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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2919.
Published online 2010 October 23. doi:  10.1107/S1600536810041899
PMCID: PMC3009234

2,2′-Biimidazolium 5-amino-2,4,6-tri­bromo­isophthalate

Abstract

In the cation of the title salt, C6H8N4 2+·C8H2Br3NO4 2−, the dihedral angle between the two five-membered rings is 2.1 (3)°. In the anion, the mean planes of the carboxyl units are twisted from the benzene ring by 84.3 (4) and 86.2 (3)°. In the crystal, the components are linked by imidazolium–carboxyl­ate N—H(...)O hydrogen bonds, generating a chain running along [1An external file that holds a picture, illustration, etc.
Object name is e-66-o2919-efi1.jpg0].

Related literature

For the structure of 5-amino-2,4,6-tribromidoisophthalic acid, see: Beck et al. (2009 [triangle]). For the structures of other 2,2′-bis­(imid­azolium) carboxyl­ates, see: Gao et al. (2009 [triangle]); Li & Yang (2007 [triangle]); Zhou et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2919-scheme1.jpg

Experimental

Crystal data

  • C6H8N4 2+·C8H2Br3NO4 2−
  • M r = 552.00
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2919-efi2.jpg
  • a = 9.0525 (10) Å
  • b = 9.2043 (10) Å
  • c = 11.5252 (12) Å
  • α = 90.262 (1)°
  • β = 108.332 (1)°
  • γ = 93.136 (1)°
  • V = 909.96 (17) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 6.68 mm−1
  • T = 293 K
  • 0.35 × 0.25 × 0.15 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.203, T max = 0.434
  • 8042 measured reflections
  • 4104 independent reflections
  • 3129 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.120
  • S = 1.12
  • 4104 reflections
  • 259 parameters
  • 6 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.81 e Å−3
  • Δρmin = −0.56 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810041899/lh5152sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041899/lh5152Isup2.hkl

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

Acknowledgments

We thank the Key Laboratory of Environmental Material and Environmental Engineering of Jiangsu Province, Yangzhou University and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The crystal structure of 5-Amino-2,4,6-tribromoiodoisophthalic acid exists as a chains in which adjacent molecules are linked by O–H···O hydrogen bonds. In addition, pairs of chains are connected by further O–H···O hydrogen bonds (Beck et al., 2009). This acid furnishes a small number of coordination compounds. An attempt to synthesize a lead(II) derivative that can be linked by 2,2'-biimidazole gave instead the title salt, [C6H8N4]2+ [C8H2NO4I3]2–(1). Other examples of crystal structure of 2,2'-bis(imidazolium) carboxylates already appear in the literature (Gao et al., 2009; Li & Yang, 2007; Zhou et al., 2009).

The asymmetric unit of (1) is shown in Fig. 1. The cation is nearly planar as its two five-membered rings are twisted along the Cimidazolyl–Cimidazolyl bond by 2.1 (3) ° only. In the anion, both –CO2 units are almost orthogonal to the bezene ring mean plane [dihedral angles between –CO2 plane and benzene ring (r.m.s. deviation 0.018 Å) are 84.3 (4)° and 86.2 (3) °]. In the crystal structure, cations and anions are linked by Nimidazolyl–H···O hydrogen bonds to generate a chain formation running along [110](Fig. 2).

Experimental

An aqueous solution of lead nitrate (0.006 g, 0.2 mmol) in water (5 ml) was added to a mixture of 5-amino-2,4,6-tribromidoisophthalic acid (0.056 g, 0.1 mmol) in water (5 ml) and sodium hydroxide (0.2 ml, 0.5 M). To this solution was added 2,2'-biimidazole (0.014 g, 0.1 mmol) in DMF (5 ml). The solution was filtered; slow evaporation yielded pale yellow crystals which were collected (30% yield). CH&N elemental analysis. Calc. for C14H10Br3N5O4: C 30.46, H 1.83, N 12.69%.; Found: C, 30.38; H, 1.91; N, 12.77%.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Ueq(C).

The imidazolyl and amino H-atoms were located in a difference Fourier map, and were refined with a distance restraint of N–H 0.88±0.01 Å; their temperature factors were refined.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C6H8N42+ C8H2NO4Br32– at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
Fig. 2.
Part of the crystal structure showing hydrogen bonds as dashed lines.

Crystal data

C6H8N42+·C8H2Br3NO42Z = 2
Mr = 552.00F(000) = 532
Triclinic, P1Dx = 2.015 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.0525 (10) ÅCell parameters from 2718 reflections
b = 9.2043 (10) Åθ = 2.4–27.4°
c = 11.5252 (12) ŵ = 6.68 mm1
α = 90.262 (1)°T = 293 K
β = 108.332 (1)°Prism, pale yellow
γ = 93.136 (1)°0.35 × 0.25 × 0.15 mm
V = 909.96 (17) Å3

Data collection

Bruker SMART APEX diffractometer4104 independent reflections
Radiation source: fine-focus sealed tube3129 reflections with I > 2σ(I)
graphiteRint = 0.025
ω scansθmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −11→11
Tmin = 0.203, Tmax = 0.434k = −11→11
8042 measured reflectionsl = −14→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 1.12w = 1/[σ2(Fo2) + (0.0618P)2 + 0.430P] where P = (Fo2 + 2Fc2)/3
4104 reflections(Δ/σ)max = 0.001
259 parametersΔρmax = 0.81 e Å3
6 restraintsΔρmin = −0.56 e Å3

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

xyzUiso*/Ueq
Br10.44985 (5)0.68067 (5)0.04955 (4)0.03399 (14)
Br20.30262 (7)0.89508 (6)0.45860 (5)0.05335 (18)
Br30.80240 (6)0.52283 (6)0.52786 (5)0.05028 (17)
O10.6388 (4)0.3751 (3)0.2311 (3)0.0364 (7)
O20.8128 (4)0.5529 (3)0.2201 (3)0.0424 (8)
O30.1481 (4)0.8223 (4)0.1385 (3)0.0419 (8)
O40.3322 (4)1.0034 (3)0.1754 (4)0.0465 (9)
N10.5757 (6)0.7119 (6)0.5998 (4)0.0536 (12)
N20.7881 (4)0.1504 (4)0.2018 (4)0.0326 (8)
N30.9353 (4)−0.0118 (4)0.1680 (4)0.0356 (9)
N41.1546 (4)0.2242 (4)0.1272 (3)0.0305 (8)
N51.0016 (4)0.3864 (4)0.1539 (3)0.0258 (7)
C10.6952 (5)0.5045 (5)0.2451 (4)0.0300 (9)
C20.6062 (5)0.6121 (4)0.2971 (4)0.0265 (8)
C30.4913 (5)0.6934 (4)0.2216 (4)0.0246 (8)
C40.4030 (5)0.7833 (4)0.2686 (4)0.0276 (9)
C50.4310 (5)0.7852 (5)0.3941 (4)0.0329 (10)
C60.5465 (5)0.7061 (5)0.4750 (4)0.0343 (10)
C70.6352 (5)0.6244 (4)0.4223 (4)0.0293 (9)
C80.2831 (5)0.8777 (4)0.1859 (4)0.0310 (9)
C90.7208 (6)0.0171 (5)0.2144 (5)0.0491 (13)
H90.6293−0.00040.23370.059*
C100.8132 (6)−0.0853 (5)0.1932 (5)0.0485 (13)
H100.7967−0.18570.19540.058*
C110.9166 (5)0.1302 (4)0.1731 (4)0.0260 (8)
C121.0206 (5)0.2449 (4)0.1518 (4)0.0253 (8)
C131.2192 (5)0.3590 (5)0.1138 (4)0.0343 (10)
H131.31180.37730.09600.041*
C141.1255 (5)0.4600 (4)0.1306 (4)0.0307 (9)
H141.14140.56040.12730.037*
H20.751 (7)0.232 (4)0.217 (5)0.068 (19)*
H31.005 (5)−0.054 (5)0.143 (5)0.054 (16)*
H41.215 (6)0.151 (5)0.139 (6)0.09 (2)*
H50.923 (4)0.424 (5)0.171 (4)0.035 (13)*
H110.519 (6)0.764 (6)0.631 (5)0.07 (2)*
H120.624 (6)0.640 (4)0.643 (4)0.056 (18)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0363 (3)0.0361 (3)0.0319 (2)0.01227 (19)0.01250 (19)−0.00142 (18)
Br20.0560 (4)0.0543 (4)0.0623 (4)0.0200 (3)0.0340 (3)−0.0138 (3)
Br30.0441 (3)0.0611 (4)0.0420 (3)0.0224 (3)0.0049 (2)0.0071 (2)
O10.0342 (17)0.0232 (15)0.060 (2)0.0058 (13)0.0254 (15)−0.0047 (14)
O20.0372 (19)0.0282 (17)0.075 (2)0.0075 (14)0.0350 (18)0.0010 (16)
O30.0223 (16)0.0374 (19)0.063 (2)0.0091 (14)0.0084 (15)−0.0072 (16)
O40.0372 (19)0.0170 (16)0.088 (3)0.0121 (14)0.0217 (18)0.0094 (16)
N10.067 (3)0.062 (3)0.036 (2)0.020 (3)0.019 (2)−0.005 (2)
N20.0230 (18)0.0250 (19)0.055 (2)0.0067 (15)0.0198 (17)−0.0002 (17)
N30.028 (2)0.0250 (19)0.059 (2)0.0073 (16)0.0192 (18)−0.0025 (17)
N40.0188 (17)0.034 (2)0.042 (2)0.0098 (15)0.0134 (15)0.0030 (16)
N50.0170 (16)0.0258 (18)0.0388 (19)0.0093 (14)0.0134 (14)0.0022 (15)
C10.034 (2)0.030 (2)0.030 (2)0.0114 (19)0.0135 (18)0.0013 (17)
C20.027 (2)0.0187 (19)0.036 (2)0.0059 (16)0.0125 (17)−0.0015 (16)
C30.028 (2)0.020 (2)0.0280 (19)0.0052 (16)0.0116 (17)−0.0030 (15)
C40.024 (2)0.021 (2)0.041 (2)0.0066 (16)0.0145 (18)−0.0016 (17)
C50.031 (2)0.030 (2)0.044 (2)0.0102 (19)0.019 (2)−0.0103 (19)
C60.034 (2)0.036 (2)0.036 (2)0.005 (2)0.015 (2)−0.0061 (19)
C70.025 (2)0.024 (2)0.039 (2)0.0078 (17)0.0091 (18)0.0007 (17)
C80.031 (2)0.020 (2)0.048 (3)0.0161 (18)0.018 (2)−0.0008 (18)
C90.041 (3)0.034 (3)0.084 (4)−0.002 (2)0.035 (3)−0.002 (3)
C100.042 (3)0.023 (2)0.088 (4)0.002 (2)0.031 (3)0.003 (2)
C110.029 (2)0.0151 (19)0.034 (2)0.0067 (16)0.0089 (17)−0.0003 (16)
C120.030 (2)0.0144 (18)0.033 (2)0.0075 (16)0.0107 (17)0.0003 (15)
C130.036 (2)0.027 (2)0.045 (3)0.0033 (19)0.019 (2)0.0031 (19)
C140.035 (2)0.0154 (19)0.042 (2)0.0045 (17)0.0125 (19)0.0054 (17)

Geometric parameters (Å, °)

Br1—C31.901 (4)N5—C121.325 (5)
Br2—C51.895 (4)N5—C141.377 (5)
Br3—C71.911 (4)N5—H50.882 (10)
O1—C11.259 (5)C1—C21.541 (5)
O2—C11.248 (5)C2—C71.386 (6)
O3—C81.250 (5)C2—C31.386 (5)
O4—C81.237 (5)C3—C41.399 (5)
N1—C61.378 (6)C4—C51.388 (6)
N1—H110.877 (10)C4—C81.517 (6)
N1—H120.879 (10)C5—C61.403 (6)
N2—C111.327 (5)C6—C71.396 (6)
N2—C91.369 (6)C9—C101.364 (7)
N2—H20.880 (10)C9—H90.9300
N3—C111.330 (5)C10—H100.9300
N3—C101.373 (6)C11—C121.449 (6)
N3—H30.879 (10)C13—C141.346 (6)
N4—C121.352 (5)C13—H130.9300
N4—C131.373 (6)C14—H140.9300
N4—H40.880 (10)
C6—N1—H11120 (4)C6—C5—Br2118.5 (3)
C6—N1—H12118 (4)N1—C6—C7121.3 (4)
H11—N1—H12119 (6)N1—C6—C5122.5 (4)
C11—N2—C9108.4 (4)C7—C6—C5116.1 (4)
C11—N2—H2129 (4)C2—C7—C6123.0 (4)
C9—N2—H2122 (4)C2—C7—Br3118.6 (3)
C11—N3—C10108.3 (4)C6—C7—Br3118.4 (3)
C11—N3—H3127 (4)O4—C8—O3127.7 (4)
C10—N3—H3124 (4)O4—C8—C4114.7 (4)
C12—N4—C13107.4 (4)O3—C8—C4117.7 (4)
C12—N4—H4132 (4)C10—C9—N2107.2 (4)
C13—N4—H4117 (4)C10—C9—H9126.4
C12—N5—C14108.8 (3)N2—C9—H9126.4
C12—N5—H5124 (3)C9—C10—N3106.9 (4)
C14—N5—H5127 (3)C9—C10—H10126.6
O2—C1—O1126.7 (4)N3—C10—H10126.6
O2—C1—C2117.9 (4)N2—C11—N3109.2 (4)
O1—C1—C2115.4 (4)N2—C11—C12125.3 (4)
C7—C2—C3118.2 (4)N3—C11—C12125.5 (4)
C7—C2—C1119.9 (4)N5—C12—N4108.7 (3)
C3—C2—C1121.8 (4)N5—C12—C11126.1 (4)
C2—C3—C4121.7 (4)N4—C12—C11125.2 (4)
C2—C3—Br1119.4 (3)C14—C13—N4108.2 (4)
C4—C3—Br1118.9 (3)C14—C13—H13125.9
C5—C4—C3117.6 (4)N4—C13—H13125.9
C5—C4—C8121.0 (3)C13—C14—N5106.9 (4)
C3—C4—C8121.3 (4)C13—C14—H14126.5
C4—C5—C6123.2 (4)N5—C14—H14126.5
C4—C5—Br2118.3 (3)
O2—C1—C2—C7−96.8 (5)C5—C6—C7—C2−4.4 (6)
O1—C1—C2—C783.9 (5)N1—C6—C7—Br3−1.2 (6)
O2—C1—C2—C386.3 (5)C5—C6—C7—Br3176.5 (3)
O1—C1—C2—C3−93.0 (5)C5—C4—C8—O485.3 (5)
C7—C2—C3—C4−1.5 (6)C3—C4—C8—O4−93.6 (5)
C1—C2—C3—C4175.4 (4)C5—C4—C8—O3−93.5 (5)
C7—C2—C3—Br1179.4 (3)C3—C4—C8—O387.6 (5)
C1—C2—C3—Br1−3.7 (5)C11—N2—C9—C100.4 (6)
C2—C3—C4—C5−2.0 (6)N2—C9—C10—N30.0 (7)
Br1—C3—C4—C5177.1 (3)C11—N3—C10—C9−0.4 (6)
C2—C3—C4—C8176.9 (4)C9—N2—C11—N3−0.7 (5)
Br1—C3—C4—C8−4.1 (5)C9—N2—C11—C12179.9 (4)
C3—C4—C5—C62.5 (6)C10—N3—C11—N20.7 (5)
C8—C4—C5—C6−176.4 (4)C10—N3—C11—C12−179.9 (4)
C3—C4—C5—Br2−175.5 (3)C14—N5—C12—N4−0.2 (5)
C8—C4—C5—Br25.6 (6)C14—N5—C12—C11179.4 (4)
C4—C5—C6—N1178.2 (5)C13—N4—C12—N50.0 (5)
Br2—C5—C6—N1−3.8 (6)C13—N4—C12—C11−179.7 (4)
C4—C5—C6—C70.6 (7)N2—C11—C12—N5−2.3 (7)
Br2—C5—C6—C7178.6 (3)N3—C11—C12—N5178.4 (4)
C3—C2—C7—C64.9 (6)N2—C11—C12—N4177.3 (4)
C1—C2—C7—C6−172.0 (4)N3—C11—C12—N4−2.0 (7)
C3—C2—C7—Br3−176.0 (3)C12—N4—C13—C140.2 (5)
C1—C2—C7—Br37.0 (5)N4—C13—C14—N5−0.4 (5)
N1—C6—C7—C2177.9 (4)C12—N5—C14—C130.4 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O10.88 (1)1.74 (2)2.608 (4)168 (6)
N3—H3···O3i0.88 (1)1.78 (2)2.624 (5)160 (5)
N4—H4···O4i0.88 (1)1.74 (1)2.614 (5)175 (7)
N5—H5···O20.88 (1)1.79 (2)2.636 (4)160 (4)

Symmetry codes: (i) x+1, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5152).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Beck, T., Herbst-Irmer, R. & Sheldrick, G. M. (2009). Acta Cryst. C65, o237–o239. [PubMed]
  • Bruker (2005). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Gao, X.-L., Lu, L.-P. & Zhu, M.-L. (2009). Acta Cryst. C65, o123–o127. [PubMed]
  • Li, Y.-P. & Yang, P. (2007). Chin. J. Chem.25, 1715–1721.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.
  • Zhou, C.-S., Ding, L.-L., Zhang, H., Cao, M.-N. & Meng, X.-G. (2009). Acta Cryst. C65, o51–o53. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography