organic compounds
2,2′,4,4′-Tetramethyl-7,7′-diazenediylbis(1,8-naphthyridin-1-ium) bis(perchlorate)
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
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
|
Refinement
|
Data collection: SMART (Bruker, 2000); cell 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
10.1107/S1600536809019485/hg2501sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809019485/hg2501Isup2.hkl
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.
Carbon bound hydrogen atoms were generated geometrically (C—H bond lengths of methylgroup fixed at 0.96Å, C—H bond lengths of naphthyridine fixed at 0.93Å), assigned appropriated isotropic thermal parameters, Uiso(H) = 1.2Ueq(C). The nitrogen proton was refined with the N—H bond length of naphthyridine fixed at 0.89 Å and with Uiso(H) = 1.5Ueq(N).
Data collection: SMART (Bruker, 2000); cell
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).C20H20N62+·2ClO4− | F(000) = 560 |
Mr = 543.32 | Dx = 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 |
Bruker SMART CCD area-detector diffractometer | 2669 independent reflections |
Radiation source: fine-focus sealed tube | 2244 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ϕ and ω scans | θmax = 27.7°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −8→10 |
Tmin = 0.946, Tmax = 0.975 | k = −16→16 |
9220 measured reflections | l = −14→14 |
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(Fo2) + (0.0581P)2 + 0.8149P] where P = (Fo2 + 2Fc2)/3 |
2669 reflections | (Δ/σ)max = 0.001 |
169 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
C20H20N62+·2ClO4− | V = 1161.9 (4) Å3 |
Mr = 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)° |
Bruker SMART CCD area-detector diffractometer | 2669 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2244 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 0.975 | Rint = 0.042 |
9220 measured reflections |
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 | Δρmax = 0.50 e Å−3 |
2669 reflections | Δρmin = −0.44 e Å−3 |
169 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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. |
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− |
Mr | 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) |
Tmin, Tmax | 0.946, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9220, 2669, 2244 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.50, −0.44 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
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.
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.