3-Amino-carbonyl-pyridinium difluoro-acetate at 123 K.

In the crystal of the title compound, C(6)H(7)N(2)O(+)·C(2)HF(2)O(2) (-), the cation adopts a catemeric N-H⋯O hydrogen-bonded chain motif involving the carboxamide group, with two further N-H⋯O hydrogen bonds connecting the cations to adjacent difluoro-acetate anions via the carboxamide and pyridinium N atoms. The carboxamide group of the nicotinamidium ion is twisted by 32.3 (6)° from the pyridine ring plane. A number of C-H⋯O and C-H⋯F interactions consolidate the packing.

Related literature

For nicotinamide, see: Wright & King (1954 ▶); Miwa et al. (1999 ▶); Hino et al. (2001 ▶). For nicotinamide solvates, co-crystals and salts, see: Bardin et al. (2009 ▶); Koman et al. (2003 ▶); Athimoolam & Natarajan (2007a ▶,b ▶); Fleischman et al. (2003 ▶); Berry et al. (2008 ▶). Identification was initially made using multi-sample foil transmission X-ray powder diffraction analysis, see: Florence et al. (2003 ▶).

Experimental

Crystal data

C6H7N2O+·C2HF2O2 −

M = 218.16

Monoclinic,

a = 4.9888 (2) Å

b = 25.6147 (12) Å

c = 7.2006 (4) Å

β = 105.912 (2)°

V = 884.88 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.15 mm−1

T = 123 K

0.30 × 0.10 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T min = 0.929, T max = 0.997

8921 measured reflections

2201 independent reflections

2087 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.091

S = 1.05

2201 reflections

152 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809043414/fl2272sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043414/fl2272Isup2.hkl

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

C6H7N2O+·C2HF2O2−	F(000) = 448
Mr = 218.16	Dx = 1.638 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6311 reflections
a = 4.9888 (2) Å	θ = 2.9–28.4°
b = 25.6147 (12) Å	µ = 0.15 mm−1
c = 7.2006 (4) Å	T = 123 K
β = 105.912 (2)°	Slab, colourless
V = 884.88 (7) Å3	0.30 × 0.10 × 0.02 mm
Z = 4

Bruker APEXII CCD diffractometer	2201 independent reflections
Radiation source: fine-focus sealed tube	2087 reflections with I > 2σ(I)
graphite	Rint = 0.015
φ and ω scans	θmax = 28.4°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −6→6
Tmin = 0.929, Tmax = 0.997	k = −32→34
8921 measured reflections	l = −8→9

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0508P)2 + 0.323P] where P = (Fo2 + 2Fc2)/3
2201 reflections	(Δ/σ)max = 0.001
152 parameters	Δρmax = 0.41 e Å−3
1 restraint	Δρmin = −0.31 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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.

	x	y	z	Uiso*/Ueq
O1	0.80371 (15)	0.74427 (3)	0.79966 (12)	0.0214 (2)
N1	0.11038 (17)	0.87200 (3)	0.62567 (12)	0.0159 (2)
N2	0.36157 (18)	0.71520 (3)	0.75584 (14)	0.0186 (3)
C1	0.19020 (19)	0.82177 (4)	0.64341 (14)	0.0146 (2)
C2	0.44978 (19)	0.80807 (4)	0.76136 (14)	0.0139 (2)
C3	0.6222 (2)	0.84727 (4)	0.86318 (15)	0.0176 (3)
C4	0.5320 (2)	0.89865 (4)	0.84480 (15)	0.0199 (3)
C5	0.2730 (2)	0.91037 (4)	0.72202 (15)	0.0187 (3)
C6	0.5522 (2)	0.75269 (4)	0.77430 (14)	0.0149 (2)
F1	0.12172 (14)	0.59643 (3)	0.66362 (11)	0.0300 (2)
F2	0.27896 (15)	0.52181 (3)	0.59164 (10)	0.0292 (2)
O2	0.73632 (16)	0.53207 (3)	0.90515 (13)	0.0238 (3)
O3	0.61539 (15)	0.61630 (3)	0.89351 (11)	0.0201 (2)
C7	0.56993 (19)	0.56809 (4)	0.85520 (14)	0.0147 (2)
C8	0.2715 (2)	0.55331 (4)	0.74290 (15)	0.0177 (3)
H1	0.06810	0.79550	0.57480	0.0180*
H1N	−0.063 (2)	0.8784 (7)	0.543 (2)	0.045 (5)*
H2N	0.185 (3)	0.7234 (6)	0.750 (2)	0.026 (4)*
H3	0.80110	0.83880	0.94500	0.0210*
H3N	0.422 (3)	0.6835 (6)	0.773 (2)	0.027 (4)*
H4	0.64680	0.92550	0.91570	0.0240*
H5	0.21060	0.94550	0.70600	0.0220*
H6	0.171 (3)	0.5363 (5)	0.822 (2)	0.017 (3)*

	U11	U22	U33	U12	U13	U23
O1	0.0136 (4)	0.0203 (4)	0.0305 (4)	0.0040 (3)	0.0065 (3)	0.0053 (3)
N1	0.0135 (4)	0.0148 (4)	0.0183 (4)	0.0022 (3)	0.0027 (3)	0.0026 (3)
N2	0.0156 (4)	0.0124 (4)	0.0281 (5)	0.0020 (3)	0.0066 (3)	0.0021 (3)
C1	0.0130 (4)	0.0137 (4)	0.0168 (4)	−0.0002 (3)	0.0034 (3)	0.0009 (3)
C2	0.0132 (4)	0.0132 (4)	0.0154 (4)	0.0012 (3)	0.0042 (3)	0.0020 (3)
C3	0.0140 (4)	0.0181 (5)	0.0186 (4)	0.0002 (3)	0.0011 (3)	0.0005 (3)
C4	0.0196 (5)	0.0156 (5)	0.0223 (5)	−0.0022 (4)	0.0023 (4)	−0.0023 (4)
C5	0.0202 (5)	0.0139 (4)	0.0218 (5)	0.0017 (3)	0.0054 (4)	0.0009 (3)
C6	0.0144 (4)	0.0152 (4)	0.0149 (4)	0.0025 (3)	0.0039 (3)	0.0021 (3)
F1	0.0183 (3)	0.0226 (3)	0.0402 (4)	0.0048 (2)	−0.0072 (3)	0.0045 (3)
F2	0.0318 (4)	0.0254 (3)	0.0267 (4)	−0.0055 (3)	0.0020 (3)	−0.0094 (3)
O2	0.0151 (4)	0.0154 (4)	0.0377 (5)	0.0025 (3)	0.0019 (3)	0.0020 (3)
O3	0.0158 (3)	0.0128 (3)	0.0276 (4)	−0.0002 (3)	−0.0007 (3)	−0.0019 (3)
C7	0.0122 (4)	0.0140 (4)	0.0175 (4)	−0.0006 (3)	0.0036 (3)	0.0005 (3)
C8	0.0146 (4)	0.0146 (4)	0.0216 (5)	−0.0006 (3)	0.0011 (4)	0.0003 (4)

F1—C8	1.3676 (13)	C1—C2	1.3851 (14)
F2—C8	1.3642 (13)	C2—C6	1.5020 (14)
O1—C6	1.2364 (13)	C2—C3	1.3928 (14)
O2—C7	1.2272 (13)	C3—C4	1.3854 (15)
O3—C7	1.2721 (13)	C4—C5	1.3838 (15)
N1—C1	1.3425 (13)	C1—H1	0.9500
N1—C5	1.3405 (13)	C3—H3	0.9500
N2—C6	1.3323 (13)	C4—H4	0.9500
N1—H1N	0.920 (12)	C5—H5	0.9500
N2—H2N	0.895 (16)	C7—C8	1.5342 (14)
N2—H3N	0.863 (15)	C8—H6	0.960 (14)
F1···C3i	3.1645 (13)	C1···O1xi	3.1802 (13)
F1···O3	2.6133 (11)	C1···N2iii	3.2748 (14)
F1···C4i	3.1997 (13)	C1···O1i	3.1763 (13)
F2···C4ii	3.2885 (13)	C1···O3i	3.3389 (13)
F2···C4iii	3.1834 (13)	C3···N1vii	3.3972 (14)
F2···F2iv	2.9535 (11)	C3···F1vi	3.1645 (13)
F2···F2v	3.0741 (11)	C4···F2x	3.1834 (13)
F2···O2	2.7472 (11)	C4···O3iii	3.4089 (13)
F2···C5iii	3.1716 (13)	C4···F2xii	3.2885 (13)
F1···H4i	2.6100	C4···F1vi	3.1997 (13)
F1···H3i	2.5300	C5···O2i	3.3464 (14)
F1···H3N	2.682 (15)	C5···C8iii	3.5712 (15)
F2···H4iii	2.8400	C5···F2x	3.1716 (13)
F2···H5iii	2.8300	C5···O3iii	3.3459 (13)
F2···H4ii	2.5000	C5···C7iii	3.4089 (14)
O1···C1vi	3.1763 (13)	C5···O2xii	3.2458 (13)
O1···C1vii	3.1802 (13)	C7···C5x	3.4089 (14)
O1···N2vii	2.9801 (12)	C7···N1vi	3.2463 (13)
O2···C8vii	3.2403 (14)	C8···C5x	3.5712 (15)
O2···F2	2.7472 (11)	C8···O2ix	3.3558 (13)
O2···O2viii	3.0848 (12)	C8···O2xi	3.2403 (14)
O2···C8ix	3.3558 (13)	C1···H2Niii	3.054 (14)
O2···C5ii	3.2458 (13)	C1···H2N	2.636 (15)
O2···N1vi	3.2275 (12)	C7···H3N	3.065 (15)
O2···C5vi	3.3464 (14)	C7···H1Nvi	2.388 (14)
O3···F1	2.6133 (11)	H1···O1i	2.3000
O3···C5x	3.3459 (13)	H1···H2N	2.2200
O3···N2	2.8836 (11)	H1···N2	2.6500
O3···N1vi	2.5921 (12)	H1···O1xi	2.6900
O3···C1vi	3.3389 (13)	H1N···O3i	1.675 (12)
O3···C4x	3.4089 (13)	H1N···C7i	2.388 (14)
O1···H2Nvii	2.099 (15)	H1N···O2i	2.589 (17)
O1···H3	2.6400	H2N···C1x	3.054 (14)
O1···H1vi	2.3000	H2N···O1xi	2.099 (15)
O1···H1vii	2.6900	H2N···C1	2.636 (15)
O2···H6ix	2.577 (13)	H2N···H1	2.2200
O2···H1Nvi	2.589 (17)	H3···O1	2.6400
O2···H6vii	2.405 (15)	H3···F1vi	2.5300
O2···H5vi	2.7900	H3N···F1	2.682 (15)
O2···H5ii	2.4000	H3N···O3	2.046 (15)
O3···H3N	2.046 (15)	H3N···C7	3.065 (15)
O3···H1Nvi	1.675 (12)	H4···F2x	2.8400
N1···C3xi	3.3972 (14)	H4···F2xii	2.5000
N1···C7i	3.2463 (13)	H4···F1vi	2.6100
N1···O2i	3.2275 (12)	H5···F2x	2.8300
N1···O3i	2.5921 (12)	H5···O2i	2.7900
N2···O3	2.8836 (11)	H5···O2xii	2.4000
N2···O1xi	2.9801 (12)	H6···O2xi	2.405 (15)
N2···C1x	3.2748 (14)	H6···O2ix	2.577 (13)
N2···H1	2.6500
C1—N1—C5	122.13 (9)	C2—C1—H1	120.00
C1—N1—H1N	115.7 (11)	C2—C3—H3	120.00
C5—N1—H1N	122.2 (11)	C4—C3—H3	120.00
C6—N2—H2N	120.1 (10)	C3—C4—H4	120.00
H2N—N2—H3N	121.9 (14)	C5—C4—H4	120.00
C6—N2—H3N	116.9 (10)	N1—C5—H5	120.00
N1—C1—C2	120.28 (9)	C4—C5—H5	120.00
C1—C2—C6	121.49 (9)	O2—C7—O3	126.89 (10)
C1—C2—C3	118.61 (9)	O2—C7—C8	116.72 (9)
C3—C2—C6	119.85 (9)	O3—C7—C8	116.32 (9)
C2—C3—C4	119.80 (10)	F1—C8—F2	106.01 (8)
C3—C4—C5	119.28 (10)	F1—C8—C7	111.16 (8)
N1—C5—C4	119.88 (9)	F2—C8—C7	109.38 (8)
O1—C6—C2	119.22 (9)	F1—C8—H6	107.4 (9)
N2—C6—C2	116.95 (9)	F2—C8—H6	109.8 (8)
O1—C6—N2	123.83 (10)	C7—C8—H6	112.9 (9)
N1—C1—H1	120.00
C5—N1—C1—C2	−1.18 (15)	C3—C2—C6—O1	−30.80 (14)
C1—N1—C5—C4	−0.15 (15)	C3—C2—C6—N2	149.70 (10)
N1—C1—C2—C3	1.24 (15)	C2—C3—C4—C5	−1.27 (15)
N1—C1—C2—C6	−176.03 (9)	C3—C4—C5—N1	1.38 (15)
C1—C2—C3—C4	−0.02 (15)	O2—C7—C8—F1	−168.25 (9)
C6—C2—C3—C4	177.30 (9)	O2—C7—C8—F2	−51.53 (12)
C1—C2—C6—O1	146.44 (10)	O3—C7—C8—F1	14.57 (12)
C1—C2—C6—N2	−33.06 (14)	O3—C7—C8—F2	131.29 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2i	0.920 (12)	2.589 (17)	3.2275 (12)	127.0 (13)
N1—H1N···O3i	0.920 (12)	1.675 (12)	2.5921 (12)	174.3 (17)
N2—H2N···O1xi	0.895 (16)	2.099 (15)	2.9801 (12)	167.9 (13)
N2—H3N···O3	0.863 (15)	2.046 (15)	2.8836 (11)	163.2 (13)
C1—H1···O1i	0.95	2.30	3.1763 (13)	154
C3—H3···F1vi	0.95	2.53	3.1645 (13)	124
C4—H4···F2xii	0.95	2.50	3.2885 (13)	141
C5—H5···O2xii	0.95	2.40	3.2458 (13)	149
C8—H6···O2xi	0.960 (14)	2.405 (15)	3.2403 (14)	145.2 (11)
C8—H6···O2ix	0.960 (14)	2.577 (13)	3.3558 (13)	138.3 (12)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2i	0.920 (12)	2.589 (17)	3.2275 (12)	127.0 (13)
N1—H1N⋯O3i	0.920 (12)	1.675 (12)	2.5921 (12)	174.3 (17)
N2—H2N⋯O1ii	0.895 (16)	2.099 (15)	2.9801 (12)	167.9 (13)
N2—H3N⋯O3	0.863 (15)	2.046 (15)	2.8836 (11)	163.2 (13)
C1—H1⋯O1i	0.95	2.30	3.1763 (13)	154
C3—H3⋯F1iii	0.95	2.53	3.1645 (13)	124
C4—H4⋯F2iv	0.95	2.50	3.2885 (13)	141
C5—H5⋯O2iv	0.95	2.40	3.2458 (13)	149
C8—H6⋯O2ii	0.960 (14)	2.405 (15)	3.2403 (14)	145.2 (11)
C8—H6⋯O2v	0.960 (14)	2.577 (13)	3.3558 (13)	138.3 (12)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .