2-{5-[N-(2-Pyridyl)carbamo­yl]pentan­amido}pyridinium hexa­fluoro­phosphate

Cheng, P.-C.; Wu, C.-J.; Chen, H.-C.; Chen, J.-D.; Wang, J.-C.

doi:10.1107/S1600536809026488

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1825

doi:10.1107/S1600536809026488

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2-{5-[N-(2-Pyridyl)carbamoyl]pentanamido}pyridinium hexafluorophosphate

Pei-Chi Cheng,^a Chia-Jun Wu,^a Huan-Ching Chen,^a Jhy-Der Chen ^a ^* and Ju-Chun Wang ^b

^aDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li, Taiwan, and ^bDepartment of Chemistry, Soochow University, Taipei, Taiwan
^*Correspondence e-mail: jdchen@cycu.edu.tw

(Received 17 June 2009; accepted 7 July 2009; online 11 July 2009)

In the crystal structure of the title compound, C₁₆H₁₉N₄O₂⁺·PF₆⁻, the cations and anions are situated on centres of inversion. Thus, the N—H H atom is disordered over both N atoms due to symmetry. In the crystal, molecules are connected via N—H⋯F and N—H⋯O hydrogen bonds. The cation adopts the ⋯AAA⋯ trans conformation in the solid state.

Related literature

For similar structures, see: Chen et al. (2007 ).

Experimental

Crystal data

C₁₆H₁₉N₄O₂⁺·PF₆⁻
M_r = 444.32
Monoclinic, P 2₁ /c
a = 6.2119 (18) Å
b = 12.9265 (11) Å
c = 11.439 (2) Å
β = 96.415 (10)°
V = 912.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 295 K
0.5 × 0.2 × 0.2 mm

Data collection

Bruker P4 diffractometer
Absorption correction: multi-scan (XSCANS; Siemens, 1995 ) T_min = 0.945, T_max = 0.962
2288 measured reflections
1612 independent reflections
1334 reflections with I > 2σ(I)
R_int = 0.020
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.096
S = 1.07
1612 reflections
133 parameters
H-atom parameters constrained
Δρ_max = 0.40 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—H1A⋯F1	0.86	1.98	2.737 (2)	145
N1—H1A⋯O	0.86	2.10	2.674 (2)	124
N2—H2A⋯F3ⁱ	0.86	1.95	2.774 (2)	161
N2—H2A⋯F1ⁱ	0.86	2.40	3.050 (2)	133
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: XSCANS (Siemens, 1995); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2008 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026488/nc2150sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026488/nc2150Isup2.hkl

checkCIF report

Comment top

The compound N¹,N²-di(2-pyridyl)adipoamide has been used as bridging ligand in coordination chemistry (Chen et al., 2007). In the present work the structure of the title compound (Fig. 1) has been determined to investigate the role of the cation-anion interaction on the ligand conformation. The molecules are connected via N—H···F and N—H···O hydrogen bonds (Tab. 1). The cation adopts the AAA trans conformation in the solid state. This conformation is the same as that found for the neutral N¹,N²-di(2-pyridyl)adipoamide ligand which cocrystallize with water (Chen et al., 2007).

Related literature top

For similar structures, see: Chen et al. (2007).

Experimental top

N¹,N²-Di(2-pyridyl)adipoamide (0.30 g, 1.00 mmol) and AgPF₆ (0.25 g, 1.00 mmol) were placed in a flask containing 20 ml of CH₂Cl₂. The mixture was refluxed for 8 h to give a white precipitate, which was then filtered and dried under vacuum. By dissolving the solid in dichloromethane, followed by allowing the solvent to evaporate slowly under air, plate colorless crystals suitable for X-ray crystallography were obtained.

Computing details top

Data collection: XSCANS (Siemens, 1995); cell refinement: XSCANS (Siemens, 1995); data reduction: SHELXTL (Sheldrick, 2008); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The title molecule with the labelling scheme. The bond to the disordered H atom is indicated by dashed open lines. The displacement ellipsoids are drawn at the 30% probability level.Symmetry codes: (i) -x,-y+1,-z; (ii) -x-1,-y,-z.

2-{5-[N-(2-Pyridyl)carbamoyl]pentanamido}pyridinium hexafluorophosphate top

Crystal data top

C₁₆H₁₉N₄O₂⁺·PF₆⁻	F(000) = 456
M_r = 444.32	D_x = 1.617 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 27 reflections
a = 6.2119 (18) Å	θ = 5.1–12.5°
b = 12.9265 (11) Å	µ = 0.23 mm⁻¹
c = 11.439 (2) Å	T = 295 K
β = 96.415 (10)°	Plate, colorless
V = 912.8 (3) Å³	0.5 × 0.2 × 0.2 mm
Z = 2

Data collection top

Bruker P4 diffractometer	1334 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 25.0°, θ_min = 2.4°
ω scans	h = −1→7
Absorption correction: multi-scan (XSCANS; Siemens, 1995)	k = −15→1
T_min = 0.945, T_max = 0.962	l = −13→13
2288 measured reflections	3 standard reflections every 97 reflections
1612 independent reflections	intensity decay: none

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0403P)² + 0.4314P] where P = (F_o² + 2F_c²)/3
1612 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₆H₁₉N₄O₂⁺·PF₆⁻	V = 912.8 (3) Å³
M_r = 444.32	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.2119 (18) Å	µ = 0.23 mm⁻¹
b = 12.9265 (11) Å	T = 295 K
c = 11.439 (2) Å	0.5 × 0.2 × 0.2 mm
β = 96.415 (10)°

Data collection top

Bruker P4 diffractometer	1334 reflections with I > 2σ(I)
Absorption correction: multi-scan (XSCANS; Siemens, 1995)	R_int = 0.020
T_min = 0.945, T_max = 0.962	3 standard reflections every 97 reflections
2288 measured reflections	intensity decay: none
1612 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.07	Δρ_max = 0.40 e Å⁻³
1612 reflections	Δρ_min = −0.30 e Å⁻³
133 parameters

Special details top

Experimental. 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.

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	Occ. (<1)
P	0.0000	0.5000	0.0000	0.0275 (2)
F1	0.0589 (2)	0.37673 (9)	−0.03443 (10)	0.0367 (3)
F2	0.2624 (2)	0.52790 (12)	0.01505 (15)	0.0549 (4)
F3	−0.0162 (3)	0.53230 (11)	−0.14390 (11)	0.0517 (4)
O	−0.0438 (3)	0.16414 (14)	0.01248 (14)	0.0526 (5)
N1	0.2814 (3)	0.26186 (14)	0.14024 (15)	0.0331 (4)
H1A	0.1777	0.2752	0.0861	0.040*	0.50
N2	0.0760 (3)	0.12150 (15)	0.20013 (15)	0.0352 (4)
H2A	0.0473	0.0858	0.2599	0.042*
C1	0.4629 (4)	0.32123 (18)	0.1488 (2)	0.0387 (5)
H1B	0.4739	0.3749	0.0957	0.046*
C2	0.6283 (4)	0.30293 (19)	0.2341 (2)	0.0410 (5)
H2B	0.7533	0.3430	0.2392	0.049*
C3	0.6078 (4)	0.22297 (19)	0.3140 (2)	0.0386 (5)
H3A	0.7187	0.2102	0.3739	0.046*
C4	0.4248 (4)	0.16336 (18)	0.30451 (18)	0.0347 (5)
H4A	0.4107	0.1102	0.3579	0.042*
C5	0.2600 (3)	0.18256 (16)	0.21465 (17)	0.0300 (5)
C6	−0.0652 (4)	0.11249 (17)	0.09912 (19)	0.0336 (5)
C7	−0.2390 (4)	0.03259 (18)	0.10327 (19)	0.0365 (5)
H7A	−0.3056	0.0409	0.1755	0.044*
H7B	−0.1743	−0.0357	0.1041	0.044*
C8	−0.4124 (4)	0.04088 (18)	−0.0011 (2)	0.0375 (5)
H8A	−0.4784	0.1089	−0.0012	0.045*
H8B	−0.3451	0.0339	−0.0733	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P	0.0269 (4)	0.0280 (4)	0.0265 (4)	−0.0007 (3)	−0.0013 (3)	−0.0024 (3)
F1	0.0443 (7)	0.0275 (6)	0.0364 (6)	0.0055 (6)	−0.0032 (5)	−0.0043 (5)
F2	0.0268 (7)	0.0474 (8)	0.0887 (12)	−0.0045 (6)	−0.0011 (7)	−0.0043 (8)
F3	0.0854 (11)	0.0420 (8)	0.0276 (7)	0.0119 (7)	0.0052 (7)	0.0018 (6)
O	0.0577 (12)	0.0553 (11)	0.0398 (9)	−0.0212 (9)	−0.0163 (8)	0.0162 (8)
N1	0.0326 (10)	0.0340 (10)	0.0319 (9)	−0.0024 (8)	−0.0009 (8)	0.0032 (8)
N2	0.0315 (10)	0.0448 (11)	0.0282 (9)	−0.0073 (9)	−0.0020 (7)	0.0074 (8)
C1	0.0428 (13)	0.0332 (12)	0.0395 (12)	−0.0057 (10)	0.0023 (10)	0.0022 (10)
C2	0.0328 (12)	0.0410 (13)	0.0482 (13)	−0.0077 (10)	−0.0002 (10)	−0.0053 (11)
C3	0.0307 (11)	0.0445 (14)	0.0381 (12)	0.0037 (10)	−0.0077 (9)	−0.0038 (10)
C4	0.0333 (12)	0.0385 (12)	0.0305 (10)	0.0014 (10)	−0.0040 (9)	0.0043 (9)
C5	0.0277 (11)	0.0336 (11)	0.0281 (10)	0.0009 (9)	0.0007 (8)	0.0005 (9)
C6	0.0325 (11)	0.0342 (11)	0.0329 (11)	0.0008 (9)	−0.0022 (9)	0.0012 (9)
C7	0.0367 (12)	0.0382 (12)	0.0330 (11)	−0.0049 (10)	−0.0023 (9)	0.0004 (10)
C8	0.0353 (11)	0.0362 (12)	0.0394 (12)	−0.0046 (10)	−0.0024 (10)	0.0009 (10)

Geometric parameters (Å, º) top

P—F2ⁱ	1.6596 (14)	C1—H1B	0.9300
P—F2	1.6596 (14)	C2—C3	1.395 (3)
P—F3	1.6902 (13)	C2—H2B	0.9300
P—F3ⁱ	1.6902 (13)	C3—C4	1.368 (3)
P—F1	1.6912 (12)	C3—H3A	0.9300
P—F1ⁱ	1.6913 (12)	C4—C5	1.389 (3)
O—C6	1.214 (3)	C4—H4A	0.9300
N1—C5	1.348 (3)	C6—C7	1.499 (3)
N1—C1	1.358 (3)	C7—C8	1.520 (3)
N1—H1A	0.8600	C7—H7A	0.9700
N2—C6	1.375 (3)	C7—H7B	0.9700
N2—C5	1.383 (3)	C8—C8ⁱⁱ	1.519 (4)
N2—H2A	0.8600	C8—H8A	0.9700
C1—C2	1.356 (3)	C8—H8B	0.9700

F2ⁱ—P—F2	180.0	C3—C2—H2B	120.5
F2ⁱ—P—F3	90.09 (8)	C4—C3—C2	120.1 (2)
F2—P—F3	89.91 (8)	C4—C3—H3A	120.0
F2ⁱ—P—F3ⁱ	89.91 (8)	C2—C3—H3A	120.0
F2—P—F3ⁱ	90.09 (8)	C3—C4—C5	119.7 (2)
F3—P—F3ⁱ	180.00 (9)	C3—C4—H4A	120.2
F2ⁱ—P—F1	90.39 (7)	C5—C4—H4A	120.2
F2—P—F1	89.61 (7)	N1—C5—N2	119.76 (18)
F3—P—F1	89.82 (6)	N1—C5—C4	119.09 (19)
F3ⁱ—P—F1	90.18 (6)	N2—C5—C4	121.14 (19)
F2ⁱ—P—F1ⁱ	89.61 (7)	O—C6—N2	121.4 (2)
F2—P—F1ⁱ	90.39 (7)	O—C6—C7	123.3 (2)
F3—P—F1ⁱ	90.18 (6)	N2—C6—C7	115.21 (18)
F3ⁱ—P—F1ⁱ	89.82 (6)	C6—C7—C8	112.12 (18)
F1—P—F1ⁱ	180.00 (8)	C6—C7—H7A	109.2
C5—N1—C1	121.58 (19)	C8—C7—H7A	109.2
C5—N1—H1A	119.2	C6—C7—H7B	109.2
C1—N1—H1A	119.2	C8—C7—H7B	109.2
C6—N2—C5	126.15 (18)	H7A—C7—H7B	107.9
C6—N2—H2A	116.9	C8ⁱⁱ—C8—C7	112.6 (2)
C5—N2—H2A	116.9	C8ⁱⁱ—C8—H8A	109.1
C2—C1—N1	120.6 (2)	C7—C8—H8A	109.1
C2—C1—H1B	119.7	C8ⁱⁱ—C8—H8B	109.1
N1—C1—H1B	119.7	C7—C8—H8B	109.1
C1—C2—C3	118.9 (2)	H8A—C8—H8B	107.8
C1—C2—H2B	120.5

Symmetry codes: (i) −x, −y+1, −z; (ii) −x−1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···F1	0.86	1.98	2.737 (2)	145
N1—H1A···O	0.86	2.10	2.674 (2)	124
N2—H2A···F3ⁱⁱⁱ	0.86	1.95	2.774 (2)	161
N2—H2A···F1ⁱⁱⁱ	0.86	2.40	3.050 (2)	133

Symmetry code: (iii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₉N₄O₂⁺·PF₆⁻
M_r	444.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	6.2119 (18), 12.9265 (11), 11.439 (2)
β (°)	96.415 (10)
V (Å³)	912.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.5 × 0.2 × 0.2

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	Multi-scan (XSCANS; Siemens, 1995)
T_min, T_max	0.945, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	2288, 1612, 1334
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.096, 1.07
No. of reflections	1612
No. of parameters	133
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.30

Computer programs: XSCANS (Siemens, 1995), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···F1	0.86	1.98	2.737 (2)	145.4
N1—H1A···O	0.86	2.10	2.674 (2)	123.9
N2—H2A···F3ⁱ	0.86	1.95	2.774 (2)	160.5
N2—H2A···F1ⁱ	0.86	2.40	3.050 (2)	133.3

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

We are grateful to the National Science Council of the Republic of China for support. This research was also supported by the project of specific research fields in Chung-Yuan Christian University, Taiwan, under grant CYCU-97-CR-CH.

References

Chen, H.-C., Hu, H.-L., Chan, Z.-K., Yeh, C.-W., Jia, H.-W., Wu, C.-P., Chen, J.-D. & Wang, J.-C. (2007). Cryst. Growth Des. 7, 698–704. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1995). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar