Nicotinium di­hydrogenphosphate

organic papers

Acta Cryst.(2005). E61, o2553–o2555 doi:10.1107/S1600536805022221 Athimoolamet al. _C

6H6NO2+H2PO4

o2553

Acta Crystallographica Section E Structure Reports

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ISSN 1600-5368

Nicotinium dihydrogenphosphate

S. Athimoolam, K. Anitha and R. K. Rajaram*

Department of Physics, Madurai Kamaraj University, Madurai 625 021, India

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 293 K

Mean(C–C) = 0.003 A˚ Rfactor = 0.030 wRfactor = 0.084 Data-to-parameter ratio = 9.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography

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In the title complex, C6H6NO2 +

H2PO4

, the nicotinium cations are sandwiched between layers of dihydrogen-phosphate anions. The structure is held together by extensive hydrogen bonding between the O and N atoms of nicotinium cations and the O atoms of the phosphate anions, and between the O atoms of the phosphate anions themselves. The nicotinium cations are packed in layers, with an interlayer distance of 3.116 (5) A˚ .

Comment

Nicotinic acid, a B vitamin also known as niacin, and its associated complexes have a variety of pharmacological properties. Principal among these is the lowering of serum cholesterol levels (Brutts & Lundholm, 1971). Niacin forms coordination complexes with Sn which have been found to have better antitumour activity than the well knowncis-platin or doxorubicin (Gielen et al., 1992). In addition, the enzyme nicotinic acid mononucleotide adenylyltransferase is essential for the synthesis of nicotinamide adenine dinucleotide in all living cells and is a potential target for antibiotics (Kimet al., 2004). The crystal structures of nicotinic acid (Wright & King, 1953; Kutoglu & Scheringer, 1983), isonicotinic acid (Taku-sagawa & Shimada, 1976), isonicotinic acid hydrazide (Bhatet al., 1974), 6-aminonicotinic acid hydrochloride (Giantsidis & Turnbull, 2000), 2-(methylsulfanyl)nicotinic acid (Basavojuet al., 2005), nicotinamide (Wright & King, 1954), 1-methyl nicotinamide iodide, chloride and picrate (Freeman & Bugg, 1974), and dinicotinamidium squarate (Bulutet al., 2003) have been reported previously. The crystal structure of nicotinic acid complexed with the protein Leghaemoglobin has also been studied (Ellis et al., 1997). The structure of the title compound, (I), is reported in the present investigation as part of a programme of work on pharmaceutical compounds.

The title compound (I), also known as 3-carboxypyridinium dihydrogenphosphate, has a nicotinium cation and a dihy-drogenphosphate anion in the asymmetric unit of the mono-clinic unit cell. One of the H atoms in the inorganic acid is transferred to the N atom of the nicotinic acid. This proton-ation is well confirmed by the C—N bond distances and C— N—C bond angle. The pyridinium ring is planar, with a mean

deviation of 0.0039 A˚ . The planar carboxyl group is twisted from the pyridinium plane, with a dihedral angle of 21.7 (2)_. The deviation from the pyridinium plane is slightly higher for atom O1B [0.427 (3) A˚ ] than for atom O1A [0.401 (3) A˚ ], probably as a result of hydrogen bonding, as in 2-aminonicotinic acid (Dobson & Gerkin, 1997). The C—O bond distances and C—C—O bond angles confirm that the H atom is connected to atom O1B(Table 1).

The P—O distances in the phosphate anions are as expected, with average single- and double-bonded P—O distances of 1.55 and 1.49 A˚ , respectively (Blessing, 1986). The lengthening of the P–O double bonds is due to the formation of strong O—H O hydrogen bonds. The tetrahedral geometry of the dihydrogenphosphate anion has also suffered due to the hydrogen-bonding interactions. All four phosphate O atoms are involved in hydrogen bonding, with two as donors and two as acceptors. The doubly-bonded O atoms of the anion act as acceptors in hydrogen bonds to both O and N donor atoms (Table 2). Two dihydrogenphosphate anions are linked by inversion-related O1—H1P O3 hydrogen bonds, while a glide-related hydrogen-bonded chain of O2P— H2P O3 bonds runs along the c axis, generating double chains along c. The cations are linked to these anion chains by

O1—H1B O4 hydrogen bonds and the classical hydrogen-bonding network is completed by N1—H1 O4 interactions. These serve to pack the nicotinium cations into layers sepa-rated by 3.116 (5) A˚ but not linked by any hydrogen bonding (Fig. 2).

Experimental

The title compound was crystallized from a mixture of nicotinic acid and orthophosphoric acid in a stoichiometric ratio of 1:1 at room temperature by slow evaporation from a solution in water.

Crystal data

C6H6NO2+H2PO4

Mr= 221.10

Monoclinic, P21=c

a= 12.158 (5) A˚ b= 10.593 (4) A˚ c= 7.001 (3) A˚

= 102.35 (3)

V= 880.8 (6) A˚3

Z= 4

Dx= 1.667 Mg m

3

Dm= 1.652 Mg m

3

Dmmeasured by flotation in a

mixture of CHBr3and CCl4

MoKradiation Cell parameters from 25

reflections

= 9.7–14.3 = 0.32 mm1 T= 293 (2) K Block, colourless 0.200.170.14 mm

Data collection

Nonius MACH3 four-circle diffractometer

!/2scans

Absorption correction: scan (Northet al., 1968) Tmin= 0.847,Tmax= 1.000

1880 measured reflections 1545 independent reflections 1317 reflections withI> 2(I)

Rint= 0.047

max= 25.0

h=14!14 k=12!1 l= 0!8

3 standard reflections frequency: 60 min intensity decay: none

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.030}

wR(F2) = 0.084 S= 1.05 1545 reflections 160 parameters

All H-atom parameters refined

w= 1/[2

(Fo2) + (0.0512P)2

+ 0.2334P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.25 e A˚

3

min=0.37 e A˚

3

Extinction correction:SHELXTL/ PC

[image:2.610.47.300.71.209.2]

Extinction coefficient: 0.131 (7)

Table 1

Selected geometric parameters (A˚ ,_).

N1—C6 1.334 (3)

N1—C2 1.340 (3)

C31—O1A 1.204 (2)

C31—O1B 1.317 (2)

P1—O4 1.5026 (13)

P1—O3 1.5135 (14)

P1—O2 1.5603 (16)

P1—O1 1.5640 (14)

C6—N1—C2 122.37 (18)

O1A—C31—C3 121.89 (17)

[image:2.610.314.567.555.621.2]

O1B—C31—C3 113.40 (16)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N1—H1 O4i 0.83 (3) 1.92 (3) 2.746 (2) 171 (2) O1B—H1B O4ii

0.81 (3) 1.78 (3) 2.586 (2) 169 (3) O1—H1P O3iii

0.83 (3) 1.78 (3) 2.613 (2) 175 (3) O2—H2P O3iv

0.84 (4) 1.73 (4) 2.561 (2) 173 (3)

Symmetry codes: (i)x;y;zþ1; (ii)xþ1;y1 2;zþ

1

2; (iii)xþ2;yþ2;z; (iv)

x;yþ3 2;zþ

1 2.

organic papers

o2554

Athimoolamet al. _C

6H6NO2+H2PO4 Acta Cryst.(2005). E61, o2553–o2555

Figure 1

The molecular structure of the title compound, showing the atom-numbering scheme and 50% probability displacement ellipsoids.

Figure 2

[image:2.610.313.567.672.727.2]

All H atoms were located and refined isotropically.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction:XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure:SHELXTL/PC

(Bruker, 2000); program(s) used to refine structure:SHELXTL/PC; molecular graphics:SHELXTL/PC; software used to prepare mate-rial for publication:SHELXTL/PC.

The authors thank the Department of Science and Tech-nology, Government of India, for establishing the Single-Crystal Diffractometer Facility at the School of Physics, Madurai Kamaraj University, Madurai, through the FIST programme.

References

Basavoju, S., Reddy, C. M. & Desiraju, G. R. (2005).Acta Cryst.E61, o822– o823.

Bhat, T. N., Singh, T. P. & Vijayan, M. (1974).Acta Cryst.B30, 2921–2922.

Blessing, R. H. (1986).Acta Cryst.B42, 613–621.

Bruker (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Brutts, R. & Lundholm, L. (1971).J. Atheroscler. Res.pp. 14–19.

Bulut, A., Yesilel, O. Z., Dege, N., Icbudak, H., Olmaz, H. & Bujukgungor, O. (2003).Acta Cryst.C59, o727–o729.

Dobson, A. J. & Gerkin, R. E. (1997).Acta Cryst.C53, 1427–1429.

Ellis, P. J., Appleby, C. A., Guss, J. M., Hunter, W. N., Ollis, D. L. & Freeman, H. C. (1997).Acta Cryst.D53, 302–310.

Enraf–Nonius (1994). CAD-4 EXPRESS. Version 5.1/1.2. Enraf–Nonius, Delft, The Netherlands.

Freeman, G. R. & Bugg, C. E. (1974).Acta Cryst.B30, 431–443. Giantsidis, J. & Turnbull, M. M. (2000).Acta Cryst.C56, 334–335.

Gielen, M., Khloufi, A. E., Biesemans, M. & Willem, R. (1992).Polyhedron, 11, 1861–1868.

Harms, K. & Wocadlo, S. (1995).XCAD4. University of Marburg, Germany. Kim, H. L., Yoon, H. J., Ha, J. Y., Lee, B. I., Lee, H. H., Mikami, B. & Suh, W. S.

(2004).Acta Cryst.D60, 948–949.

Kutoglu, A. & Scheringer, C. (1983).Acta Cryst.C39, 232–234.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351– 359.

Takusagawa, F. & Shimada, A. (1976).Acta Cryst.B32, 1925–1927. Wright, W. B. & King, G. S. D. (1953).Acta Cryst.6, 305–310. Wright, W. B. & King, G. S. D. (1954).Acta Cryst.7, 283–288.

organic papers

Acta Cryst.(2005). E61, o2553–o2555 Athimoolamet al. _C

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Acta Cryst. (2005). E61, o2553–o2555

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Acta Cryst. (2005). E61, o2553–o2555 [https://doi.org/10.1107/S1600536805022221]

Nicotinium dihydrogenphosphate

S. Athimoolam, K. Anitha and R. K. Rajaram

3-carboxypyridinium dihydrogenphosphate

Crystal data

C6H6NO2+·H2PO4−

Mr = 221.10 Monoclinic, P21/c

a = 12.158 (5) Å b = 10.593 (4) Å c = 7.001 (3) Å β = 102.35 (3)° V = 880.8 (6) Å3

Z = 4 F(000) = 456

Dx = 1.667 Mg m−3

Dm = 1.652 Mg m−3

Dm measured by flotation in CHBr3 and CCl4

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections θ = 9.7–14.3°

µ = 0.32 mm−1

T = 293 K Needle, colourless 0.20 × 0.17 × 0.14 mm

Data collection

Nonius MACH3 sealed-tube diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/2θ scans

Absorption correction: ψ scan (North et al., 1968)

Tmin = 0.847, Tmax = 1.000

1880 measured reflections

1545 independent reflections 1317 reflections with I > 2σ(I) Rint = 0.047

θmax = 25.0°, θmin = 2.6°

h = −14→14 k = −12→1 l = 0→8

3 standard reflections every 60 min intensity decay: none

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.030}

wR(F2_{) = 0.084}

S = 1.05 1545 reflections 160 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

All H-atom parameters refined w = 1/[σ2_(F

o2) + (0.0512P)2 + 0.2334P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.25 e Å−3

Δρmin = −0.37 e Å−3

Extinction correction: SHELXTL/PC (Bruker, 2000), Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

supporting information

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Acta Cryst. (2005). E61, o2553–o2555 Special details

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

N1 0.72318 (13) 0.57178 (16) 0.9647 (2) 0.0357 (4) H1 0.7311 (19) 0.649 (2) 0.989 (3) 0.040 (6)* C2 0.62653 (16) 0.53386 (18) 0.8483 (3) 0.0345 (5) H2 0.569 (2) 0.595 (2) 0.800 (3) 0.044 (6)* C3 0.61118 (15) 0.40873 (17) 0.7980 (3) 0.0290 (4) C4 0.69727 (16) 0.32384 (19) 0.8715 (3) 0.0359 (4) H4 0.687 (2) 0.236 (3) 0.839 (4) 0.059 (7)* C5 0.79443 (18) 0.3665 (2) 0.9921 (3) 0.0424 (5) H5 0.854 (2) 0.315 (2) 1.044 (3) 0.051 (6)* C6 0.80657 (17) 0.4919 (2) 1.0363 (3) 0.0386 (5) H6 0.877 (2) 0.530 (2) 1.127 (4) 0.056 (7)* C31 0.50543 (15) 0.36374 (17) 0.6669 (3) 0.0310 (4) O1A 0.50164 (11) 0.26655 (13) 0.5767 (2) 0.0419 (4) O1B 0.41945 (12) 0.44044 (14) 0.6607 (3) 0.0446 (4) H1B 0.366 (3) 0.405 (3) 0.593 (5) 0.069 (9)* P1 0.87510 (3) 0.88988 (4) 0.05786 (6) 0.0245 (2) O1 0.85483 (12) 1.03547 (12) 0.0364 (2) 0.0349 (4) H1P 0.916 (2) 1.074 (3) 0.055 (4) 0.058 (8)* O2 0.93597 (11) 0.87378 (13) 0.2765 (2) 0.0354 (4) H2P 0.943 (3) 0.800 (3) 0.318 (5) 0.084 (10)* O3 0.95263 (11) 0.84746 (12) −0.07246 (19) 0.0351 (3) O4 0.76205 (10) 0.82621 (12) 0.0151 (2) 0.0359 (4)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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Acta Cryst. (2005). E61, o2553–o2555

O1 0.0295 (7) 0.0239 (7) 0.0500 (8) 0.0014 (5) 0.0054 (6) 0.0013 (5) O2 0.0353 (7) 0.0317 (7) 0.0355 (8) −0.0059 (6) −0.0011 (6) 0.0030 (6) O3 0.0335 (7) 0.0299 (7) 0.0436 (8) −0.0046 (5) 0.0122 (6) −0.0084 (6) O4 0.0219 (6) 0.0306 (7) 0.0516 (8) −0.0037 (5) −0.0004 (5) 0.0004 (6)

Geometric parameters (Å, º)

N1—C6 1.334 (3) C6—H6 1.03 (3)

N1—C2 1.340 (3) C31—O1A 1.204 (2)

N1—H1 0.83 (3) C31—O1B 1.317 (2)

C2—C3 1.374 (3) O1B—H1B 0.81 (3)

C2—H2 0.96 (2) P1—O4 1.5026 (13)

C3—C4 1.392 (3) P1—O3 1.5135 (14)

C3—C31 1.489 (3) P1—O2 1.5603 (16)

C4—C5 1.373 (3) P1—O1 1.5640 (14)

C4—H4 0.96 (3) O1—H1P 0.83 (3)

C5—C6 1.364 (3) O2—H2P 0.84 (4)

C5—H5 0.91 (3)

C6—N1—C2 122.37 (18) N1—C6—C5 119.73 (19)

C6—N1—H1 119.8 (16) N1—C6—H6 116.8 (14)

C2—N1—H1 117.8 (16) C5—C6—H6 123.5 (14)

N1—C2—C3 119.89 (18) O1A—C31—O1B 124.71 (18)

N1—C2—H2 119.5 (14) O1A—C31—C3 121.89 (17)

C3—C2—H2 120.6 (14) O1B—C31—C3 113.40 (16)

C2—C3—C4 118.57 (18) C31—O1B—H1B 106 (2)

C2—C3—C31 121.25 (17) O4—P1—O3 114.08 (8)

C4—C3—C31 120.18 (17) O4—P1—O2 111.58 (8)

C5—C4—C3 119.64 (19) O3—P1—O2 109.45 (8)

C5—C4—H4 120.8 (15) O4—P1—O1 107.75 (8)

C3—C4—H4 119.6 (15) O3—P1—O1 109.92 (8)

C6—C5—C4 119.79 (19) O2—P1—O1 103.52 (8)

C6—C5—H5 116.9 (16) P1—O1—H1P 110.2 (19)

C4—C5—H5 123.3 (16) P1—O2—H2P 116 (2)

C6—N1—C2—C3 −0.4 (3) C2—N1—C6—C5 −0.4 (3)

N1—C2—C3—C4 0.5 (3) C4—C5—C6—N1 1.1 (3)

N1—C2—C3—C31 −179.18 (17) C2—C3—C31—O1A 158.11 (19) C2—C3—C4—C5 0.3 (3) C4—C3—C31—O1A −21.5 (3) C31—C3—C4—C5 179.91 (18) C2—C3—C31—O1B −21.6 (3) C3—C4—C5—C6 −1.1 (3) C4—C3—C31—O1B 158.73 (18)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1—H1···O4i _{0.83 (3) 1.92 (3) 2.746 (2) 171 (2)}

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Acta Cryst. (2005). E61, o2553–o2555

O1—H1P···O3iii _{0.83 (3) 1.78 (3) 2.613 (2) 175 (3)}

O2—H2P···O3iv _{0.84 (4) 1.73 (4) 2.561 (2) 173 (3)}