Nicotinium nitrate monohydrate

Jebas, S.R.; Balasubramanian, T.; Light, M.E.

doi:10.1107/S1600536806027474

organic compounds

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Volume 62| Part 8| August 2006| Pages o3481-o3482

https://doi.org/10.1107/S1600536806027474

Nicotinium nitrate monohydrate

Samuel Robinson Jebas,^a Thailampillai Balasubramanian ^b ^* and Mark E. Light ^c

^aDepartment of Electronics, St Joseph's College, Tiruchirappalli 620 002, India, ^bDepartment of Physics, National Institute of Technology, Tiruchirappalli 620 015, India, and ^cSchool of Chemistry, University of Southampton, Highfield SO17 1BJ, England
^*Correspondence e-mail: bala@nitt.edu

(Received 4 July 2006; accepted 15 July 2006; online 26 July 2006)

In the title compound, C₆H₆NO₂⁺·NO₃⁻·H₂O, the nicotinium cation is essentially planar. N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds link the molecules into layers parallel to the (10 $[\overline{1}]$ ) plane.

Comment

Nicotinic acid (vitamin B3), known as niacin, is a lipid lowering agent widely used to treat hypertriglyceridemia by the inhibition of lipolysis in adipose tissue (Athimoolam & Rajaram, 2005 ). The nicotinic acid complex 5-methylpyrazine-2-carboxylic acid-4-oxide is a commonly used drug for the treatment of hypercholesterolemia (Lorenzen et al., 2001 ). Coordination complexes of nicotinic acid with metals such as Sn possess antitumour activity greater than the well known cis-platin or doxorubicin (Gielen et al., 1992 ). The enzyme nicotinic acid mononucleotide adenyltransferase is essential for the synthesis of nicotinamide adenine dinucleotide in all living cells and is a potential target for antibiotics (Kim et al., 2004 ). As a part of our investigation of inorganic salts of nicotinic acid, we report here the crystal structure of nicotinium nitrate monohydrate, (I).

The asymetric unit of (I) contains a nicotinium cation, a nitrate anion and a water molecule (Fig. 1). Protonation of atom N1 of nicotine results in a widening of the C2—N1—C6 angle to 122.9 (3)°, compared with 118.9 (3)° in unprotonated nicotinic acid (Kutoglu & Scheringer, 1983 ). The nicotinium cation is essentially planar, with a maximum deviation from the mean plane of 0.048 (2) Å for atom O1.

The crystal packing is stabilized by N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds (Table 1), which link the molecules into layers parallel to the (10 $[\overline{1}]$ ) plane (Fig. 2).

Figure 1
The asymmetric unit of (I)

, showing the atom-numbering scheme, with 50% probability displacement ellipsoids. Hydrogen bonds are drawn as dashed lines.

Figure 2
A packing diagram for (I)

, viewed down the b axis. Hydrogen bonds are drawn as dashed lines.

Experimental

Nitric acid was added dropwise to an aqueous solution of nicotinic acid, in stoichiometric amounts. The solution was heated at 323 K for 2 h. Colourless block-shaped crystals of (I) were obtained by slow evaporation over a period of one week.

Crystal data

C₆H₆NO₂⁺·NO₃⁻·H₂O
M_r = 204.14
Monoclinic, P 2₁ /n
a = 6.6539 (7) Å
b = 12.3682 (15) Å
c = 10.1814 (15) Å
β = 100.967 (7)°
V = 822.59 (18) Å³
Z = 4
D_x = 1.641 Mg m⁻³
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 120 (2) K
Block, colourless
0.2 × 0.2 × 0.07 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.970, T_max = 0.990
6153 measured reflections
1604 independent reflections
894 reflections with I > 2σ(I)
R_int = 0.109
θ_max = 26.1°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.137
S = 0.98
1604 reflections
135 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0639P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.86	1.93	2.782 (3)	170
O1—H1A⋯O6	0.82	1.77	2.587 (3)	180
O6—H6A⋯O5	0.93 (5)	1.92 (5)	2.843 (3)	171 (4)
O6—H6B⋯O3ⁱⁱ	0.88 (5)	1.96 (5)	2.825 (3)	173 (5)
C2—H2⋯O2ⁱⁱⁱ	0.93	2.43	3.173 (4)	137
C4—H4⋯O1^iv	0.93	2.46	3.262 (4)	144
C6—H6⋯O5ⁱ	0.93	2.35	3.051 (4)	132
C6—H6⋯O4^iv	0.93	2.32	3.013 (4)	131
Symmetry codes: (i) x, y-1, z; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Water H atoms were located in a difference map and refined freely [O—H = 0.88 (5) and 0.93 (5) Å]. All other H atoms were placed in calculated positions, with C—H = 0.93 Å, O—H = 0.82 Å and N—H = 0.86 Å, and refined using a riding model, with U_iso(H) = 1.2U_eq(C,N) and 1.5U_eq(O).

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806027474/ci2097sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806027474/ci2097Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Nicotinium nitrate monohydrate top

Crystal data top

C₆H₆NO₂⁺·NO₃⁻·H₂O	F(000) = 424
M_r = 204.14	D_x = 1.641 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 6.6539 (7) Å	θ = 1.0–26.0°
b = 12.3682 (15) Å	µ = 0.15 mm⁻¹
c = 10.1814 (15) Å	T = 120 K
β = 100.967 (7)°	Block, colourless
V = 822.59 (18) Å³	0.2 × 0.2 × 0.07 mm
Z = 4

Data collection top

Bruker–Nonius FR591 rotating anode diffractometer	R_int = 0.109
φ and ω scans	θ_max = 26.1°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
T_min = 0.970, T_max = 0.990	k = −14→14
6153 measured reflections	l = −12→9
1604 independent reflections	3 standard reflections every 60 reflections
894 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.055	w = 1/[σ²(F_o²) + (0.0639P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.137	(Δ/σ)_max < 0.001
S = 0.98	Δρ_max = 0.26 e Å⁻³
1604 reflections	Δρ_min = −0.30 e Å⁻³
135 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O1	0.0945 (3)	0.36210 (16)	0.3701 (2)	0.0259 (6)
H1A	0.0866	0.4279	0.3602	0.039*
O2	−0.0994 (3)	0.36163 (16)	0.1648 (2)	0.0258 (6)
N1	0.1318 (3)	0.03157 (19)	0.3733 (3)	0.0205 (7)
H1	0.2044	−0.001	0.4406	0.025*
C2	0.1259 (4)	0.1401 (2)	0.3736 (3)	0.0196 (7)
H2	0.1984	0.1786	0.4458	0.023*
C3	0.0112 (4)	0.1940 (2)	0.2659 (3)	0.0167 (7)
C4	−0.0953 (4)	0.1334 (2)	0.1597 (3)	0.0211 (8)
H4	−0.1732	0.168	0.0861	0.025*
C5	−0.0851 (4)	0.0216 (2)	0.1637 (3)	0.0219 (8)
H5	−0.1556	−0.0191	0.0929	0.026*
C6	0.0292 (4)	−0.0283 (2)	0.2724 (3)	0.0209 (8)
H6	0.0361	−0.1034	0.2764	0.025*
C7	−0.0042 (4)	0.3138 (2)	0.2603 (3)	0.0181 (7)
N2	0.3245 (4)	0.8028 (2)	0.5438 (3)	0.0235 (7)
O3	0.3502 (3)	0.90208 (16)	0.5744 (2)	0.0243 (6)
O4	0.4266 (3)	0.73309 (17)	0.6135 (2)	0.0342 (7)
O5	0.1940 (3)	0.77703 (17)	0.4435 (2)	0.0268 (6)
O6	0.0695 (4)	0.56951 (18)	0.3383 (3)	0.0264 (6)
H6A	0.124 (6)	0.634 (4)	0.377 (4)	0.067 (14)*
H6B	0.002 (6)	0.584 (4)	0.258 (5)	0.082 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0344 (12)	0.0150 (12)	0.0236 (14)	0.0002 (10)	−0.0062 (10)	−0.0002 (10)
O2	0.0352 (12)	0.0176 (12)	0.0210 (13)	0.0032 (10)	−0.0040 (10)	0.0015 (10)
N1	0.0219 (14)	0.0155 (14)	0.0227 (16)	0.0005 (11)	0.0003 (11)	0.0030 (12)
C2	0.0169 (16)	0.0196 (17)	0.0207 (18)	−0.0013 (13)	−0.0002 (13)	−0.0022 (14)
C3	0.0182 (16)	0.0153 (17)	0.0163 (18)	−0.0003 (12)	0.0023 (13)	−0.0026 (13)
C4	0.0198 (16)	0.0225 (18)	0.0204 (19)	0.0011 (13)	0.0021 (13)	0.0017 (15)
C5	0.0252 (17)	0.0186 (18)	0.0200 (18)	−0.0050 (14)	−0.0008 (13)	−0.0035 (14)
C6	0.0237 (17)	0.0125 (16)	0.0265 (19)	−0.0012 (13)	0.0048 (14)	0.0011 (14)
C7	0.0187 (16)	0.0168 (16)	0.0179 (18)	−0.0021 (13)	0.0015 (14)	0.0003 (14)
N2	0.0266 (15)	0.0199 (16)	0.0235 (17)	−0.0015 (12)	0.0037 (13)	0.0010 (13)
O3	0.0339 (12)	0.0131 (12)	0.0227 (13)	−0.0011 (10)	−0.0027 (9)	0.0000 (10)
O4	0.0420 (14)	0.0201 (13)	0.0351 (16)	0.0088 (11)	−0.0065 (12)	0.0080 (11)
O5	0.0318 (13)	0.0226 (12)	0.0225 (14)	−0.0040 (10)	−0.0039 (11)	−0.0027 (10)
O6	0.0303 (13)	0.0179 (13)	0.0276 (15)	−0.0025 (10)	−0.0027 (11)	0.0000 (11)

Geometric parameters (Å, º) top

O1—C7	1.326 (3)	C4—C5	1.384 (4)
O1—H1A	0.82	C4—H4	0.93
O2—C7	1.209 (3)	C5—C6	1.365 (4)
N1—C2	1.342 (4)	C5—H5	0.93
N1—C6	1.343 (4)	C6—H6	0.93
N1—H1	0.86	N2—O4	1.235 (3)
C2—C3	1.383 (4)	N2—O5	1.249 (3)
C2—H2	0.93	N2—O3	1.271 (3)
C3—C4	1.393 (4)	O6—H6A	0.93 (5)
C3—C7	1.486 (4)	O6—H6B	0.88 (5)

C7—O1—H1A	109.5	C6—C5—C4	119.5 (3)
C2—N1—C6	122.9 (3)	C6—C5—H5	120.2
C2—N1—H1	118.6	C4—C5—H5	120.2
C6—N1—H1	118.6	N1—C6—C5	119.6 (3)
N1—C2—C3	119.4 (3)	N1—C6—H6	120.2
N1—C2—H2	120.3	C5—C6—H6	120.2
C3—C2—H2	120.3	O2—C7—O1	123.9 (3)
C2—C3—C4	118.6 (3)	O2—C7—C3	122.7 (3)
C2—C3—C7	122.3 (3)	O1—C7—C3	113.4 (2)
C4—C3—C7	119.0 (3)	O4—N2—O5	120.8 (2)
C5—C4—C3	119.9 (3)	O4—N2—O3	120.0 (2)
C5—C4—H4	120	O5—N2—O3	119.2 (2)
C3—C4—H4	120	H6A—O6—H6B	108 (4)

C6—N1—C2—C3	−0.5 (5)	C2—N1—C6—C5	0.8 (5)
N1—C2—C3—C4	0.0 (5)	C4—C5—C6—N1	−0.6 (5)
N1—C2—C3—C7	179.3 (3)	C2—C3—C7—O2	177.8 (3)
C2—C3—C4—C5	0.1 (5)	C4—C3—C7—O2	−2.9 (5)
C7—C3—C4—C5	−179.2 (3)	C2—C3—C7—O1	−2.8 (4)
C3—C4—C5—C6	0.2 (5)	C4—C3—C7—O1	176.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.86	1.93	2.782 (3)	170
O1—H1A···O6	0.82	1.77	2.587 (3)	180
O6—H6A···O5	0.93 (5)	1.92 (5)	2.843 (3)	171 (4)
O6—H6B···O3ⁱⁱ	0.88 (5)	1.96 (5)	2.825 (3)	173 (5)
C2—H2···O2ⁱⁱⁱ	0.93	2.43	3.173 (4)	137
C4—H4···O1^iv	0.93	2.46	3.262 (4)	144
C6—H6···O5ⁱ	0.93	2.35	3.051 (4)	132
C6—H6···O4^iv	0.93	2.32	3.013 (4)	131

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

References

Athimoolam, S. & Rajaram, R. K. (2005). Acta Cryst. E61, o2764–o2767. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Gottingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Gottingen, Germany. Google Scholar
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ISSN: 2056-9890

Volume 62| Part 8| August 2006| Pages o3481-o3482

https://doi.org/10.1107/S1600536806027474

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Nicotinium nitrate monohydrate

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds