2-thienylquinoxaline in a 1:2 molar ratio. The combined solution was pipetted into test tubes, which were then placed into amber vials and loosely sealed until small colorless crystals were observed. Crystals were harvested and used immediately since the silver salts deteriorate in light over days. When measuring of melting points was attempted, the crystals decomposed.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The perchlorate disorder was treated by suppressing the generation of additional solvent atoms due to the anion's position on the symmetry axis. The perchlorate bond distances and oxygen-to-oxygen distances were restrained to 1.41 (1) and 2.30 (2) Å, respectively.

Table 1
Experimental details

Crystal data
Chemical formula	[Ag(C₁₂H₈N₂S)₂]ClO₄
M_r	631.85
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	29.8739 (8), 10.6344 (4), 7.6425 (4)
β (°)	99.930 (4)
V (Å³)	2391.58 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.17
Crystal size (mm)	0.31 × 0.30 × 0.22

Data collection
Diffractometer	Xcalibur CCD, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 $[Agilent (2014). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ )
T_min, T_max	0.770, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13270, 3957, 2441
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.753

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.072, 0.82
No. of reflections	3957
No. of parameters	187
No. of restraints	10
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.29
Computer programs: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXS97 (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ), and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2248354

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314623002468/bt4134sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623002468/bt4134Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Bis[2-(thiophen-2-yl)quinoxaline-κN⁴]silver(I) perchlorate top

Crystal data top

[Ag(C₁₂H₈N₂S)₂]ClO₄	F(000) = 1264
M_r = 631.85	D_x = 1.755 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 29.8739 (8) Å	Cell parameters from 5344 reflections
b = 10.6344 (4) Å	θ = 4.1–32.4°
c = 7.6425 (4) Å	µ = 1.17 mm⁻¹
β = 99.930 (4)°	T = 293 K
V = 2391.58 (17) Å³	Block, colorless
Z = 4	0.31 × 0.30 × 0.22 mm

Data collection top

Xcalibur CCD, Sapphire3 diffractometer	3957 independent reflections
Radiation source: fine-focus sealed tube	2441 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 32.4°, θ_min = 4.2°
Absorption correction: multi-scan (CrysAlisPRO; Agilent, 2014)	h = −44→44
T_min = 0.770, T_max = 1.000	k = −15→15
13270 measured reflections	l = −11→10

Refinement top

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 0.82	w = 1/[σ²(F_o²) + (0.0428P)²] where P = (F_o² + 2F_c²)/3
3957 reflections	(Δ/σ)_max < 0.001
187 parameters	Δρ_max = 0.36 e Å⁻³
10 restraints	Δρ_min = −0.29 e Å⁻³

Special details top

Experimental. Hydrogen atoms were included in calculated positions with a C-H distance of 0.93 Å and were included in the refinement in riding motion approximation with U_iso = 1.2U_eq of the carrier atom. Anion disorder treated with PART -1 and DFIX restraints.

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.

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 > 2sigma(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. Hydrogen atoms were placed in calculated positions with a C—H distance of 0.93 Å and were included in the refinement in a riding model approximation with U_iso = 1.2 U_eq(C). Difference maps and oblong thermal parameters indicated that the perchlorate anion was disordered about a twofold axis.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ag1	1.0000	0.15837 (2)	0.2500	0.05278 (10)
S1	0.774221 (15)	0.02088 (5)	−0.17950 (8)	0.04958 (14)
N1	0.92717 (5)	0.18494 (14)	0.1583 (2)	0.0404 (4)
N2	0.83748 (4)	0.22291 (14)	−0.0167 (2)	0.0382 (4)
C1	0.90225 (6)	0.09241 (18)	0.0828 (3)	0.0413 (4)
H1	0.9148	0.0123	0.0854	0.050*
C2	0.85637 (5)	0.11036 (17)	−0.0035 (3)	0.0353 (4)
C3	0.86277 (6)	0.32029 (16)	0.0635 (3)	0.0372 (4)
C4	0.84337 (7)	0.44149 (18)	0.0619 (3)	0.0458 (5)
H4	0.8137	0.4548	0.0043	0.055*
C5	0.86803 (8)	0.53904 (19)	0.1447 (3)	0.0503 (5)
H5	0.8550	0.6186	0.1424	0.060*
C6	0.91271 (8)	0.52096 (19)	0.2333 (3)	0.0514 (5)
H6	0.9292	0.5887	0.2881	0.062*
C7	0.93217 (6)	0.40506 (19)	0.2397 (3)	0.0472 (5)
H7	0.9617	0.3935	0.3000	0.057*
C8	0.90762 (5)	0.30265 (17)	0.1553 (3)	0.0366 (4)
C9	0.82923 (6)	0.00112 (16)	−0.0714 (3)	0.0373 (4)
C10	0.83990 (6)	−0.12423 (17)	−0.0520 (3)	0.0436 (5)
H10	0.8681	−0.1542	0.0031	0.052*
C11	0.80301 (7)	−0.2030 (2)	−0.1258 (3)	0.0509 (5)
H11	0.8043	−0.2904	−0.1234	0.061*
C12	0.76607 (7)	−0.1374 (2)	−0.1993 (3)	0.0514 (5)
H12	0.7391	−0.1742	−0.2547	0.062*
Cl1	0.9978 (2)	−0.17969 (10)	0.2283 (8)	0.0577 (9)	0.50
O1	1.00756 (19)	−0.0707 (4)	0.1315 (7)	0.1067 (16)	0.50
O2	1.00003 (13)	−0.2842 (3)	0.1151 (5)	0.0727 (10)	0.50
O3	0.95369 (19)	−0.1661 (5)	0.2619 (11)	0.124 (2)	0.50
O4	1.0300 (3)	−0.1931 (7)	0.3832 (9)	0.163 (3)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.02387 (9)	0.05375 (14)	0.07518 (19)	0.000	−0.00703 (9)	0.000
S1	0.0328 (2)	0.0521 (3)	0.0581 (4)	−0.00168 (19)	−0.0080 (2)	0.0023 (2)
N1	0.0255 (6)	0.0442 (9)	0.0494 (10)	0.0015 (5)	0.0002 (6)	0.0004 (7)
N2	0.0285 (6)	0.0427 (8)	0.0410 (10)	0.0017 (6)	−0.0006 (6)	0.0004 (7)
C1	0.0281 (7)	0.0404 (10)	0.0531 (13)	0.0023 (7)	0.0007 (8)	0.0003 (9)
C2	0.0274 (7)	0.0420 (9)	0.0355 (10)	−0.0003 (7)	0.0023 (7)	0.0003 (8)
C3	0.0325 (8)	0.0417 (10)	0.0366 (11)	0.0030 (7)	0.0036 (7)	0.0020 (8)
C4	0.0430 (10)	0.0450 (10)	0.0468 (13)	0.0074 (8)	0.0007 (9)	0.0023 (9)
C5	0.0588 (12)	0.0395 (10)	0.0521 (14)	0.0082 (9)	0.0080 (10)	−0.0001 (9)
C6	0.0549 (12)	0.0460 (11)	0.0529 (14)	−0.0096 (9)	0.0077 (10)	−0.0094 (10)
C7	0.0353 (9)	0.0502 (11)	0.0535 (14)	−0.0054 (8)	0.0003 (9)	−0.0055 (10)
C8	0.0283 (7)	0.0421 (9)	0.0389 (11)	−0.0002 (6)	0.0043 (7)	0.0004 (8)
C9	0.0273 (7)	0.0459 (10)	0.0374 (11)	−0.0007 (7)	0.0016 (7)	0.0006 (8)
C10	0.0342 (8)	0.0433 (10)	0.0510 (13)	−0.0003 (7)	0.0012 (8)	−0.0034 (9)
C11	0.0516 (11)	0.0433 (10)	0.0545 (14)	−0.0052 (9)	−0.0002 (10)	−0.0024 (10)
C12	0.0429 (9)	0.0547 (12)	0.0527 (14)	−0.0124 (9)	−0.0030 (9)	−0.0010 (10)
Cl1	0.0621 (12)	0.0518 (5)	0.053 (3)	0.0063 (9)	−0.0079 (17)	−0.0050 (8)
O1	0.152 (4)	0.055 (2)	0.132 (4)	−0.002 (3)	0.078 (4)	−0.005 (2)
O2	0.088 (2)	0.0528 (19)	0.074 (3)	0.0035 (19)	0.006 (2)	−0.0154 (18)
O3	0.116 (4)	0.105 (4)	0.172 (7)	0.036 (3)	0.082 (4)	0.035 (4)
O4	0.206 (8)	0.177 (7)	0.081 (4)	0.003 (6)	−0.045 (5)	−0.009 (4)

Geometric parameters (Å, º) top

Ag1—N1	2.1860 (13)	C5—C6	1.402 (3)
Ag1—N1ⁱ	2.1861 (13)	C6—H6	0.9300
S1—C9	1.7202 (17)	C6—C7	1.360 (3)
S1—C12	1.704 (2)	C7—H7	0.9300
N1—C1	1.307 (2)	C7—C8	1.406 (3)
N1—C8	1.380 (2)	C9—C10	1.373 (3)
N2—C2	1.320 (2)	C10—H10	0.9300
N2—C3	1.364 (2)	C10—C11	1.421 (3)
C1—H1	0.9300	C11—H11	0.9300
C1—C2	1.427 (2)	C11—C12	1.344 (3)
C2—C9	1.460 (2)	C12—H12	0.9300
C3—C4	1.412 (2)	Cl1—O1	1.432 (5)
C3—C8	1.414 (2)	Cl1—O2	1.417 (5)
C4—H4	0.9300	Cl1—O3	1.392 (7)
C4—C5	1.363 (3)	Cl1—O4	1.399 (6)
C5—H5	0.9300

N1—Ag1—N1ⁱ	165.14 (8)	C6—C7—H7	120.0
C12—S1—C9	91.83 (9)	C6—C7—C8	119.98 (18)
C1—N1—Ag1	120.27 (12)	C8—C7—H7	120.0
C1—N1—C8	117.94 (14)	N1—C8—C3	119.39 (15)
C8—N1—Ag1	121.17 (11)	N1—C8—C7	120.63 (15)
C2—N2—C3	117.24 (13)	C7—C8—C3	119.98 (17)
N1—C1—H1	118.9	C2—C9—S1	119.97 (13)
N1—C1—C2	122.13 (16)	C10—C9—S1	110.81 (13)
C2—C1—H1	118.9	C10—C9—C2	129.05 (16)
N2—C2—C1	121.37 (16)	C9—C10—H10	123.8
N2—C2—C9	119.37 (14)	C9—C10—C11	112.34 (17)
C1—C2—C9	119.20 (16)	C11—C10—H10	123.8
N2—C3—C4	119.64 (15)	C10—C11—H11	123.7
N2—C3—C8	121.78 (15)	C12—C11—C10	112.58 (18)
C4—C3—C8	118.53 (16)	C12—C11—H11	123.7
C3—C4—H4	119.9	S1—C12—H12	123.8
C5—C4—C3	120.16 (17)	C11—C12—S1	112.43 (15)
C5—C4—H4	119.9	C11—C12—H12	123.8
C4—C5—H5	119.6	O2—Cl1—O1	106.5 (5)
C4—C5—C6	120.87 (19)	O3—Cl1—O1	107.2 (4)
C6—C5—H5	119.6	O3—Cl1—O2	109.9 (5)
C5—C6—H6	119.8	O3—Cl1—O4	112.9 (6)
C7—C6—C5	120.47 (18)	O4—Cl1—O1	110.4 (6)
C7—C6—H6	119.8	O4—Cl1—O2	109.8 (4)

Ag1—N1—C1—C2	−170.09 (15)	C2—N2—C3—C8	0.8 (3)
Ag1—N1—C8—C3	167.57 (14)	C2—C9—C10—C11	175.2 (2)
Ag1—N1—C8—C7	−11.3 (3)	C3—N2—C2—C1	−3.4 (3)
S1—C9—C10—C11	0.0 (3)	C3—N2—C2—C9	173.90 (18)
N1ⁱ—Ag1—N1—C1	162.84 (16)	C3—C4—C5—C6	−0.4 (3)
N1ⁱ—Ag1—N1—C8	−7.97 (15)	C4—C3—C8—N1	−179.96 (19)
N1—C1—C2—N2	2.6 (3)	C4—C3—C8—C7	−1.1 (3)
N1—C1—C2—C9	−174.71 (19)	C4—C5—C6—C7	−0.6 (4)
N2—C2—C9—S1	3.9 (3)	C5—C6—C7—C8	0.8 (4)
N2—C2—C9—C10	−170.9 (2)	C6—C7—C8—N1	179.0 (2)
N2—C3—C4—C5	178.7 (2)	C6—C7—C8—C3	0.1 (3)
N2—C3—C8—N1	2.6 (3)	C8—N1—C1—C2	1.0 (3)
N2—C3—C8—C7	−178.51 (19)	C8—C3—C4—C5	1.2 (3)
C1—N1—C8—C3	−3.5 (3)	C9—S1—C12—C11	0.7 (2)
C1—N1—C8—C7	177.7 (2)	C9—C10—C11—C12	0.5 (3)
C1—C2—C9—S1	−178.79 (16)	C10—C11—C12—S1	−0.8 (3)
C1—C2—C9—C10	6.4 (4)	C12—S1—C9—C2	−176.09 (18)
C2—N2—C3—C4	−176.53 (19)	C12—S1—C9—C10	−0.42 (18)

Symmetry code: (i) −x+2, y, −z+1/2.

Funding information

Funding for this research was provided by: CSU-AAUP Research Grant .

References

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