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Acta Cryst. (2007). E63, m2102-m2103    [ doi:10.1107/S1600536807032771 ]

2,3-Dimethylquinoxalinediium hexabromidostannate(IV) trihydrate

B. F. Ali, R. Al-Far and S. W. Ng

Abstract top

In the title compound, (C10H12N2)[SnBr6]·3H2O, the asymmetric unit contains one cation, one anion and three water molecules, and the Sn atom has a distorted octahedral environment. In the crystal structure, intra- and intermolecular hydrogen bonds and Br...Br interactions [Br...Br = 3.6726 (19), 3.6913 (18) and 3.6517 (21) Å] lead to the formation of a supramolecular architecture.

Comment top

Noncovalent interactions play an important role in organizing structural units in both natural and artificial systems (Desiraju, 1997). In connection with ongoing studies (Ali et al., 2007; Ali & Al-Far, 2007; Al-Far & Ali, 2007a,b) of the structural aspects of bromo metal anions salts, we herein report the crystal structure of the title compound, (I).

The asymmetric unit of the title compound, (I), contains one cation, one anion and three water molecules, where the Sn atom has a distorted octahedral environment (Fig. 1, Table 1). The bond lengths and angles (Table 1) are generally within normal ranges (Allen et al., 1987). In the anion, the Sn1—Br1 [2.4406 (12) Å] and Sn1—Br3 [2.4605 (12) Å] bonds are shorter than the other Sn—Br bonds, in which they are within the range of Sn—Br bonds reported previously for compounds containing [SnBr6]2− anions (Ali & Al-Far, 2007; Al-Far & Ali, 2007a,b; Al-Far et al., 2007; Tudela & Khan, 1991; Willey et al., 1998). In the cation, the bond lengths and angles are in accordance with the corresponding values (Al-Far & Ali, 2007a,b; Ali et al., 2007). The cation is, of course, planar, in which C1 and C10 atoms are also coplanar.

The packing of the structure can be regarded as alternating layers of anions and cations (Fig. 2). The anions within each layer (Fig. 3) interact via Br1···Br3iv = 3.6726 (19) Å [symmetry code: (iv) x, 3/2 + y, 1/2 + z] interactions parallel to c axis. Each anionic layer further interacts via Br2···Br6v = 3.6913 (18) Å [symmetry code: (v) −x + 3, 1/2 + y, 1/2 − z] and Br4···Br4vi = 3.6517 (21) Å [symmetry code: (vi) −x + 2, −y + 1, −z] interactions to form a two-dimensional anionic network parallel to ac plane (Fig. 3).

The crystal supramolecularity is represented in the significantly short hydrogen bonds (Table 2, Fig. 4) along with Br···Br interactions that allow the formation of supramolecular assembly of the anion, cation and water molecules in three-dimensional structure, in which they may be effective in the stabilization of the crystal structure.

Related literature top

For related literature, see: Desiraju (1997); Ali et al. (2007); Ali & Al-Far (2007); Al-Far & Ali (2007a,b); Al-Far et al. (2007); Tudela & Khan (1991); Willey et al. (1998). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of (I), tin metal (0.119 mg, 1 mmol) dissolved in absolute ethanol (10 ml), HBr (60%, 5 ml) and liquid Br2 (60%, 2 ml), was added dropwise to a stirred hot solution of 2,3-dimethylquinoxalinium (0.158 mg, 1 mmol) dissolved in ethanol (10 ml) and HBr (60%, 2 ml). After refluxing for 1 h, the mixture was filtered off, and then allowed to stand undisturbed at room temperature. The salt crystallized over 1 d as yellow crystals. Crystals were filtered off, washed with diethylether and dried under vacuum (yield; 0.750 mg; 92.4%).

Refinement top

H atoms were positioned geometrically, with O—H = 0.84–0.90 Å (for H2O), N—H = 0.86 Å (for NH) and C—H = 0.95 and 0.98 Å, for aromatic and methylene H atoms, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,O,N), where x = 1.2 for NH and aromatic H atoms, and x = 1.5 for all other H atoms.

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. A partial packing diagram of (I). Hydrogen bonds and Br···Br interactions are shown as dashed lines. Viewed down c axis, where a and b axes are horizontal and vertical, respectively.
[Figure 3] Fig. 3. Anion network of Br···Br interactions. Viewed down b axis, where c and a axes are horizontal and vertical, respectively [Symmetry codes: (iv) x, 3/2 + y, 1/2 + z; (v) −x + 3, 1/2 + y, 1/2 − z; (vi) −x + 2, −y + 1, −z].
[Figure 4] Fig. 4. Anion, cation and water molecules intermolecular interactions. Sn—Br···H—O, H2O···H—OH, H2O···H—N and Br···Br (parallel to c axis) intermolecular interactions are shown as dashed lines. Viewed down b axis, where c and a axes are horizontal and vertical, respectively. H atoms are omitted for clarity. Oxygen atoms of water molecules shown as balls.
'2,3-Dimethylquinoxalinediium hexabromostannate(IV) trihydrate' top
Crystal data top
(C10H12N2)[SnBr6]·3H2OF(000) = 1504
Mr = 812.37Dx = 2.558 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybcCell parameters from 4210 reflections
a = 9.898 (3) Åθ = 1.3–27.9°
b = 13.620 (5) ŵ = 12.59 mm−1
c = 16.098 (6) ÅT = 84 K
β = 103.599 (6)°Needle, yellow
V = 2109.3 (13) Å30.30 × 0.20 × 0.10 mm
Z = 4
Data collection top
Rigaku Mercury CCD
diffractometer		4633 independent reflections
Radiation source: fine-focus sealed tube4210 reflections with I > 2σ(I)
graphiteRint = 0.045
Detector resolution: 14.6306 pixels mm-1θmax = 27.5°, θmin = 2.1°
dtintegrate.ref scansh = −12→11
Absorption correction: multi-scan
Shape Tracing Software		k = −17→17
Tmin = 0.055, Tmax = 0.277l = −20→20
27021 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)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 1.20 w = 1/[σ2(Fo2) + (0.0478P)2 + 7.030P]
where P = (Fo2 + 2Fc2)/3
4633 reflections(Δ/σ)max = 0.001
201 parametersΔρmax = 1.41 e Å−3
0 restraintsΔρmin = −1.11 e Å−3
Crystal data top
(C10H12N2)[SnBr6]·3H2OV = 2109.3 (13) Å3
Mr = 812.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.898 (3) ŵ = 12.59 mm−1
b = 13.620 (5) ÅT = 84 K
c = 16.098 (6) Å0.30 × 0.20 × 0.10 mm
β = 103.599 (6)°
Data collection top
Rigaku Mercury CCD
diffractometer		4633 independent reflections
Absorption correction: multi-scan
Shape Tracing Software		4210 reflections with I > 2σ(I)
Tmin = 0.055, Tmax = 0.277Rint = 0.045
27021 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.062H-atom parameters constrained
wR(F2) = 0.132Δρmax = 1.41 e Å−3
S = 1.20Δρmin = −1.11 e Å−3
4633 reflectionsAbsolute structure: ?
201 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Sn11.23031 (5)0.73783 (4)0.15141 (3)0.03598 (16)
Br11.17497 (9)0.68693 (8)0.28495 (5)0.0562 (3)
Br21.41637 (10)0.86480 (7)0.24513 (6)0.0600 (3)
Br31.28560 (9)0.79729 (8)0.01892 (5)0.0594 (3)
Br41.04854 (9)0.61509 (7)0.05744 (6)0.0573 (3)
Br51.02270 (9)0.87143 (7)0.11762 (6)0.0538 (2)
Br61.43853 (9)0.60996 (7)0.18886 (6)0.0529 (2)
O1W0.5390 (9)0.6748 (7)0.4150 (5)0.099 (3)
H1W10.59170.62710.40630.149*
H1W20.45680.65020.41070.149*
O2W0.7208 (12)0.5361 (8)0.4048 (8)0.150 (5)
H2W10.69410.49850.36240.226*
H2W20.74080.50020.45100.226*
O3W0.9249 (12)0.6547 (9)0.3909 (5)0.134 (4)
H3W10.93950.70590.42770.201*
H3W21.00600.62900.39610.201*
N10.6611 (6)0.7296 (5)0.5744 (4)0.0432 (15)
H1N0.61440.71090.52490.052*
N20.8084 (7)0.7870 (5)0.7326 (4)0.0457 (16)
H2N0.85340.80500.78270.055*
C10.6530 (10)0.5601 (7)0.6141 (7)0.067 (3)
H1A0.58790.55840.55790.101*
H1B0.60760.53370.65720.101*
H1C0.73490.52020.61260.101*
C20.6965 (8)0.6629 (7)0.6361 (6)0.049 (2)
C30.6962 (7)0.8271 (6)0.5865 (5)0.0399 (17)
C40.6556 (9)0.8934 (7)0.5197 (5)0.050 (2)
H40.60450.87360.46460.060*
C50.6936 (10)0.9891 (8)0.5380 (7)0.063 (3)
H50.66901.03670.49390.075*
C60.7682 (10)1.0201 (7)0.6201 (8)0.067 (3)
H60.78991.08780.62890.080*
C80.7744 (7)0.8569 (6)0.6704 (5)0.0399 (17)
C70.8110 (9)0.9554 (7)0.6884 (6)0.055 (2)
H70.86130.97660.74320.066*
C90.7761 (8)0.6942 (6)0.7202 (5)0.0453 (19)
C100.8231 (11)0.6235 (8)0.7927 (6)0.073 (3)
H10A0.79280.64690.84290.109*
H10B0.92480.61860.80640.109*
H10C0.78260.55870.77610.109*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0316 (3)0.0490 (3)0.0301 (3)−0.0024 (2)0.0128 (2)−0.0062 (2)
Br10.0512 (5)0.0851 (7)0.0392 (4)0.0018 (4)0.0247 (4)0.0052 (4)
Br20.0516 (5)0.0684 (6)0.0626 (6)−0.0193 (4)0.0188 (4)−0.0240 (5)
Br30.0540 (5)0.0901 (7)0.0412 (4)−0.0031 (5)0.0252 (4)0.0099 (4)
Br40.0517 (5)0.0687 (6)0.0546 (5)−0.0196 (4)0.0184 (4)−0.0223 (4)
Br50.0447 (5)0.0622 (5)0.0588 (5)0.0063 (4)0.0210 (4)−0.0041 (4)
Br60.0473 (5)0.0622 (5)0.0540 (5)0.0130 (4)0.0217 (4)0.0009 (4)
O1W0.106 (6)0.134 (7)0.054 (4)0.010 (6)0.013 (4)−0.019 (5)
O2W0.175 (11)0.107 (8)0.209 (13)−0.005 (7)0.123 (10)−0.016 (8)
O3W0.151 (9)0.206 (11)0.043 (4)0.017 (8)0.016 (5)0.017 (6)
N10.035 (3)0.056 (4)0.040 (3)0.003 (3)0.011 (3)−0.004 (3)
N20.038 (4)0.070 (5)0.032 (3)0.001 (3)0.013 (3)0.000 (3)
C10.059 (6)0.056 (6)0.094 (8)−0.003 (5)0.030 (5)−0.005 (5)
C20.031 (4)0.059 (5)0.059 (5)−0.001 (4)0.016 (4)0.011 (4)
C30.032 (4)0.049 (4)0.045 (4)0.004 (3)0.021 (3)0.002 (4)
C40.046 (5)0.065 (6)0.042 (4)0.007 (4)0.017 (4)0.012 (4)
C50.054 (6)0.071 (7)0.070 (6)0.013 (5)0.030 (5)0.023 (5)
C60.065 (6)0.047 (5)0.103 (8)0.003 (4)0.049 (6)0.001 (5)
C80.027 (4)0.061 (5)0.036 (4)0.002 (3)0.015 (3)0.001 (3)
C70.049 (5)0.061 (5)0.065 (6)−0.005 (4)0.032 (4)−0.015 (5)
C90.036 (4)0.060 (5)0.043 (4)−0.001 (4)0.017 (3)0.007 (4)
C100.063 (6)0.099 (8)0.060 (6)0.009 (6)0.023 (5)0.037 (6)
Geometric parameters (Å, °) top
Sn1—Br12.4405 (12)C1—H1A0.9800
Sn1—Br32.4603 (12)C1—H1B0.9800
Sn1—Br42.6534 (11)C1—H1C0.9800
Sn1—Br62.6570 (12)C2—C91.461 (12)
Sn1—Br52.7026 (12)C3—C41.391 (11)
Sn1—Br22.7114 (11)C3—C81.447 (11)
O1W—H1W10.86000C4—C51.368 (13)
O1W—H1W20.87000C4—H40.9500
O2W—H2W10.84000C5—C61.418 (14)
O2W—H2W20.87000C5—H50.9500
O3W—H3W10.90000C6—C71.395 (14)
O3W—H3W20.86000C6—H60.9500
N1—C21.330 (10)C8—C71.403 (12)
N1—C31.375 (10)C7—H70.9500
N1—H1N0.8600C9—C101.500 (11)
N2—C91.308 (11)C10—H10A0.9800
N2—C81.365 (10)C10—H10B0.9800
N2—H2N0.8600C10—H10C0.9800
C1—C21.483 (13)
Br1—Sn1—Br3177.29 (4)N1—C2—C9118.9 (8)
Br1—Sn1—Br493.48 (4)N1—C2—C1117.1 (8)
Br3—Sn1—Br488.41 (4)C9—C2—C1124.0 (8)
Br1—Sn1—Br686.37 (4)N1—C3—C4120.0 (8)
Br3—Sn1—Br695.38 (4)N1—C3—C8117.8 (7)
Br4—Sn1—Br695.87 (4)C4—C3—C8122.2 (7)
Br1—Sn1—Br592.93 (3)C5—C4—C3115.9 (8)
Br3—Sn1—Br585.26 (4)C5—C4—H4122.0
Br4—Sn1—Br585.87 (4)C3—C4—H4122.0
Br6—Sn1—Br5178.17 (3)C4—C5—C6122.7 (9)
Br1—Sn1—Br287.41 (4)C4—C5—H5118.6
Br3—Sn1—Br290.69 (4)C6—C5—H5118.6
Br4—Sn1—Br2179.08 (4)C7—C6—C5122.8 (9)
Br6—Sn1—Br284.41 (4)C7—C6—H6118.6
Br5—Sn1—Br293.86 (4)C5—C6—H6118.6
H1W1—O1W—H1W2106.70N2—C8—C7120.5 (8)
H2W1—O2W—H2W2108.30N2—C8—C3118.3 (7)
H3W1—O3W—H3W2104.40C7—C8—C3121.1 (8)
C2—N1—C3122.6 (7)C6—C7—C8115.2 (9)
C2—N1—H1N118.7C6—C7—H7122.4
C3—N1—H1N118.7C8—C7—H7122.4
C9—N2—C8123.5 (7)N2—C9—C2118.9 (7)
C9—N2—H2N118.2N2—C9—C10118.8 (8)
C8—N2—H2N118.2C2—C9—C10122.4 (8)
C2—C1—H1A109.5C9—C10—H10A109.5
C2—C1—H1B109.5C9—C10—H10B109.5
H1A—C1—H1B109.5H10A—C10—H10B109.5
C2—C1—H1C109.5C9—C10—H10C109.5
H1A—C1—H1C109.5H10A—C10—H10C109.5
H1B—C1—H1C109.5H10B—C10—H10C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2W0.861.782.640 (14)170.00
O1W—H1W2···Br3i0.872.793.348 (9)123.1 (5)
O2W—H2W1···Br2ii0.842.573.401 (12)167.4 (7)
O2W—H2W2···Br3ii0.872.833.482 (11)132.9 (7)
O3W—H3W2···Br10.862.833.349 (11)120.00
N1—H1N···O1W0.861.822.672 (10)172
N2—H2N···O3Wiii0.861.812.660 (11)172
Symmetry codes: (i) x−1, −y+3/2, z+1/2; (ii) −x+2, y−1/2, −z+1/2; (iii) x, −y+3/2, z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Sn1—Br12.4405 (12)Sn1—Br62.6570 (12)
Sn1—Br32.4603 (12)Sn1—Br52.7026 (12)
Sn1—Br42.6534 (11)Sn1—Br22.7114 (11)
Br1—Sn1—Br3177.29 (4)Br4—Sn1—Br585.87 (4)
Br1—Sn1—Br493.48 (4)Br6—Sn1—Br5178.17 (3)
Br3—Sn1—Br488.41 (4)Br1—Sn1—Br287.41 (4)
Br1—Sn1—Br686.37 (4)Br3—Sn1—Br290.69 (4)
Br3—Sn1—Br695.38 (4)Br4—Sn1—Br2179.08 (4)
Br4—Sn1—Br695.87 (4)Br6—Sn1—Br284.41 (4)
Br1—Sn1—Br592.93 (3)Br5—Sn1—Br293.86 (4)
Br3—Sn1—Br585.26 (4)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2W0.861.782.640 (14)170.00
O1W—H1W2···Br3i0.872.793.348 (9)123.1 (5)
O2W—H2W1···Br2ii0.842.573.401 (12)167.4 (7)
O2W—H2W2···Br3ii0.872.833.482 (11)132.9 (7)
O3W—H3W2···Br10.862.833.349 (11)120.00
N1—H1N···O1W0.861.822.672 (10)172
N2—H2N···O3Wiii0.861.812.660 (11)172
Symmetry codes: (i) x−1, −y+3/2, z+1/2; (ii) −x+2, y−1/2, −z+1/2; (iii) x, −y+3/2, z+1/2.
Acknowledgements top

Al al-Bayt University and Al-Balqa'a Applied University are thanked for their support.

references
References top

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