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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2252–o2253.
Published online 2010 August 11. doi:  10.1107/S1600536810030989
PMCID: PMC3007988

Bis(2-amino-5-bromo­pyridinium) fumarate dihydrate

Abstract

In the title compound, 2C5H6BrN2 +·C4H2O4 2−·2H2O, the complete fumarate dianion is generated by crystallographic inversion symmetry. The cation is approximately planar, with a maximum deviation of 0.036 (1) Å. In the anion, the carboxyl­ate group is twisted slightly away from the attached plane; the dihedral angle between carboxyl­ate and (E)-but-2-ene planes is 6.11 (14)°. In the crystal, the carboxyl­ate O atoms form bifurcated (N—H(...)O and C—H(...)O) and N—H(...)O hydrogen bonds with the cations. The crystal packing is stabilized by R 2 2(8) ring motifs which are generated by pairs of N—H(...)O hydrogen bonds. The crystal structure is further consolidated by water mol­ecules via O(water)—H(...)O and N—H(...)O(water) hydrogen bonds. The components are linked by these inter­actions into three-dimensional network.

Related literature

For details of hydrogen bonding, see: Goswami & Ghosh (1997 [triangle]); Goswami et al. (1998 [triangle]). For applications of fumaric acid, see: Batchelor et al. (2000 [triangle]). For related structures, see: Büyükgüngör et al. (2004 [triangle]); Büyükgüngör & Odabąsoğlu (20065); Hemamalini & Fun, (2010a,b); Quah et al. (2008 [triangle]; 2010a,b). For bond-length data, see: Allen et al. (1987 [triangle]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2252-scheme1.jpg

Experimental

Crystal data

  • 2C5H6BrN2 +·C4H2O4 2−·H2O
  • M r = 498.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2252-efi1.jpg
  • a = 8.3717 (1) Å
  • b = 16.5354 (2) Å
  • c = 6.7846 (1) Å
  • β = 108.336 (1)°
  • V = 891.50 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 4.59 mm−1
  • T = 100 K
  • 0.39 × 0.15 × 0.12 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.271, T max = 0.618
  • 15040 measured reflections
  • 3942 independent reflections
  • 3252 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.059
  • S = 1.03
  • 3942 reflections
  • 138 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.54 e Å−3
  • Δρmin = −0.39 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810030989/bt5312sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030989/bt5312Isup2.hkl

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

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (1001/PFIZIK/811012). CKQ also thanks USM for the award of a USM fellowship and HM also thanks USM for the award of a postdoctoral fellowship.

supplementary crystallographic information

Comment

Hydrogen bonding plays a key role in molecular recognition (Goswami & Ghosh, 1997) and crystal engineering research (Goswami et al., 1998). Fumaric acid, the E isomer of butenedioic acid, is of interest since it is known to form supramolecular assemblies with N-aromatic compounds (Batchelor et al., 2000). It tends to form infinite chains arranged in a nearly coplanar manner via pairs of strong O—H···O hydrogen bonds. The crystal structures of 2-aminopyridinium-fumarate-fumaric acid (2/1/1) (Büyükgüngör et al., 2004) and 2,6-diamino pyridinium hydrogen fumarate (Büyükgüngör & Odabąsoǧlu, 2006) have been reported in the literature. We have recently reported the crystal structures of 2-amino-5-chloropyridine-fumaric acid (1/2) (Hemamalini & Fun, 2010a) and 2-amino-4-methylpyridinium (E)-3-carboxyprop-2-enoate (Hemamalini & Fun, 2010b) from our laboratory. In order to study some interesting hydrogen bonding interactions, the synthesis and structure of the title compound, (I), is presented here.

The asymmetric unit of title compound (Fig. 1), consist of a protonated 2-amino-5-bromopyridinium cation, a half molecule of fumarate anion and a water molecule. The fumarate anion is lying about an inversion center (symmetry code: -x + 1, -y + 1, -z). In the 2-amino-5-bromopyridinium cation, protonatation of N1 atom has lead to a slight increase in the C1–N1–C5 angle to 122.64 (11)°. The 2-amino-5-bromopyridinium cation is approximately planar, with a maximum deviation of 0.036 (1) Å for atom N2. In fumarate anion, C6/C7/C6A/C7A plane is planar with an r.m.s deviation of <0.001 (1) Å. This plane makes a dihedral angle of 6.90 (6)° with 2-amino-5-bromopyridinium cation. In the anion, the carboxylate group is twisted slightly away from the attached plane; the dihedral angle between C6/C7/C6A/C7A and O1/O2/C6/C7 planes is 6.11 (14)°.

In the crystal packing (Fig. 2), the carboxylate oxygen atoms, O2 and O3 form bifurcated (N2–H1N2···O2 and C3–H3A···O2) and N1–H1N1···O1 hydrogen bonds, respectively, with cations. The crystal packing is stabilized by R22(8) ring motifs (Bernstein et al., 1995) which are generated by pairs of N–H···O hydrogen bonds (Table 1). The crystal structure is further consolidated by water molecules via O1W–H1W1···O1, O1W–H2W1···O1 and N2–H2N2···O1W hydrogen bonds. The anions, cations and water molecules are linked by these interactions into three-dimensional network.

Experimental

A hot methanol solution (20 ml) of 2-amino-5-bromopyridine (86 mg, Aldrich) and fumaric acid (58 mg, Merck) was mixed and warmed over a magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound appeared after a few days.

Refinement

O– and N– bound H atoms were located in a difference Fourier map and allowed to refined freely. The rest of the hydrogen atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C). The highest residual electron density peak is located at 0.66 Å from C6 and the deepest hole is located at 1.19 Å from Br1.

Figures

Fig. 1.
The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme. Symmetry code: ($) -x + 1, -y + 1, -z. Intramolecular interactions are shown as dashed lines.
Fig. 2.
The crystal structure of the title compound viewed along the a axis. H atoms not involved in intermolecular interactions (dashed lines) have been omitted for clarity.

Crystal data

2C5H6BrN2+·C4H2O42·2H2OF(000) = 496
Mr = 498.14Dx = 1.856 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5779 reflections
a = 8.3717 (1) Åθ = 2.6–34.6°
b = 16.5354 (2) ŵ = 4.59 mm1
c = 6.7846 (1) ÅT = 100 K
β = 108.336 (1)°Block, colourless
V = 891.50 (2) Å30.39 × 0.15 × 0.12 mm
Z = 2

Data collection

Bruker SMART APEXII CCD area-detector diffractometer3942 independent reflections
Radiation source: fine-focus sealed tube3252 reflections with I > 2σ(I)
graphiteRint = 0.028
[var phi] and ω scansθmax = 35.2°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −13→12
Tmin = 0.271, Tmax = 0.618k = −26→23
15040 measured reflectionsl = −10→10

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)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0265P)2 + 0.2048P] where P = (Fo2 + 2Fc2)/3
3942 reflections(Δ/σ)max = 0.001
138 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = −0.39 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
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)

xyzUiso*/Ueq
Br10.741696 (15)1.042853 (7)0.08809 (2)0.01677 (4)
N10.78272 (13)0.79718 (7)0.17705 (16)0.01325 (19)
H1N10.712 (2)0.7551 (11)0.133 (3)0.022 (4)*
N20.99471 (14)0.70859 (7)0.34946 (18)0.0152 (2)
H2N21.091 (3)0.7028 (12)0.426 (3)0.031 (5)*
H1N20.926 (2)0.6673 (12)0.296 (3)0.036 (5)*
C10.72188 (15)0.87250 (8)0.11482 (19)0.0142 (2)
H1A0.61120.87900.03010.017*
C20.82285 (16)0.93842 (8)0.1764 (2)0.0139 (2)
C30.99045 (15)0.92827 (8)0.3065 (2)0.0148 (2)
H3A1.06060.97290.34860.018*
C41.04836 (15)0.85246 (8)0.36957 (19)0.0144 (2)
H4A1.15750.84550.45850.017*
C50.94285 (15)0.78397 (8)0.30010 (18)0.0127 (2)
O1W0.34331 (12)0.71054 (7)0.61811 (17)0.0206 (2)
H2W10.392 (3)0.6972 (13)0.729 (3)0.038 (6)*
H1W10.396 (3)0.7487 (15)0.594 (4)0.043 (6)*
O10.55652 (11)0.67725 (5)0.02333 (15)0.01630 (18)
O20.75988 (11)0.58655 (6)0.15601 (16)0.01766 (18)
C60.48381 (16)0.53893 (7)−0.0202 (2)0.0139 (2)
H6AA0.37630.5537−0.10260.017*
C70.61164 (15)0.60438 (7)0.06033 (19)0.0127 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.01516 (6)0.01024 (6)0.02259 (7)0.00028 (4)0.00262 (4)0.00195 (5)
N10.0112 (4)0.0107 (5)0.0165 (5)−0.0015 (4)0.0023 (4)−0.0004 (4)
N20.0124 (5)0.0108 (5)0.0201 (5)−0.0002 (4)0.0017 (4)0.0006 (4)
C10.0128 (5)0.0124 (5)0.0161 (5)0.0000 (4)0.0027 (4)0.0010 (4)
C20.0137 (5)0.0103 (5)0.0170 (5)0.0005 (4)0.0040 (4)0.0008 (4)
C30.0129 (5)0.0123 (5)0.0182 (6)−0.0025 (4)0.0035 (4)−0.0017 (4)
C40.0117 (5)0.0129 (6)0.0162 (5)−0.0016 (4)0.0011 (4)−0.0019 (4)
C50.0111 (5)0.0128 (5)0.0139 (5)−0.0003 (4)0.0036 (4)−0.0005 (4)
O1W0.0163 (5)0.0189 (5)0.0221 (5)−0.0039 (4)−0.0003 (4)0.0050 (4)
O10.0134 (4)0.0097 (4)0.0228 (5)0.0004 (3)0.0014 (3)−0.0001 (3)
O20.0120 (4)0.0126 (4)0.0245 (5)0.0001 (3)0.0002 (3)−0.0001 (4)
C60.0112 (5)0.0111 (5)0.0176 (5)−0.0005 (4)0.0016 (4)−0.0011 (4)
C70.0130 (5)0.0105 (5)0.0138 (5)−0.0010 (4)0.0030 (4)−0.0001 (4)

Geometric parameters (Å, °)

Br1—C21.8832 (13)C3—H3A0.9300
N1—C51.3556 (15)C4—C51.4223 (17)
N1—C11.3616 (16)C4—H4A0.9300
N1—H1N10.899 (18)O1W—H2W10.77 (2)
N2—C51.3278 (16)O1W—H1W10.81 (2)
N2—H2N20.81 (2)O1—C71.2863 (15)
N2—H1N20.89 (2)O2—C71.2416 (14)
C1—C21.3620 (17)C6—C6i1.326 (2)
C1—H1A0.9300C6—C71.4990 (17)
C2—C31.4130 (17)C6—H6AA0.9300
C3—C41.3635 (18)
C5—N1—C1122.64 (11)C2—C3—H3A120.3
C5—N1—H1N1119.8 (11)C3—C4—C5120.37 (11)
C1—N1—H1N1117.5 (12)C3—C4—H4A119.8
C5—N2—H2N2116.7 (14)C5—C4—H4A119.8
C5—N2—H1N2119.8 (13)N2—C5—N1119.22 (11)
H2N2—N2—H1N2123.4 (19)N2—C5—C4122.97 (11)
N1—C1—C2120.10 (11)N1—C5—C4117.81 (11)
N1—C1—H1A119.9H2W1—O1W—H1W1105 (2)
C2—C1—H1A120.0C6i—C6—C7123.34 (14)
C1—C2—C3119.67 (12)C6i—C6—H6AA118.3
C1—C2—Br1120.62 (9)C7—C6—H6AA118.3
C3—C2—Br1119.71 (9)O2—C7—O1124.24 (11)
C4—C3—C2119.37 (11)O2—C7—C6120.03 (11)
C4—C3—H3A120.3O1—C7—C6115.72 (11)
C5—N1—C1—C2−0.12 (18)C1—N1—C5—N2−178.04 (12)
N1—C1—C2—C3−0.51 (19)C1—N1—C5—C41.59 (17)
N1—C1—C2—Br1178.98 (9)C3—C4—C5—N2177.11 (13)
C1—C2—C3—C4−0.42 (19)C3—C4—C5—N1−2.50 (18)
Br1—C2—C3—C4−179.92 (10)C6i—C6—C7—O26.0 (2)
C2—C3—C4—C51.93 (19)C6i—C6—C7—O1−173.89 (16)

Symmetry codes: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N1···O10.902 (18)1.815 (18)2.7136 (14)174.1 (19)
N2—H2N2···O1Wii0.82 (2)2.11 (2)2.9143 (16)169.7 (19)
N2—H1N2···O20.893 (19)1.946 (19)2.8348 (15)173.2 (19)
O1W—H2W1···O1iii0.77 (2)2.07 (2)2.8213 (15)169 (2)
O1W—H1W1···O1iv0.82 (3)1.99 (3)2.7865 (14)167 (3)
C3—H3A···O2v0.932.413.3089 (17)162.

Symmetry codes: (ii) x+1, y, z; (iii) x, y, z+1; (iv) x, −y+3/2, z+1/2; (v) −x+2, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5312).

References

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