supplementary materials


zs2248 scheme

Acta Cryst. (2013). E69, m164    [ doi:10.1107/S1600536813004510 ]

Bis[2-(thiophen-2-yl)quinoxaline-[kappa]N4]silver(I) tetrafluoridoborate

G. Crundwell

Abstract top

In the title compound, [Ag(C12H8N2S)2]BF4, the two-coordinate AgI ion lies on a crystallographic inversion center and is linearly bonded to the N-donor atoms of two separate quinoxaline ligands. The thiophenyl ring of the ligand is nearly coplanar with the quinoxaline ring system [dihedral angle = 9.15 (13)°]. In the crystal, the complex molecules pack in layers parallel to (-102) and form weak [pi]-[pi] ring stacking interactions [minimum ring centroid separation = 3.7054 (17) Å]. The tetrafluoridoroborate anion is equally disordered about an inversion center.

Comment top

In the title compound, [Ag(C12H8N2S)2] BF4, the Ag+ lies on a crystallographic inversion center and is linearly bonded to the N donor atoms of two separate quinoxaline ligands [Ag—N, 2.166 (2) Å] (Fig. 1). The thiophenyl substituent ring of the ligand is nearly coplanar with the quinoxaline ring [dihedral angle = 9.15(0.13)°]. All bond lengths and angles fall within the typical ranges found in similar complexes (Wang, 2012). In the crystal, the complex molecules pack in layers and give weak ππ ring stacking interactions [minimum ring centroid separation = 3.7054 (17) Å]. The tetrafluoroborate anion is 50% disordered about an inversion center.

Related literature top

For the synthesis of the title compound, see: Bhogala et al. (2003). For the structure of a similar compound, see: Wang (2012).

Experimental top

In a 50 mL beaker, 0.471 mmol of 2-(2-thiophenyl)quinoxaline (100 mg) was added to a 20 mL of near boiling absolute ethanol. In a seperate 50 mL beaker, 0.236 mmol of AgBF4 (39 mg) was added to 15 mL of near boiling absolute ethanol. The two solutions were combined then pipetted into several test tubes placed inside amber vials. Over the course of days, small colourless block-shaped crystals had formed.

Refinement top

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 motion approximation with Uiso = 1.2Ueq of the carrier atom. Difference maps indicated that the tetrafluoridoroborate atom was disordered about an inversion center in the lattice. The disorder was treated by the use of several similarity restraints.

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: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound (Spek, 2009). Displacement ellipsoids are drawn at the 50% probability level. The disordered tetrafluoridoroborate anion is omitted for clarity. For symmetry code (i): -x+5/2, -y+1/2, -z+1.
Bis[2-(thiophen-2-yl)quinoxaline-κN4]silver(I) tetrafluoridoborate top
Crystal data top
[Ag(C12H8N2S)2]BF4F(000) = 1232
Mr = 619.21Dx = 1.648 Mg m3
Monoclinic, C2/cMelting point: 395 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 14.1249 (19) ÅCell parameters from 7201 reflections
b = 13.1972 (16) Åθ = 4.3–33.4°
c = 13.739 (2) ŵ = 1.03 mm1
β = 102.991 (15)°T = 293 K
V = 2495.5 (6) Å3Plate, white
Z = 40.32 × 0.22 × 0.17 mm
Data collection top
Oxford Diffraction Xcalibur Sapphire3 CCD
diffractometer
4624 independent reflections
Radiation source: fine-focus sealed tube2670 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
Detector resolution: 16.1790 pixels mm-1θmax = 33.4°, θmin = 4.3°
ω scansh = 2121
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
k = 2020
Tmin = 0.657, Tmax = 1.000l = 2120
30081 measured reflections
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)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.204H-atom parameters constrained
S = 0.93 w = 1/[σ2(Fo2) + (0.1425P)2]
where P = (Fo2 + 2Fc2)/3
4624 reflections(Δ/σ)max < 0.001
187 parametersΔρmax = 0.68 e Å3
55 restraintsΔρmin = 0.51 e Å3
Crystal data top
[Ag(C12H8N2S)2]BF4V = 2495.5 (6) Å3
Mr = 619.21Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.1249 (19) ŵ = 1.03 mm1
b = 13.1972 (16) ÅT = 293 K
c = 13.739 (2) Å0.32 × 0.22 × 0.17 mm
β = 102.991 (15)°
Data collection top
Oxford Diffraction Xcalibur Sapphire3 CCD
diffractometer
4624 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
2670 reflections with I > 2σ(I)
Tmin = 0.657, Tmax = 1.000Rint = 0.045
30081 measured reflectionsθmax = 33.4°
Refinement top
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.204Δρmax = 0.68 e Å3
S = 0.93Δρmin = 0.51 e Å3
4624 reflectionsAbsolute structure: ?
187 parametersFlack parameter: ?
55 restraintsRogers parameter: ?
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 a riding motion approximation with Uiso = 1.2Ueq of the carrier atom.

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*/UeqOcc. (<1)
Ag11.25000.25000.50000.0834 (2)
N11.11733 (17)0.16642 (18)0.44213 (18)0.0522 (5)
C11.0346 (2)0.2103 (2)0.4009 (2)0.0519 (6)
H11.03080.28060.40340.062*
C80.95133 (18)0.15564 (19)0.35281 (18)0.0456 (5)
N20.95235 (14)0.05545 (16)0.34896 (15)0.0439 (4)
C71.03648 (17)0.00867 (19)0.39162 (17)0.0423 (5)
C21.12040 (17)0.0612 (2)0.43877 (18)0.0457 (5)
C31.2080 (2)0.0087 (3)0.4793 (2)0.0599 (7)
H31.26370.04410.50990.072*
C41.2094 (2)0.0938 (3)0.4727 (3)0.0680 (8)
H41.26660.12880.49900.082*
C51.1263 (3)0.1472 (2)0.4270 (3)0.0661 (8)
H51.12890.21750.42340.079*
C61.0418 (2)0.0988 (2)0.3877 (2)0.0527 (6)
H60.98700.13600.35810.063*
S10.76065 (6)0.13484 (8)0.25355 (7)0.0682 (3)
C90.8619 (2)0.2074 (2)0.3038 (2)0.0526 (6)
C100.8465 (3)0.3134 (3)0.2847 (2)0.0727 (10)
H100.89200.36440.30530.087*
C110.7490 (3)0.3275 (3)0.2284 (3)0.0787 (11)
H110.72330.39090.20810.094*
C120.6976 (3)0.2410 (3)0.2073 (3)0.0757 (11)
H120.63360.23940.17080.091*
B11.0011 (7)0.5432 (7)0.4307 (12)0.174 (6)0.50
F11.0535 (5)0.4612 (6)0.4342 (12)0.234 (7)0.50
F20.9766 (15)0.5583 (11)0.5186 (14)0.405 (13)0.50
F30.9165 (7)0.5285 (7)0.3685 (14)0.331 (10)0.50
F41.0358 (6)0.6261 (5)0.4077 (10)0.244 (7)0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0568 (2)0.0772 (3)0.1093 (4)0.03177 (17)0.0040 (2)0.01481 (19)
N10.0466 (11)0.0521 (12)0.0570 (13)0.0126 (9)0.0097 (9)0.0046 (9)
C10.0569 (15)0.0423 (12)0.0570 (15)0.0105 (11)0.0137 (12)0.0031 (11)
C80.0446 (11)0.0505 (13)0.0422 (12)0.0028 (10)0.0109 (9)0.0012 (10)
N20.0370 (9)0.0493 (11)0.0444 (11)0.0053 (8)0.0070 (8)0.0035 (8)
C70.0390 (10)0.0458 (12)0.0432 (12)0.0061 (9)0.0112 (9)0.0023 (9)
C20.0362 (10)0.0539 (13)0.0460 (12)0.0082 (9)0.0073 (9)0.0011 (10)
C30.0417 (13)0.0758 (19)0.0595 (16)0.0039 (12)0.0059 (11)0.0041 (14)
C40.0509 (16)0.081 (2)0.0702 (19)0.0120 (15)0.0093 (14)0.0139 (16)
C50.072 (2)0.0529 (15)0.075 (2)0.0122 (14)0.0215 (17)0.0108 (14)
C60.0554 (14)0.0446 (13)0.0563 (15)0.0060 (11)0.0089 (12)0.0045 (11)
S10.0499 (4)0.0782 (6)0.0718 (5)0.0075 (3)0.0036 (3)0.0082 (4)
C90.0533 (14)0.0571 (15)0.0479 (14)0.0086 (12)0.0124 (11)0.0011 (12)
C100.079 (2)0.082 (2)0.0557 (17)0.0280 (19)0.0122 (16)0.0003 (15)
C110.085 (2)0.076 (2)0.075 (2)0.032 (2)0.0171 (19)0.0093 (18)
C120.066 (2)0.087 (3)0.071 (2)0.0307 (18)0.0072 (17)0.0093 (16)
B10.057 (5)0.087 (6)0.361 (17)0.015 (4)0.015 (8)0.096 (9)
F10.063 (4)0.091 (5)0.53 (2)0.003 (3)0.017 (7)0.064 (8)
F20.66 (4)0.145 (10)0.48 (2)0.088 (16)0.29 (2)0.150 (14)
F30.130 (7)0.121 (7)0.64 (3)0.002 (5)0.133 (11)0.059 (11)
F40.125 (6)0.077 (4)0.55 (2)0.037 (4)0.123 (10)0.048 (7)
Geometric parameters (Å, º) top
Ag1—N12.166 (2)C5—C61.355 (4)
Ag1—N1i2.166 (2)C5—H50.9300
N1—C11.313 (4)C6—H60.9300
N1—C21.391 (3)S1—C121.705 (3)
C1—C81.411 (4)S1—C91.731 (3)
C1—H10.9300C9—C101.432 (5)
C8—N21.323 (3)C10—C111.432 (6)
C8—C91.460 (4)C10—H100.9300
N2—C71.350 (3)C11—C121.349 (6)
C7—C21.400 (3)C11—H110.9300
C7—C61.421 (4)C12—H120.9300
C2—C31.418 (4)B1—F41.267 (11)
C3—C41.357 (5)B1—F11.307 (11)
C3—H30.9300B1—F31.317 (11)
C4—C51.391 (5)B1—F21.343 (13)
C4—H40.9300
N1—Ag1—N1i179.998 (2)C6—C5—H5119.4
C1—N1—C2117.2 (2)C4—C5—H5119.4
C1—N1—Ag1123.11 (18)C5—C6—C7120.3 (3)
C2—N1—Ag1119.34 (18)C5—C6—H6119.8
N1—C1—C8122.9 (3)C7—C6—H6119.8
N1—C1—H1118.5C12—S1—C990.6 (2)
C8—C1—H1118.5C10—C9—C8128.5 (3)
N2—C8—C1120.9 (2)C10—C9—S1112.9 (2)
N2—C8—C9117.7 (2)C8—C9—S1118.5 (2)
C1—C8—C9121.4 (2)C9—C10—C11108.3 (4)
C8—N2—C7117.1 (2)C9—C10—H10125.8
N2—C7—C2123.1 (2)C11—C10—H10125.8
N2—C7—C6119.3 (2)C12—C11—C10114.4 (4)
C2—C7—C6117.7 (2)C12—C11—H11122.8
N1—C2—C7118.7 (2)C10—C11—H11122.8
N1—C2—C3120.3 (2)C11—C12—S1113.8 (3)
C7—C2—C3120.9 (3)C11—C12—H12123.1
C4—C3—C2119.0 (3)S1—C12—H12123.1
C4—C3—H3120.5F4—B1—F1118.4 (9)
C2—C3—H3120.5F4—B1—F3108.1 (11)
C3—C4—C5120.8 (3)F1—B1—F3109.0 (9)
C3—C4—H4119.6F4—B1—F2106.8 (10)
C5—C4—H4119.6F1—B1—F2110.4 (12)
C6—C5—C4121.3 (3)F3—B1—F2103.0 (10)
Symmetry code: (i) x+5/2, y+1/2, z+1.
Acknowledgements top

This research was funded by a CCSU–AAUP research grant.

references
References top

Bhogala, B. R., Thallapally, P. K. & Nangia, A. (2003). Cryst. Growth Des. 4, 215–218.

Oxford Diffraction (2009). CrysAlis CCD, CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Wang, Z.-J. (2012). Acta Cryst. E68, m4.