4,4′-Bipyridine-1,1′-diium 2,3,5,6-tetra­bromo­terephthalate dihydrate

Kumagai, H.; Kawata, S.

doi:10.1107/S1600536811035926

organic compounds

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Volume 67| Part 10| October 2011| Page o2636

https://doi.org/10.1107/S1600536811035926

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4,4′-Bipyridine-1,1′-diium 2,3,5,6-tetrabromoterephthalate dihydrate

Hitoshi Kumagai ^a ^* and Satoshi Kawata ^b

^aInstitute for Molecular Science, 38 Nishigounaka Okazaki, Aichi, Japan, and ^bDepartment of Chemistry, Fukuoka University, Fukuoka 814-0180, Japan
^*Correspondence e-mail: e1254@mosk.tytlabs.co.jp

(Received 9 July 2011; accepted 2 September 2011; online 14 September 2011)

The title compound, C₁₀H₁₀N₂²⁺·C₈Br₄O₄²⁻·2H₂O, consists of a tetrabromoterephthalate dianion, a 4,4′-bipyridinium dication and two solvent water molecules. 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, intermolecular N—H⋯O hydrogen-bonding interactions between tetrabromoterephthalate dianions and protonated 4,4′-bipyridinium dications result in the formation of a chain-like structure. Further O—H⋯O hydrogen bonds between carboxylate O atoms and water molecules 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

C₁₀H₁₀N₂²⁺·C₈Br₄O₄²⁻·2H₂O
M_r = 673.93
Triclinic, $[P \overline 1]$
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 F² > 2.0σ(F²)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.086
S = 1.19
2336 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −1.55 e Å⁻³

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) -x+1, -y+1, -z+2; (ii) x+1, y, z.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811035926/im2306sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035926/im2306Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811035926/im2306Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S1600536811035926/im2306Isup4.cml

checkCIF report

Comment top

Hydrogen bonded inorganic and organic compounds are of great current interest in recent years due to fundamental scientific and technological applications (Desiraju & Steiner,1999; Kawata et al., 2002). Here we report the synthesis and single-crystal structure of the title compound [(C₈Br₄O₄)(C₁₀H₁₀N₂).2H₂O)]. It consists of a tetrabromoterephthalate dianion, a 4,4'-bipyridinium dication and solvent water molecules. Intermolecular N–H···O hydrogen bonding interactions between tetrabromoterephthalate dianions and protonated 4,4'-bipyridinium dications result in the formation of a one-dimensional chain-like structure. Further O–H···O hydrogen bonds between oxygen atoms of carboxylates and water molecules lead to the formation of a two-dimensional network in the crystal structure.

Related literature top

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 top

An aqueous solution (2 ml) of cerium nitrate hexahydrate (0.43 g, 1 mmolL^-1) was transferred to a glass tube, then a mixture of tetrabromoterephthalic acid (0.48 g, 1 mmolL^-1), NaOH (0.08 g, 2 mmolL^-1) and 4,4'-bpy (0.15 g, 1 mmolL^-1) in ethanol/water (2 ml) was poured into the glass tube without mixing the two solutions. Colorless crystals began to form at ambient temperature during 1 month. One of these crystals was used for X-ray crystallography.

Structure description top

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

Computing details top

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

Figures top

	Fig. 1. ORTEP drawing of the title compound showing 50% probability displacement ellipsoids.
	Fig. 2. Hydrogen bonding interactions for the title compound.

4,4'-Bipyridine-1,1'-diium 2,3,5,6-tetrabromoterephthalate dihydrate top

Crystal data top

C₁₀H₁₀N₂²⁺·C₈Br₄O₄²⁻·2H₂O	Z = 1
M_r = 673.93	F(000) = 324.00
Triclinic, P1	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0449P)² + 0.1173P] where P = (F_o² + 2F_c²)/3
2336 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −1.55 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₀H₁₀N₂²⁺·C₈Br₄O₄²⁻·2H₂O	γ = 73.737 (14)°
M_r = 673.93	V = 517.9 (4) Å³
Triclinic, P1	Z = 1
a = 6.503 (3) Å	Mo Kα radiation
b = 9.249 (4) Å	µ = 7.83 mm⁻¹
c = 9.987 (4) Å	T = 293 K
α = 64.119 (14)°	0.30 × 0.20 × 0.20 mm
β = 85.868 (18)°

Data collection top

Rigaku Mercury70 diffractometer	2336 independent reflections
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	2116 reflections with F² > 2.0σ(F²)
T_min = 0.126, T_max = 0.209	R_int = 0.027
5065 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.19	Δρ_max = 0.48 e Å⁻³
2336 reflections	Δρ_min = −1.55 e Å⁻³
136 parameters

Special details top

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).

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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···O1^vi	1.670
O1···H5^iv	2.828	H5···O1^iv	2.828
O2···H5ⁱⁱⁱ	2.737	H5···O2^vi	2.737
O2···H6^v	1.944	H6···O2^v	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)

Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+2, −z+1; (v) −x+1, −y+1, −z+2; (vi) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H6···O2^v	0.963	1.944	2.822 (4)	150.5
O3—H7···O2	1.002	1.765	2.766 (3)	177.2
N1—H5···O1^vi	0.941	1.670	2.606 (4)	172.9

Symmetry codes: (v) −x+1, −y+1, −z+2; (vi) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₂²⁺·C₈Br₄O₄²⁻·2H₂O
M_r	673.93
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.503 (3), 9.249 (4), 9.987 (4)
α, β, γ (°)	64.119 (14), 85.868 (18), 73.737 (14)
V (Å³)	517.9 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	7.83
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury70
Absorption correction	Multi-scan (REQAB; Rigaku, 1998)
T_min, T_max	0.126, 0.209
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	5065, 2336, 2116
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.086, 1.19
No. of reflections	2336
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −1.55

Computer programs: CrystalClear (Rigaku/MSC, 2005), IL MILIONE (Burla et al., 2007), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku, 2010), CrystalMaker (Palmer, 2004).

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y+1, −z+2; (ii) x+1, y, z.

Acknowledgements

HK thanks the Japan Society for the Promotion of Science for his postdoctoral fellowship.

References

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