2-Amino-3-carboxy­pyridinium dihydrogen­phosphate

Akriche, S.; Rzaigui, M.

doi:10.1107/S1600536807032862

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2-Amino-3-carboxypyridinium dihydrogenphosphate

S. Akriche and M. Rzaigui

The structure of a new monophosphate with an organic cation, C₆H₇N₂O₂⁺·H₂PO₄^-, is built up of organic (2-NH₂C₅NH₄CO₂H⁺) and inorganic (H₂PO₄^-) entities located in planes parallel to (10 $\overline 1$ ). There are (H₂PO₄^-)_n polyanions resulting from the aggregation of dihydrogenphosphate groups through strong hydrogen bonds, and these form infinite ribbons parallel to the b direction.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032862/gw2015sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032862/gw2015Isup2.hkl Contains datablock I

CCDC reference: 657737

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.003 Å
R factor = 0.032
wR factor = 0.086
Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT213_ALERT_2_C Atom O3      has ADP max/min Ratio .............       3.30 prola
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.21

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           29.96
           From the CIF: _reflns_number_total               1646
           From the CIF: _diffrn_reflns_limit_ max hkl   17.    6.    9.
           From the CIF: _diffrn_reflns_limit_ min hkl  -18.   -6.    0.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   18.    6.   22.
           Calculated minimum hkl  -18.   -6.  -22.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Intermolecular and intramolecular H-bonds constitute an important factor to understand and interprate the properties of biological and pharmacological materials. For that purpose, organic phosphate could be used as interesting models. In the presence of organic cations, the formation of (H₂PO₄–)_n polyanions is observed. These polymeric anions could provide interesting supramolecular networks with a variety of novel structural features (Blessing, (1986); Adams, (1977); Desiraju, (1989) and (1995)).

As part of our study of organic cation monophosphate, we have synthesized a new compound,2-amino-3-nicotinium acid dihydrogenmonophosphate (I). The formula unit (I) constitute the assymetric unit which is built of one (H₂PO₄)_- anion and one (C₅N₂H₆CO₂H)₊ cation (Fig. 1).

The main geometrical features of anions and cations are reported in table 1. The monophosphate anions have slightly distorted tetrahedral geometry, with the P—O bond lengths ranging from 1.5049 (16)–1.5628 (14)Å and the O—P—O angles ranging from 106.46 (9)–115.27 (10)°. As expected, the geometric parameters of the H₂PO_4- anion agree with those previously observed for monophosphate polyanions with no internal symmetry (Hebert, (1978); Masse and Durif, (1990)).

The H₂P O_4- tetrahedra are interconnected by strong hydrogen bonds in way to form infinite ribbons extending along the b axis. These ribbons, which are organized in planes parallel to (101), are interconnected by the organic molecules so to form thick layers of hybrid organic-inorganic entities parallel to the (10–1) plane (Fig. 2). These entities manifest multiple hydtogen bonds of types N—H···O, O—H···O and C—H···O to keep up the network cohesion.

Each H₂PO₄ group is linked to four adjacent phosphoric groups by two donors and two acceptors strong hydrogen bonds in which the corresponding O···O distances lie in the range 2.504 (3)–2.560 (3) Å on one side, and to two organic cations by three acceptors weak hydrogen bonds on the other side.

The hydrogen atoms belonging to NH₂ groups participate in addition in intramolecular interaction with N2—H2B···O5 = 2.086 Å distance to maintain the cohesion of organic cations.

Related literature top

For related literature, see: Adams (1977); Blessing (1986); Desiraju (1989, 1995); Hebert (1978); Masse & Durif (1990).

Experimental top

A solution of 2-amino nicotinic acid (0.036 mmol) in ethanol (5 ml) is added drop by drop under stirring to a dilute solution of H₃PO₄ (0.25 mmol) in water (20 ml). The obtained solution is slowly evaporated at the ambiant temperature. After some days, transparent thin single crystals of the title compound are formed in the reactionnel midle.

Structure description top

The hydrogen atoms belonging to NH₂ groups participate in addition in intramolecular interaction with N2—H2B···O5 = 2.086 Å distance to maintain the cohesion of organic cations.

For related literature, see: Adams (1977); Blessing (1986); Desiraju (1989, 1995); Hebert (1978); Masse & Durif (1990).

Computing details top

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: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. view of (I) with atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level
	Fig. 2. Projection of (I) along b axis.

2-Amino-3-carboxypyridinium dihydrogenphosphate top

Crystal data top

C₆H₇N₂O₂⁺·H₂PO₄⁻	F(000) = 488
M_r = 236.12	D_x = 1.659 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 12.877 (3) Å	θ = 10–13°
b = 4.658 (3) Å	µ = 0.30 mm⁻¹
c = 15.978 (2) Å	T = 295 K
β = 99.43 (3)°	Prism, colourless
V = 945.4 (7) Å³	0.21 × 0.19 × 0.17 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.013
Radiation source: fine-focus sealed tube	θ_max = 30.0°, θ_min = 3.2°
Graphite monochromator	h = −18→17
non–profiled ω scans	k = −6→6
3295 measured reflections	l = 0→9
1646 independent reflections	2 standard reflections every 120 min
1317 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0465P)² + 0.4272P] where P = (F_o² + 2F_c²)/3
1646 reflections	(Δ/σ)_max = 0.0001
136 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₆H₇N₂O₂⁺·H₂PO₄⁻	V = 945.4 (7) Å³
M_r = 236.12	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.877 (3) Å	µ = 0.30 mm⁻¹
b = 4.658 (3) Å	T = 295 K
c = 15.978 (2) Å	0.21 × 0.19 × 0.17 mm
β = 99.43 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.013
3295 measured reflections	2 standard reflections every 120 min
1646 independent reflections	intensity decay: 1%
1317 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.04	Δρ_max = 0.27 e Å⁻³
1646 reflections	Δρ_min = −0.32 e Å⁻³
136 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.

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) top

	x	y	z	U_iso*/U_eq
P1	0.36597 (3)	0.04985 (10)	0.83326 (5)	0.0235 (3)
O1	0.25963 (9)	−0.0708 (3)	0.85358 (11)	0.0311 (5)
H1	0.2435	−0.2157	0.8253	0.047*
O2	0.45370 (9)	−0.1750 (3)	0.86498 (11)	0.0320 (5)
H2	0.4428	−0.3224	0.8368	0.048*
O3	0.36107 (10)	0.0954 (3)	0.73904 (14)	0.0301 (6)
O4	0.39050 (10)	0.3137 (3)	0.88724 (11)	0.0301 (5)
O5	0.50372 (11)	0.2632 (4)	0.57748 (13)	0.0443 (6)
N1	0.79601 (11)	0.0029 (4)	0.51515 (14)	0.0299 (6)
H1A	0.8213	0.0704	0.4726	0.036*
O6	0.53099 (11)	−0.0514 (4)	0.68426 (12)	0.0407 (6)
H6	0.4738	0.0078	0.6931	0.061*
C2	0.66074 (13)	−0.0149 (4)	0.59914 (17)	0.0245 (7)
N2	0.65346 (12)	0.2958 (4)	0.47661 (14)	0.0352 (6)
H2A	0.6827	0.3573	0.4354	0.042*
H2B	0.5931	0.3619	0.4837	0.042*
C1	0.70085 (13)	0.1010 (4)	0.52881 (16)	0.0257 (7)
C6	0.55708 (14)	0.0821 (4)	0.61901 (18)	0.0299 (8)
C5	0.85289 (14)	−0.1939 (5)	0.56455 (19)	0.0359 (8)
H5	0.9179	−0.2509	0.5521	0.043*
C3	0.71970 (14)	−0.2165 (5)	0.64914 (17)	0.0318 (7)
H3	0.6941	−0.2926	0.6956	0.038*
C4	0.81747 (15)	−0.3097 (5)	0.63169 (19)	0.0372 (8)
H4	0.8566	−0.4472	0.6654	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.02042 (19)	0.02154 (19)	0.0302 (9)	−0.00039 (15)	0.0089 (2)	0.0020 (2)
O1	0.0264 (6)	0.0365 (7)	0.0336 (17)	−0.0095 (5)	0.0141 (6)	−0.0093 (7)
O2	0.0266 (6)	0.0235 (6)	0.0452 (16)	0.0005 (5)	0.0037 (6)	0.0048 (7)
O3	0.0315 (6)	0.0500 (9)	0.0118 (18)	0.0117 (6)	0.0124 (7)	0.0124 (9)
O4	0.0345 (6)	0.0237 (6)	0.0354 (16)	−0.0055 (5)	0.0151 (7)	−0.0034 (7)
O5	0.0368 (7)	0.0500 (9)	0.0501 (18)	0.0181 (6)	0.0190 (8)	0.0159 (9)
N1	0.0252 (7)	0.0370 (9)	0.0306 (19)	0.0019 (6)	0.0136 (8)	0.0003 (9)
O6	0.0332 (7)	0.0656 (11)	0.0281 (19)	0.0147 (7)	0.0190 (8)	0.0142 (10)
C2	0.0244 (7)	0.0343 (9)	0.016 (2)	0.0023 (6)	0.0075 (8)	−0.0010 (9)
N2	0.0319 (8)	0.0428 (9)	0.034 (2)	0.0079 (7)	0.0154 (8)	0.0131 (10)
C1	0.0224 (7)	0.0310 (9)	0.024 (2)	0.0004 (6)	0.0063 (9)	−0.0020 (9)
C6	0.0247 (8)	0.0375 (10)	0.029 (3)	0.0024 (7)	0.0078 (9)	−0.0027 (11)
C5	0.0236 (8)	0.0451 (11)	0.039 (3)	0.0068 (7)	0.0065 (10)	0.0005 (12)
C3	0.0307 (8)	0.0442 (11)	0.022 (2)	0.0048 (8)	0.0078 (9)	0.0059 (11)
C4	0.0297 (9)	0.0507 (13)	0.031 (3)	0.0112 (9)	0.0041 (11)	0.0076 (13)

Geometric parameters (Å, º) top

P1—O1	1.5627 (14)	C2—C3	1.377 (3)
P1—O2	1.5628 (14)	C2—C1	1.418 (3)
P1—O3	1.511 (2)	C2—C6	1.492 (3)
P1—O4	1.5049 (16)	N2—C1	1.313 (3)
O1—H1	0.8200	N2—H2A	0.8600
O2—H2	0.8200	N2—H2B	0.8600
O5—C6	1.214 (3)	C5—C4	1.346 (4)
N1—C5	1.346 (3)	C5—H5	0.9300
N1—C1	1.358 (2)	C3—C4	1.402 (3)
N1—H1A	0.8600	C3—H3	0.9300
O6—C6	1.304 (3)	C4—H4	0.9300
O6—H6	0.8200

O4—P1—O3	115.27 (10)	H2A—N2—H2B	120.0
O4—P1—O1	106.46 (9)	N2—C1—N1	117.9 (2)
O3—P1—O1	111.25 (9)	N2—C1—C2	125.07 (17)
O4—P1—O2	106.78 (9)	N1—C1—C2	117.04 (18)
O3—P1—O2	109.09 (9)	O5—C6—O6	124.83 (19)
O1—P1—O2	107.64 (9)	O5—C6—C2	122.7 (2)
P1—O1—H1	109.5	O6—C6—C2	112.48 (18)
P1—O2—H2	109.5	C4—C5—N1	121.19 (19)
C5—N1—C1	123.6 (2)	C4—C5—H5	119.4
C5—N1—H1A	118.2	N1—C5—H5	119.4
C1—N1—H1A	118.2	C2—C3—C4	121.6 (2)
C6—O6—H6	109.5	C2—C3—H3	119.2
C3—C2—C1	118.77 (18)	C4—C3—H3	119.2
C3—C2—C6	120.7 (2)	C5—C4—C3	117.8 (2)
C1—C2—C6	120.53 (19)	C5—C4—H4	121.1
C1—N2—H2A	120.0	C3—C4—H4	121.1
C1—N2—H2B	120.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.82	1.79	2.504 (3)	145
O2—H2···O4ⁱⁱ	0.82	2.04	2.560 (3)	121
O6—H6···O3	0.82	1.78	2.579 (3)	165
N1—H1A···O4ⁱⁱⁱ	0.86	1.83	2.684 (3)	173
N2—H2A···O1ⁱⁱⁱ	0.86	2.03	2.873 (3)	169
N2—H2B···O5	0.86	2.09	2.712 (3)	129
N2—H2B···O5^iv	0.86	2.27	2.914 (3)	132
C3—H3···O6	0.93	2.36	2.694 (3)	101
C5—H5···O4^v	0.93	2.52	3.268 (3)	138

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

Experimental details

Crystal data
Chemical formula	C₆H₇N₂O₂⁺·H₂PO₄⁻
M_r	236.12
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	12.877 (3), 4.658 (3), 15.978 (2)
β (°)	99.43 (3)
V (Å³)	945.4 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.21 × 0.19 × 0.17

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3295, 1646, 1317
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.086, 1.04
No. of reflections	1646
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.32

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.820	1.786	2.504 (3)	145.30
O2—H2···O4ⁱⁱ	0.820	2.038	2.560 (3)	121.19
O6—H6···O3	0.820	1.778	2.579 (3)	164.82
N1—H1A···O4ⁱⁱⁱ	0.860	1.829	2.684 (3)	172.49
N2—H2A···O1ⁱⁱⁱ	0.860	2.025	2.873 (3)	168.51
N2—H2B···O5	0.860	2.086	2.712 (3)	129.20
N2—H2B···O5^iv	0.860	2.271	2.914 (3)	131.53
C3—H3···O6	0.9300	2.3600	2.694 (3)	101.00
C5—H5···O4^v	0.9300	2.5200	3.268 (3)	138.00

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

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