2,2′,4,4′-Tetra­methyl-7,7′-diazenediylbis(1,8-naphthyridin-1-ium) bis­(perchlorate)

Mo, J.; Yuan, L.; Liu, J.-H.; Chen, W.; Li, X.-S.

doi:10.1107/S1600536809019485

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1500

doi:10.1107/S1600536809019485

Open

access

2,2′,4,4′-Tetramethyl-7,7′-diazenediylbis(1,8-naphthyridin-1-ium) bis(perchlorate)

Juan Mo,^a ^* Li Yuan,^a Jian-Hua Liu,^a Wen Chen ^a and Xin-Sheng Li ^a

^aCollege of Animal Husbandry and Veterinary Studies, Henan Agricultural University, Zhengzhou, Henan Province 450002, People's Republic of China
^*Correspondence e-mail: mojuan52@126.com

(Received 13 April 2009; accepted 22 May 2009; online 6 June 2009)

In the title salt, C₂₀H₂₀N₆²⁺·2ClO₄⁻, the cation is disposed about a center of symmetry at the mid-point of the N=N bond. The 1,8-naphthyridine systems are planar and the ten atoms have a mean deviation of 0.01 Å from the least-squares plane. The two planar 1,8-naphthyridine units are parallel but extend in opposite directions from the diazene bridge. The 1,8-naphthyridine aminium groups interact with perchlorate O atoms through N—H⋯O hydrogen bonds.

Related literature

For 1,8-naphthyridine and its derivatives, see: Baker & Norman (2004 ); Ferrarini et al. (1997 ); Gavrilova & Bosnich (2004 ); Stadie et al. (2007 ).

Experimental

Crystal data

C₂₀H₂₀N₆²⁺·2ClO₄⁻
M_r = 543.32
Monoclinic, P 2₁ /n
a = 8.2008 (16) Å
b = 13.042 (3) Å
c = 11.133 (2) Å
β = 102.63 (3)°
V = 1161.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 113 K
0.16 × 0.12 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.946, T_max = 0.975
9220 measured reflections
2669 independent reflections
2244 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.123
S = 1.06
2669 reflections
169 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.891 (10)	2.080 (15)	2.907 (2)	154
N1—H1⋯O3ⁱ	0.891 (10)	2.56 (2)	3.277 (3)	138
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019485/hg2501sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019485/hg2501Isup2.hkl

checkCIF report

Comment top

1,8-Naphthyridine and its derivatives are used for binding of mismatched guanine or used as versatile ligands which are able to form metal aggregates with monodentates fashion or chelating bidentate fashion (Ferrarini et al., 1997; Gavrilova & Bosnich, 2004; Baker & Norman, 2004; Stadie et al., 2007). We report here a new 1,8-Naphthyridine compound, Fig. 1.

The title compound reveals 1,8-naphthyridine rings are linked by azo double bond, compound (I) is coplanar between two 1,8-naphthyridine rings. Each 1,8-naphthyridine ring is an almost planar group in which the ten atoms forming the 1,8-naphthyridine ring have mean deviation of 0.01 Å from the least-squares plane calculated using the ten atoms. The cation part sits on a center of symmetry at the mid-point of the N—N bond. To balance hydrogen ion charge of two 1,8-naphthyridine rings, there are two perchlorate groups in the crystal cell. The structure shows N-H···O hydrogen bonds between the amines ions of 1,8-naphthyridine groups and O atoms of perchlorate anions.

Related literature top

For related literature, see: Baker & Norman (2004); Ferrarini et al. (1997); Gavrilova & Bosnich (2004); Stadie et al. (2007).

Experimental top

Single crystals of (I) suitable for an X-ray study were obtained by slow evaporation of an aqueous ethanol solution (30% v/v) in the presence of perchloric acid at 293 K over a period of four weeks.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. Molecular structure of the title compound showing the atom-numbering scheme and displacement ellipsoids drawn at the 40% probability level. The hydrogen bond is shown as a dashed line. [Symmetry codes: (i) 1 - x, 1 - y, 2 - z; (ii) 0.5 + x, 1.5 - y, -0.5 + z; (iii) 0.5 - x, -0.5 + y, 2.5 - z].

