Bis(2,6-diamino-3,5-dibromo-pyridinium) hexa-bromidostannate(IV).

The asymmetric unit of the title compound, (C(5)H(6)Br(2)N(3))(2)[SnBr(6)], contains one cation and one half-anion in which the Sn atom is located on a crystallographic centre of inversion and is in a quasi-octa-hedral geometry. The crystal structure is assembled via hydrogen-bonding inter-actions of two kinds, N(pyridine/amine)-H⋯Br-Sn, along with C-Br⋯Br-Sn interactions [3.4925 (19) Å]. The cations are involved in π-π stacking, which adds an extra supra-molecularity as it presents a strong case of offset-face-to-face motifs [centroid-centroid distance = 3.577 (3) Å]. The inter-molecular hydrogen bonds, short Br⋯Br inter-actions and π-π stacking result in the formation of a three-dimensional supra-molecular architecture.

Related literature

For general background to hybrid organic–inorganic compounds, see: Aruta et al. (2005 ▶); Hill (1998 ▶); Kagan et al. (1999 ▶); Knutson et al. (2005 ▶); Raptopoulou et al. (2002 ▶). For related structures, see: Al-Far & Ali (2007 ▶); Al-Far, Ali & Al-Sou’od (2007 ▶); Ali & Al-Far (2007 ▶); Ali et al. (2008 ▶); Ali, Al-Far & Ng (2007 ▶); Awwadi et al. (2007 ▶); Tudela & Khan (1991 ▶); Willey et al. (1998 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

(C5H6Br2N3)2[SnBr6]

M = 1133.97

Monoclinic,

a = 8.3696 (14) Å

b = 16.720 (2) Å

c = 9.5814 (15) Å

β = 112.556 (12)°

V = 1238.3 (3) Å3

Z = 2

Mo Kα radiation

μ = 17.18 mm−1

T = 295 K

0.30 × 0.30 × 0.20 mm

Data collection

Bruker P4 diffractometer

Absorption correction: ψ scan (XSCANS; Bruker, 1996 ▶) T min = 0.007, T max = 0.035

2825 measured reflections

2162 independent reflections

1437 reflections with I > 2σ(I)

R int = 0.078

3 standard reflections every 97 reflections intensity decay: 0.01%

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.146

S = 1.00

2162 reflections

124 parameters

H-atom parameters constrained

Δρmax = 0.97 e Å−3

Δρmin = −1.63 e Å−3

Data collection: XSCANS (Bruker, 1996 ▶); cell refinement: XSCAn class="Chemical">NS; data reduction: SHELXTL (Sheldrick, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015189/hk2669sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015189/hk2669Isup2.hkl

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

(C5H6Br2N3)2[SnBr6]	F(000) = 1028
Mr = 1133.97	Dx = 3.042 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 29 reflections
a = 8.3696 (14) Å	θ = 5.7–12.5°
b = 16.720 (2) Å	µ = 17.18 mm−1
c = 9.5814 (15) Å	T = 295 K
β = 112.556 (12)°	Parallelepiped, yellow
V = 1238.3 (3) Å3	0.30 × 0.30 × 0.20 mm
Z = 2

Bruker P4 diffractometer	1437 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.078
graphite	θmax = 25.0°, θmin = 2.4°
ω scans	h = −9→1
Absorption correction: ψ scan (XSCANS; Bruker, 1996)	k = −19→1
Tmin = 0.008, Tmax = 0.035	l = −10→11
2825 measured reflections	3 standard reflections every 97 reflections
2162 independent reflections	intensity decay: 0.01%

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0766P)2] where P = (Fo2 + 2Fc2)/3
2162 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 0.97 e Å−3
0 restraints	Δρmin = −1.62 e Å−3

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.

	x	y	z	Uiso*/Ueq
Sn1	1.0000	0.5000	0.5000	0.0284 (3)
Br1	1.06913 (19)	0.61962 (8)	0.68737 (17)	0.0445 (4)
Br2	1.03622 (19)	0.59582 (8)	0.30353 (17)	0.0447 (4)
Br3	0.66959 (17)	0.53289 (8)	0.39554 (18)	0.0423 (4)
Br4	0.7063 (2)	0.32003 (9)	−0.12875 (19)	0.0510 (5)
Br5	0.2397 (2)	0.45315 (8)	0.10813 (18)	0.0483 (4)
N1	0.3496 (13)	0.2261 (5)	0.0181 (12)	0.032 (3)
H1	0.3148	0.1789	0.0281	0.039*
N2	0.5374 (16)	0.1644 (6)	−0.0743 (13)	0.047 (3)
H2A	0.6200	0.1663	−0.1066	0.056*
H2B	0.4940	0.1190	−0.0650	0.056*
N3	0.1518 (14)	0.2743 (6)	0.1119 (13)	0.044 (3)
H3A	0.1211	0.2259	0.1191	0.053*
H3B	0.1029	0.3134	0.1386	0.053*
C1	0.4759 (17)	0.2325 (7)	−0.0381 (15)	0.034 (3)
C2	0.5364 (17)	0.3061 (7)	−0.0492 (17)	0.036 (3)
C3	0.4653 (17)	0.3720 (8)	−0.0099 (15)	0.040 (4)
H3	0.5047	0.4227	−0.0212	0.048*
C4	0.3354 (18)	0.3649 (7)	0.0466 (15)	0.034 (3)
C5	0.2745 (17)	0.2888 (8)	0.0595 (15)	0.039 (3)

	U11	U22	U33	U12	U13	U23
Sn1	0.0293 (7)	0.0234 (6)	0.0365 (8)	0.0000 (5)	0.0169 (6)	−0.0002 (5)
Br1	0.0485 (9)	0.0374 (7)	0.0537 (10)	−0.0074 (7)	0.0264 (8)	−0.0159 (7)
Br2	0.0494 (9)	0.0430 (8)	0.0499 (10)	−0.0016 (7)	0.0279 (8)	0.0093 (7)
Br3	0.0271 (7)	0.0319 (7)	0.0677 (10)	0.0009 (6)	0.0180 (7)	−0.0014 (7)
Br4	0.0472 (9)	0.0493 (9)	0.0706 (11)	−0.0030 (8)	0.0381 (9)	−0.0045 (8)
Br5	0.0480 (9)	0.0333 (7)	0.0680 (11)	0.0059 (7)	0.0272 (9)	−0.0091 (7)
N1	0.037 (6)	0.018 (5)	0.055 (8)	−0.003 (5)	0.032 (6)	−0.002 (5)
N2	0.061 (9)	0.029 (6)	0.059 (8)	0.003 (6)	0.032 (7)	−0.011 (6)
N3	0.042 (7)	0.035 (6)	0.069 (9)	−0.014 (6)	0.037 (7)	−0.017 (6)
C1	0.035 (8)	0.024 (6)	0.042 (9)	0.007 (6)	0.012 (7)	−0.002 (6)
C2	0.037 (8)	0.016 (6)	0.063 (9)	0.004 (6)	0.028 (7)	0.001 (6)
C3	0.038 (9)	0.032 (7)	0.048 (9)	−0.018 (7)	0.015 (8)	0.007 (6)
C4	0.049 (9)	0.017 (6)	0.034 (8)	−0.002 (6)	0.013 (7)	−0.004 (5)
C5	0.032 (8)	0.046 (8)	0.030 (8)	−0.003 (7)	0.004 (6)	−0.012 (6)

Sn1—Br1	2.6002 (13)	N3—H3A	0.8600
Sn1—Br1i	2.6002 (13)	N3—H3B	0.8600
Sn1—Br2	2.5768 (14)	C1—N1	1.362 (16)
Sn1—Br2i	2.5768 (14)	C1—N2	1.349 (15)
Sn1—Br3	2.6131 (14)	C1—C2	1.350 (17)
Sn1—Br3i	2.6131 (14)	C2—Br4	1.868 (12)
N1—C5	1.357 (15)	C2—C3	1.372 (18)
N1—H1	0.8600	C3—C4	1.392 (18)
N2—H2A	0.8600	C3—H3	0.9300
N2—H2B	0.8600	C4—Br5	1.878 (12)
N3—C5	1.328 (16)	C4—C5	1.394 (18)
Br1—Sn1—Br1i	180.0	H2A—N2—H2B	120.0
Br1i—Sn1—Br3	88.56 (5)	C5—N3—H3A	120.0
Br1—Sn1—Br3i	88.56 (5)	C5—N3—H3B	120.0
Br1—Sn1—Br3	91.44 (5)	H3A—N3—H3B	120.0
Br1i—Sn1—Br3i	91.44 (5)	N2—C1—C2	123.9 (12)
Br2—Sn1—Br1	88.21 (5)	N2—C1—N1	117.8 (11)
Br2i—Sn1—Br1i	88.21 (5)	C2—C1—N1	118.3 (10)
Br2i—Sn1—Br1	91.79 (5)	C1—C2—Br4	120.9 (9)
Br2—Sn1—Br1i	91.79 (5)	C1—C2—C3	119.7 (11)
Br2i—Sn1—Br2	180.0	C3—C2—Br4	119.3 (9)
Br2—Sn1—Br3	89.60 (5)	C2—C3—C4	121.6 (11)
Br2i—Sn1—Br3i	89.61 (5)	C2—C3—H3	119.2
Br2i—Sn1—Br3	90.39 (5)	C4—C3—H3	119.2
Br2—Sn1—Br3i	90.39 (5)	C3—C4—Br5	123.1 (9)
Br3i—Sn1—Br3	180.0	C3—C4—C5	118.6 (11)
C1—N1—H1	117.6	C5—C4—Br5	118.3 (10)
C5—N1—C1	124.9 (10)	N1—C5—C4	116.9 (12)
C5—N1—H1	117.6	N3—C5—N1	118.8 (12)
C1—N2—H2A	120.0	N3—C5—C4	124.2 (12)
C1—N2—H2B	120.0
N2—C1—N1—C5	−179.9 (12)	C2—C3—C4—C5	−2(2)
C2—C1—N1—C5	2(2)	C2—C3—C4—Br5	177.8 (11)
N2—C1—C2—C3	179.9 (14)	C1—N1—C5—N3	179.6 (13)
N1—C1—C2—C3	−3(2)	C1—N1—C5—C4	−2(2)
N2—C1—C2—Br4	4(2)	C3—C4—C5—N3	179.8 (13)
N1—C1—C2—Br4	−178.7 (10)	Br5—C4—C5—N3	0.4 (19)
C1—C2—C3—C4	2(2)	C3—C4—C5—N1	1.2 (19)
Br4—C2—C3—C4	178.5 (11)	Br5—C4—C5—N1	−178.2 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br3ii	0.86	2.54	3.354 (9)	159
N2—H2B···Br3ii	0.86	2.88	3.612 (12)	144
N3—H3A···Br2ii	0.86	2.79	3.608 (10)	160
N3—H3B···Br1iii	0.86	2.82	3.604 (10)	153

Table 1

Selected geometric parameters (Å, °)

Sn1—Br1	2.6002 (13)
Sn1—Br2	2.5768 (14)
Sn1—Br3	2.6131 (14)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br3ii	0.86	2.54	3.354 (9)	159
N2—H2B⋯Br3ii	0.86	2.88	3.612 (12)	144
N3—H3A⋯Br2ii	0.86	2.79	3.608 (10)	160
N3—H3B⋯Br1iii	0.86	2.82	3.604 (10)	153

Symmetry codes: (ii) ; (iii) .