3-Carbamoyl-1-(2-nitrobenzyl)pyridin­ium bromide

Kyung Beom Kim; Kwang-Deog Jung; Cheal Kim; Youngmee Kim

doi:10.1107/S1600536812015917

. 2012 Apr 18;68(Pt 5):o1441–o1442. doi: 10.1107/S1600536812015917

3-Carbamoyl-1-(2-nitrobenzyl)pyridinium bromide

Kyung Beom Kim ^a, Kwang-Deog Jung ^b, Cheal Kim ^a,^*, Youngmee Kim ^c,^*

PMCID: PMC3344559 PMID: 22590321

Abstract

In the title compound, C₁₃H₁₂N₃O₃ ⁺·Br⁻, the benzene and pyridinium rings form a dihedral angle of 82.0 (1)°. In the crystal, N—H⋯Br and N—H⋯O hydrogen bonds link the components into chains along [001]. In addition, weak C—H⋯O and C—H⋯Br hydrogen bonds are observed.

Related literature

The title compound was prepared as an NAD⁺ (nicotinamide adenine dinucleotide) model. For effective regeneration systems for co-enzymes (e.g. NADH), see: Hollmann et al. (2001 ▶); Lee et al. (2011 ▶); Maenaka et al. (2012 ▶); Park et al. (2008 ▶); Ruppert et al. (1988 ▶); Zhu et al. (2006 ▶). For the mechanisms of redox interconversions (NADH/NAD⁺), see: Zhu et al. (2003 ▶); Song et al. (2008 ▶).

Experimental

Crystal data

C₁₃H₁₂N₃O₃ ⁺·Br⁻
M _r = 338.17
Monoclinic,
a = 17.576 (4) Å
b = 7.9990 (16) Å
c = 10.152 (2) Å
β = 105.88 (3)°
V = 1372.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 3.01 mm⁻¹
T = 293 K
0.15 × 0.15 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.661, T _max = 0.753
7399 measured reflections
2684 independent reflections
2081 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.086
S = 1.04
2684 reflections
187 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812015917/lh5450sup1.cif

e-68-o1441-sup1.cif^{(22.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015917/lh5450Isup2.hkl

e-68-o1441-Isup2.hkl^{(131.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812015917/lh5450Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1ⁱ	0.86 (1)	2.30 (1)	3.143 (4)	168 (4)
N1—H1A⋯Br1ⁱⁱ	0.86 (1)	2.61 (1)	3.454 (3)	166 (3)
C4—H4⋯Br1	0.93	2.82	3.743 (3)	173
C7—H7B⋯Br1ⁱⁱⁱ	0.97	2.82	3.595 (3)	137
C5—H5⋯O2^iv	0.93	2.36	3.271 (4)	167
C3—H3⋯O1ⁱ	0.93	2.27	3.150 (4)	157

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

Financial support from the Converging Research Center Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2011 K000675 and 2011 K000660), and Seoul National University of Science & Technology is gratefully acknowledged.

supplementary crystallographic information

Comment

One of the most important challenges in applying mono-oxygenases reactions in vitro is to find an effective regeneration system for the necessary co-enzyme (mostly NAD(P)H) (Hollmann et al., 2001; Lee et al.,2011; Maenaka et al., 2012; Park et al., 2008; Ruppert et al., 1988; Zhu et al., 2006). The well established methods for the regeneration of the nicotinamide co-enzyme mainly consist of an enzyme-coupled approach utilizing formate dehydrogenase or glucose-6-phosphate dehydrogenase. Because the redox coenzyme couple NADH/NAD⁺ is ubiquitous and controls so much of our oxidation/reduction nature, there has been a long-standing interest in the mechanisms of the redox interconversions (Zhu et al., 2003). The high cost of these co-factors, however, is prohibitive of industrialization of many promising enzymatic processes. An efficient method of their in situ regeneration is the only means for making the processes economically and industrially feasible (Song et al., 2008). Therefore, many researchers have given considerable attention to the chemistry of NADH and its models (Hollmann et al., 2001). In this work, we have synthesized the title compound as a NAD⁺ model and report herein its crystal structure.

The molecular structure of the title compound is shown in Fig. 1. The benzene ring (C8-C13) and pyridine ring (N3/C2-C6) form a dihedral angle of 82.0 (1)°. In the crystal, intermolecular N—H···Br and N—H···O hydrogen bonds link the components to form chains along [001]. In addition, weak C—H···O and C—H···Br hydrogen bonds are observed.

Experimental

Nicotinamide (123.4 mg, 1 mmol) was dissolved in 10 ml acetonitrile. After stirring for a few minutes, 2-nitrobenzyl bromide (220.4 mg, 1 mmol) was carefully added to the reaction mixture. The solution was stirred for 3 h at 353K. The precipitate was filtered, washed three times with methylene chloride, and dried under vacuum. Crystals suitable for X-ray analysis were obtained from a methanol soution of the title compound in a few days.