2,2',4,4'-Tetramethyl-7,7'-diazenediylbis(1,8-naphthyridin-1-ium) bis(perchlorate) top

Crystal data top

C₂₀H₂₀N₆²⁺·2ClO₄⁻	F(000) = 560
M_r = 543.32	D_x = 1.553 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3246 reflections
a = 8.2008 (16) Å	θ = 2.4–27.7°
b = 13.042 (3) Å	µ = 0.34 mm⁻¹
c = 11.133 (2) Å	T = 113 K
β = 102.63 (3)°	Prism, yellow
V = 1161.9 (4) Å³	0.16 × 0.12 × 0.06 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	2669 independent reflections
Radiation source: fine-focus sealed tube	2244 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 27.7°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→10
T_min = 0.946, T_max = 0.975	k = −16→16
9220 measured reflections	l = −14→14

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0581P)² + 0.8149P] where P = (F_o² + 2F_c²)/3
2669 reflections	(Δ/σ)_max = 0.001
169 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₂₀H₂₀N₆²⁺·2ClO₄⁻	V = 1161.9 (4) Å³
M_r = 543.32	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.2008 (16) Å	µ = 0.34 mm⁻¹
b = 13.042 (3) Å	T = 113 K
c = 11.133 (2) Å	0.16 × 0.12 × 0.06 mm
β = 102.63 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2669 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2244 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.975	R_int = 0.042
9220 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.50 e Å⁻³
2669 reflections	Δρ_min = −0.44 e Å⁻³
169 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
N1	0.6259 (2)	0.83991 (12)	0.80976 (14)	0.0192 (4)
N2	0.5576 (2)	0.68663 (12)	0.88762 (14)	0.0166 (3)
N3	0.4967 (2)	0.52789 (12)	0.95394 (14)	0.0177 (3)
C1	0.6950 (3)	0.99037 (16)	0.70209 (19)	0.0290 (5)
H1A	0.7525	0.9466	0.6557	0.044*
H1B	0.7573	1.0526	0.7228	0.044*
H1C	0.5860	1.0063	0.6537	0.044*
C2	0.6780 (3)	0.93708 (15)	0.81696 (17)	0.0198 (4)
C3	0.7132 (3)	0.98554 (15)	0.93190 (18)	0.0214 (4)
H3	0.7480	1.0536	0.9372	0.026*
C4	0.6978 (2)	0.93524 (15)	1.03682 (17)	0.0199 (4)
C5	0.6409 (2)	0.83139 (14)	1.02677 (16)	0.0167 (4)
C6	0.6177 (3)	0.77045 (15)	1.12667 (17)	0.0196 (4)
