4,4'-Bipyridine-1,1'-diium 2,3,5,6-tetra-bromo-terephthalate dihydrate.

The title compound, C(10)H(10)N(2) (2+)·C(8)Br(4)O(4) (2-)·2H(2)O, consists of a tetra-bromo-terephthalate dianion, a 4,4'-bipyridinium dication and two solvent water mol-ecules. Crystallographic inversion centers are situated at the center of the aromatic ring of the dianion as well as at the midpoint of the carbon-carbon bond connecting the pyridine rings in the dication. In the crystal, inter-molecular N-H⋯O hydrogen-bonding inter-actions between tetra-bromo-terephthalate dianions and protonated 4,4'-bipyridinium dications result in the formation of a chain-like structure. Further O-H⋯O hydrogen bonds between carboxyl-ate O atoms and water mol-ecules lead to the formation of a two-dimensional network in the crystal structure.

Related literature

For hydrogen-bonded assemblies, see: Desiraju & Steiner (1999 ▶); Jia et al. (2009 ▶); Soleimannejad et al. (2009 ▶). For proton transfer, see: Kawata et al. (2002 ▶).

Experimental

Crystal data

C10H10N2 2+·C8Br4O4 2−·2H2O

M = 673.93

Triclinic,

a = 6.503 (3) Å

b = 9.249 (4) Å

c = 9.987 (4) Å

α = 64.119 (14)°

β = 85.868 (18)°

γ = 73.737 (14)°

V = 517.9 (4) Å3

Z = 1

Mo Kα radiation

μ = 7.83 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury70 diffractometer

Absorption correction: multi-scan (REQAB; Rigaku, 1998 ▶) T min = 0.126, T max = 0.209

5065 measured reflections

2336 independent reflections

2116 reflections with F 2 > 2.0σ(F 2)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.086

S = 1.19

2336 reflections

136 parameters

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −1.55 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: IL MILIONE (Burla et al., 2007 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalMaker (Palmer, 2004 ▶); software used to prepare material for publication: CrystalStructure (Rigaku, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811035926/im2306sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035926/im2306Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811035926/im2306Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536811035926/im2306Isup4.cml

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

C10H10N22+·C8Br4O42−·2H2O	Z = 1
Mr = 673.93	F(000) = 324.00
Triclinic, P1	Dx = 2.161 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 6.503 (3) Å	Cell parameters from 1137 reflections
b = 9.249 (4) Å	θ = 3.3–27.5°
c = 9.987 (4) Å	µ = 7.83 mm−1
α = 64.119 (14)°	T = 293 K
β = 85.868 (18)°	Prism, colorless
γ = 73.737 (14)°	0.30 × 0.20 × 0.20 mm
V = 517.9 (4) Å3

Rigaku Mercury70 diffractometer	2116 reflections with F2 > 2.0σ(F2)
Detector resolution: 7.314 pixels mm-1	Rint = 0.027
ω scans	θmax = 27.5°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −8→8
Tmin = 0.126, Tmax = 0.209	k = −12→12
5065 measured reflections	l = −12→12
2336 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086	H-atom parameters constrained
S = 1.19	w = 1/[σ2(Fo2) + (0.0449P)2 + 0.1173P] where P = (Fo2 + 2Fc2)/3
2336 reflections	(Δ/σ)max = 0.001
136 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −1.55 e Å−3
Primary atom site location: structure-invariant direct methods

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

	x	y	z	Uiso*/Ueq
Br1	0.10645 (4)	0.42116 (4)	0.71999 (3)	0.03083 (11)
Br2	0.32963 (5)	0.18104 (4)	0.54456 (3)	0.03350 (12)
O1	0.1557 (4)	0.8335 (3)	0.5839 (3)	0.0351 (5)
O2	0.3797 (4)	0.6584 (3)	0.7830 (3)	0.0422 (6)
O3	0.7487 (4)	0.4074 (3)	0.9249 (3)	0.0446 (6)
N1	0.8843 (4)	0.9226 (3)	0.7575 (3)	0.0306 (6)
C1	0.8549 (6)	1.0592 (5)	0.7789 (4)	0.0409 (8)
C2	0.7080 (5)	1.0919 (4)	0.8752 (4)	0.0368 (7)
C3	0.5825 (4)	0.9836 (4)	0.9480 (3)	0.0236 (6)
C4	0.6149 (5)	0.8444 (5)	0.9214 (4)	0.0367 (7)
C5	0.7679 (6)	0.8159 (4)	0.8268 (4)	0.0377 (7)
C6	0.4067 (4)	0.6003 (3)	0.5735 (3)	0.0221 (5)
C7	0.3331 (4)	0.4652 (4)	0.5922 (3)	0.0229 (5)
C8	0.4251 (4)	0.3656 (4)	0.5196 (3)	0.0231 (5)
C9	0.3056 (5)	0.7067 (4)	0.6539 (3)	0.0262 (6)
H1	0.9351	1.1338	0.7277	0.0491*
H2	0.6927	1.1859	0.8916	0.0442*
H3	0.5329	0.7698	0.9677	0.0441*
H4	0.7906	0.7208	0.8110	0.0452*
H5	0.9899	0.8937	0.6971	0.0367*
H6	0.7539	0.3878	1.0277	0.0670*
H7	0.6152	0.4970	0.8711	0.0670*

	U11	U22	U33	U12	U13	U23
Br1	0.02820 (17)	0.03494 (19)	0.03224 (19)	−0.01138 (13)	0.01655 (12)	−0.01780 (14)
Br2	0.03620 (19)	0.03384 (19)	0.0411 (2)	−0.01650 (14)	0.01468 (14)	−0.02352 (15)
O1	0.0340 (11)	0.0330 (11)	0.0321 (11)	0.0036 (9)	0.0083 (9)	−0.0172 (9)
O2	0.0477 (13)	0.0549 (14)	0.0277 (12)	−0.0052 (11)	0.0025 (10)	−0.0266 (11)
O3	0.0460 (14)	0.0483 (14)	0.0416 (14)	−0.0126 (11)	0.0168 (11)	−0.0237 (12)
N1	0.0286 (12)	0.0356 (13)	0.0320 (13)	−0.0080 (10)	0.0150 (10)	−0.0211 (11)
C1	0.0426 (18)	0.0430 (18)	0.050 (2)	−0.0230 (15)	0.0297 (16)	−0.0292 (17)
C2	0.0434 (17)	0.0342 (16)	0.0468 (19)	−0.0185 (14)	0.0247 (15)	−0.0287 (15)
C3	0.0239 (13)	0.0270 (13)	0.0226 (13)	−0.0063 (10)	0.0070 (11)	−0.0145 (11)
C4	0.0438 (17)	0.0400 (16)	0.0412 (18)	−0.0220 (14)	0.0226 (15)	−0.0276 (15)
C5	0.0479 (18)	0.0391 (17)	0.0413 (18)	−0.0177 (14)	0.0192 (15)	−0.0302 (15)
C6	0.0204 (12)	0.0252 (12)	0.0200 (13)	−0.0012 (10)	0.0033 (10)	−0.0127 (11)
C7	0.0197 (12)	0.0283 (13)	0.0208 (13)	−0.0048 (10)	0.0067 (10)	−0.0127 (11)
C8	0.0225 (12)	0.0226 (12)	0.0245 (13)	−0.0046 (10)	0.0043 (10)	−0.0121 (11)
C9	0.0277 (14)	0.0307 (14)	0.0274 (15)	−0.0097 (11)	0.0122 (11)	−0.0196 (12)

Br1—C7	1.892 (3)	C6—C7	1.394 (5)
Br2—C8	1.887 (4)	C6—C8ii	1.396 (4)
O1—C9	1.248 (3)	C6—C9	1.516 (5)
O2—C9	1.249 (4)	C7—C8	1.395 (5)
N1—C1	1.332 (6)	O3—H6	0.963
N1—C5	1.331 (5)	O3—H7	1.002
C1—C2	1.374 (6)	N1—H5	0.941
C2—C3	1.392 (5)	C1—H1	0.930
C3—C3i	1.501 (4)	C2—H2	0.930
C3—C4	1.382 (6)	C4—H3	0.930
C4—C5	1.374 (5)	C5—H4	0.930
O1···H5iii	1.670	H5···O1vi	1.670
O1···H5iv	2.828	H5···O1iv	2.828
O2···H5iii	2.737	H5···O2vi	2.737
O2···H6v	1.944	H6···O2v	1.944
O2···H7	1.765	H7···O2	1.765
C1—N1—C5	120.5 (3)	C6ii—C8—C7	120.4 (3)
N1—C1—C2	121.2 (4)	O1—C9—O2	126.8 (4)
C1—C2—C3	119.6 (4)	O1—C9—C6	116.2 (3)
C2—C3—C3i	121.2 (4)	O2—C9—C6	116.9 (3)
C2—C3—C4	117.7 (3)	H6—O3—H7	110.0
C3i—C3—C4	121.1 (3)	C1—N1—H5	122.8
C3—C4—C5	120.1 (4)	C5—N1—H5	116.6
N1—C5—C4	120.9 (4)	N1—C1—H1	119.417
C7—C6—C8ii	118.8 (3)	C2—C1—H1	119.409
C7—C6—C9	120.1 (3)	C1—C2—H2	120.212
C8ii—C6—C9	121.1 (3)	C3—C2—H2	120.215
Br1—C7—C6	117.8 (3)	C3—C4—H3	119.938
Br1—C7—C8	121.4 (3)	C5—C4—H3	119.934
C6—C7—C8	120.8 (3)	N1—C5—H4	119.564
Br2—C8—C6ii	118.1 (3)	C4—C5—H4	119.572
Br2—C8—C7	121.6 (2)
C1—N1—C5—C4	0.2 (5)	C8ii—C6—C7—C8	−0.0 (4)
C5—N1—C1—C2	1.5 (5)	C7—C6—C9—O1	−93.1 (3)
N1—C1—C2—C3	−2.2 (5)	C7—C6—C9—O2	86.7 (4)
C1—C2—C3—C3i	−178.9 (3)	C9—C6—C7—Br1	−0.1 (3)
C1—C2—C3—C4	1.1 (4)	C9—C6—C7—C8	−179.68 (19)
C2—C3—C3i—C4i	0.0 (4)	C8ii—C6—C9—O1	87.3 (4)
C2—C3—C4—C5	0.5 (4)	C8ii—C6—C9—O2	−93.0 (3)
C3i—C3—C4—C5	−179.5 (3)	C9—C6—C8ii—Br2ii	−0.8 (3)
C4—C3—C3i—C2i	−0.0 (4)	C9—C6—C8ii—C7ii	179.68 (19)
C3—C4—C5—N1	−1.2 (5)	Br1—C7—C8—Br2	−0.1 (3)
C7—C6—C8ii—Br2ii	179.51 (18)	Br1—C7—C8—C6ii	−179.58 (14)
C7—C6—C8ii—C7ii	0.0 (4)	C6—C7—C8—Br2	179.49 (18)
C8ii—C6—C7—Br1	179.59 (18)	C6—C7—C8—C6ii	0.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H6···O2v	0.963	1.944	2.822 (4)	150.5
O3—H7···O2	1.002	1.765	2.766 (3)	177.2
N1—H5···O1vi	0.941	1.670	2.606 (4)	172.9

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H6⋯O2i	0.963	1.944	2.822 (4)	150.5
O3—H7⋯O2	1.002	1.765	2.766 (3)	177.2
N1—H5⋯O1ii	0.941	1.670	2.606 (4)	172.9

Symmetry codes: (i) ; (ii) .