H6	0.6356	0.7978	1.2056	0.024*
C7	0.5685 (3)	0.67085 (15)	1.10573 (16)	0.0191 (4)
H7	0.5524	0.6293	1.1701	0.023*
C8	0.5425 (2)	0.63213 (14)	0.98489 (15)	0.0156 (4)
C9	0.6065 (2)	0.78426 (14)	0.91017 (16)	0.0156 (4)
C10	0.7442 (3)	0.98621 (16)	1.15997 (19)	0.0291 (5)
H10A	0.8410	0.9532	1.2088	0.044*
H10B	0.6529	0.9809	1.2008	0.044*
H10C	0.7686	1.0572	1.1493	0.044*
Cl1	0.07021 (6)	0.72566 (4)	0.98120 (4)	0.02260 (17)
O1	0.1777 (3)	0.76617 (13)	1.09150 (15)	0.0440 (5)
O2	0.1613 (2)	0.65386 (14)	0.92339 (14)	0.0372 (4)
O3	−0.0642 (2)	0.67208 (14)	1.01881 (17)	0.0407 (5)
O4	0.0056 (2)	0.80751 (14)	0.89857 (15)	0.0380 (4)
H1	0.607 (3)	0.8059 (18)	0.7387 (15)	0.037 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0273 (9)	0.0158 (8)	0.0153 (7)	−0.0011 (7)	0.0063 (6)	−0.0005 (6)
N2	0.0196 (8)	0.0150 (8)	0.0155 (7)	−0.0003 (6)	0.0049 (6)	0.0008 (6)
N3	0.0214 (8)	0.0162 (8)	0.0157 (7)	−0.0016 (6)	0.0043 (6)	0.0014 (6)
C1	0.0447 (14)	0.0198 (10)	0.0250 (10)	−0.0061 (9)	0.0129 (10)	0.0031 (8)
C2	0.0226 (10)	0.0160 (9)	0.0216 (9)	0.0005 (8)	0.0068 (7)	0.0031 (7)
C3	0.0240 (10)	0.0153 (9)	0.0248 (9)	−0.0026 (8)	0.0049 (8)	−0.0002 (7)
C4	0.0204 (10)	0.0182 (9)	0.0196 (9)	0.0002 (8)	0.0011 (7)	−0.0022 (7)
C5	0.0167 (9)	0.0162 (9)	0.0163 (8)	0.0016 (7)	0.0013 (7)	−0.0004 (7)
C6	0.0232 (10)	0.0221 (10)	0.0132 (8)	0.0010 (8)	0.0031 (7)	−0.0003 (7)
C7	0.0244 (10)	0.0198 (9)	0.0131 (8)	−0.0002 (8)	0.0043 (7)	0.0021 (7)
C8	0.0170 (9)	0.0154 (9)	0.0142 (8)	0.0001 (7)	0.0031 (7)	0.0009 (6)
C9	0.0169 (9)	0.0154 (9)	0.0154 (8)	0.0015 (7)	0.0052 (7)	0.0014 (7)
C10	0.0414 (13)	0.0221 (10)	0.0213 (10)	−0.0069 (10)	0.0011 (9)	−0.0048 (8)
Cl1	0.0238 (3)	0.0264 (3)	0.0174 (2)	0.00234 (19)	0.00408 (19)	−0.00095 (17)
O1	0.0653 (13)	0.0319 (9)	0.0272 (9)	−0.0120 (9)	−0.0067 (8)	−0.0026 (7)
O2	0.0414 (10)	0.0470 (10)	0.0264 (8)	0.0175 (8)	0.0142 (7)	−0.0006 (7)
O3	0.0293 (9)	0.0441 (11)	0.0529 (11)	0.0024 (8)	0.0183 (8)	0.0112 (8)
O4	0.0429 (11)	0.0393 (10)	0.0317 (8)	0.0102 (8)	0.0081 (8)	0.0129 (7)

Geometric parameters (Å, º) top

N1—C2	1.334 (3)	C4—C10	1.496 (3)
N1—C9	1.371 (2)	C5—C9	1.408 (2)
N1—H1	0.891 (10)	C5—C6	1.414 (3)
N2—C8	1.324 (2)	C6—C7	1.365 (3)
N2—C9	1.342 (2)	C6—H6	0.9300
N3—N3ⁱ	1.249 (3)	C7—C8	1.409 (2)
N3—C8	1.432 (2)	C7—H7	0.9300
C1—C2	1.489 (3)	C10—H10A	0.9600
C1—H1A	0.9600	C10—H10B	0.9600
C1—H1B	0.9600	C10—H10C	0.9600
C1—H1C	0.9600	Cl1—O4	1.4329 (17)
C2—C3	1.400 (3)	Cl1—O2	1.4348 (16)
C3—C4	1.370 (3)	Cl1—O3	1.4423 (17)
C3—H3	0.9300	Cl1—O1	1.4460 (17)
C4—C5	1.429 (3)

C2—N1—C9	123.14 (16)	C7—C6—H6	120.4
C2—N1—H1	121.3 (18)	C5—C6—H6	120.4
C9—N1—H1	115.5 (18)	C6—C7—C8	118.79 (17)
C8—N2—C9	115.72 (15)	C6—C7—H7	120.6
N3ⁱ—N3—C8	113.16 (19)	C8—C7—H7	120.6
C2—C1—H1A	109.5	N2—C8—C7	124.55 (17)
C2—C1—H1B	109.5	N2—C8—N3	112.30 (15)
H1A—C1—H1B	109.5	C7—C8—N3	123.16 (16)
C2—C1—H1C	109.5	N2—C9—N1	115.66 (16)
H1A—C1—H1C	109.5	N2—C9—C5	125.33 (16)
H1B—C1—H1C	109.5	N1—C9—C5	119.01 (17)
N1—C2—C3	118.89 (17)	C4—C10—H10A	109.5
N1—C2—C1	118.73 (17)	C4—C10—H10B	109.5
C3—C2—C1	122.37 (18)	H10A—C10—H10B	109.5
C4—C3—C2	121.63 (18)	C4—C10—H10C	109.5
C4—C3—H3	119.2	H10A—C10—H10C	109.5
C2—C3—H3	119.2	H10B—C10—H10C	109.5
C3—C4—C5	118.47 (17)	O4—Cl1—O2	110.72 (10)
C3—C4—C10	121.09 (18)	O4—Cl1—O3	110.40 (11)
C5—C4—C10	120.42 (17)	O2—Cl1—O3	108.64 (11)
C9—C5—C6	116.46 (17)	O4—Cl1—O1	110.13 (11)
C9—C5—C4	118.84 (17)	O2—Cl1—O1	109.81 (12)
C6—C5—C4	124.70 (17)	O3—Cl1—O1	107.05 (12)
C7—C6—C5	119.10 (17)

C9—N1—C2—C3	−0.7 (3)	C9—N2—C8—N3	−177.58 (16)
C9—N1—C2—C1	179.94 (19)	C6—C7—C8—N2	−2.1 (3)
N1—C2—C3—C4	1.0 (3)	C6—C7—C8—N3	177.69 (18)
C1—C2—C3—C4	−179.7 (2)	N3ⁱ—N3—C8—N2	171.1 (2)
C2—C3—C4—C5	−1.3 (3)	N3ⁱ—N3—C8—C7	−8.7 (3)
C2—C3—C4—C10	176.8 (2)	C8—N2—C9—N1	178.50 (17)
C3—C4—C5—C9	1.3 (3)	C8—N2—C9—C5	−0.4 (3)
C10—C4—C5—C9	−176.81 (19)	C2—N1—C9—N2	−178.19 (18)
C3—C4—C5—C6	−179.40 (19)	C2—N1—C9—C5	0.7 (3)
C10—C4—C5—C6	2.4 (3)	C6—C5—C9—N2	−1.6 (3)
C9—C5—C6—C7	1.7 (3)	C4—C5—C9—N2	177.76 (18)
C4—C5—C6—C7	−177.61 (19)	C6—C5—C9—N1	179.63 (17)
C5—C6—C7—C8	0.0 (3)	C4—C5—C9—N1	−1.1 (3)
C9—N2—C8—C7	2.2 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	0.89 (1)	2.08 (2)	2.907 (2)	154
N1—H1···O3ⁱⁱ	0.89 (1)	2.56 (2)	3.277 (3)	138

Symmetry code: (ii) x+1/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₀N₆²⁺·2ClO₄⁻
M_r	543.32
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	8.2008 (16), 13.042 (3), 11.133 (2)
β (°)	102.63 (3)
V (Å³)	1161.9 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.16 × 0.12 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.946, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	9220, 2669, 2244
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.654

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.123, 1.06
No. of reflections	2669
No. of parameters	169
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.44

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.891 (10)	2.080 (15)	2.907 (2)	154
N1—H1···O3ⁱ	0.891 (10)	2.56 (2)	3.277 (3)	138

Symmetry code: (i) x+1/2, −y+3/2, z−1/2.

Acknowledgements

The authors thank Henan Agricultural University for the generous support of this study.

References

Baker, R. S. & Norman, R. E. (2004). Acta Cryst. E60, m1761–m1763. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ferrarini, P. L., Mori, C., Badawneh, M., Manera, C., Martinelli, A., Miceli, M., Ramagnoli, F. & Saccomanni, G. (1997). J. Heterocycl. Chem. 34, 1501–1504. CrossRef CAS Google Scholar
Gavrilova, E. L. & Bosnich, B. (2004). Chem. Rev. 104, 349–383. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stadie, N. P., Sanchez-Smith, R. & Groy, T. L. (2007). Acta Cryst. E63, m2153–m2154. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1500

doi:10.1107/S1600536809019485

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

2,2′,4,4′-Tetra­methyl-7,7′-diazenediylbis(1,8-naphthyridin-1-ium) bis­­(perchlorate)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2,2′,4,4′-Tetramethyl-7,7′-diazenediylbis(1,8-naphthyridin-1-ium) bis(perchlorate)