Acta Cryst.(2004). E60, o645±o646 DOI: 10.1107/S1600536804006300 Guo, Geng and Feng C10H10N3+ClO4ÿ
o645
organic papers
Acta Crystallographica Section E
Structure Reports
Online ISSN 1600-5368
2-(2-Pyridylamino)pyridinium perchlorate
displaying a one-dimensional hydrogen-bonding
supramolecular chain
Ya-Mei Guo,* Zhi-Gang Geng and Xia Feng
School of Science, Tianjin University, Tianjin 300072, People's Republic of China
Correspondence e-mail: ymguo@public.tpt.tj.cn
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.008 AÊ Disorder in main residue
Rfactor = 0.069
wRfactor = 0.199
Data-to-parameter ratio = 10.2
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
In the crystal structure of the title compound, C10H10N3+ClO4ÿ, the cation adopts the normal trans±trans
con®guration and an approximately planar geometry. Hydro-gen-bonding interactions between the cations and perchlorate anions extend this structure into a one-dimensional chain architecture.
Comment
Chelating ligands containing aromatic nitrogen heterocycles, such as the well known compounds 2,20-bipyridine and 1,10-phenanthroline, have given a great impetus to coordination chemistry. Among them, bis(2-pyridyl)amine has attracted much interest in the formation of directly bonded linear chains of metal centers (Cotton et al., 1997, 1998) or photo-luminescent materials (Du & Zhao, 2004a). On the other hand, aromatic compounds of this type usually exhibit inter-esting proton-sponge properties (Du & Zhao, 2004b), i.e.
represent a species that can act as proton acceptors through the formation of NÐH Y hydrogen bonds. Very recently, the crystal structure of the nitrate salt of protonated bis(2-pyridyl)amine was determined (Du & Zhao, 2004c). In the present contribution, we report the molecular and supramol-ecular structure of the perchlorate salt of protonated bis(2-pyridyl)amine, (I).
The crystal structure of (I) consists of a monoprotonated cation, [C10H10N3]+, and a perchlorate anion. The cation
adopts the normaltrans±transcon®guration; all non-H atoms within the cation are almost coplanar and the mean deviation of any atom from the least-squares plane is 0.014 (6) AÊ. The dihedral angle between the pyridine and pyridyl rings is only 1.5 (5). Selected bond lengths and angles are listed in Table 1. Analysis of the crystal packing of the title compound shows the existence of NÐH N and NÐH O hydrogen-bonding interactions, which connect the cation and perchlorate anions into a one-dimensional chain motif. As depicted in Fig. 1, within the monoprotonated cation, an intramolecular N1Ð H1A N3 hydrogen bond is observed. The protonated NH group also forms an intermolecular N1ÐH1A O2i(Table 2)
hydrogen bond with the adjacent perchlorate anion. Addi-tionally, the amide group is involved in an N2ÐH2A O4
hydrogen bond with the perchlorate anion. Thus the perchlorate anions bridge the cations to form a one-dimen-sional supramolecular chainviahydrogen bonds (Fig. 1). The relevant hydrogen-bonding geometric details are listed in Table 2; these values are in the normal range for such hydrogen-bonding interactions (Desiraju & Steiner, 1999). Examination of this structure with PLATON (Spek, 2003) shows that there are no solvent-accessible voids or signi®cant
±stacking interactions.
Experimental
Several drops of a dilute aqueous solution of HClO4were added to a
solution of bis(2-pyridyl)amine in CH3CN/CH3OH. Afterca10 min
of mixing, the resulting clear solution was ®ltered and set aside, affording colorless lamellar single crystals of (I) suitable for X-ray diffraction within one week. Analysis calculated for the title compound: C 44.21, H 3.71, N 15.46%; found: C 44.07, H 3.99, N 15.39%. FT±IR (KBr pellet, cmÿ1): 3074 (w), 2945 (w), 1665 (s), 1602
(s), 1561 (s), 1508 (m), 1483 (w), 1454 (s), 1427 (w), 1304 (w), 1244 (s), 1202 (w), 1146 (s), 1114 (s), 1087 (s), 1037 (s), 1030 (m), 1004 (w), 931 (w), 900 (w), 882 (w), 840 (w), 809 (w), 776 (s), 737 (w), 624 (m).
Crystal data C10H10N3+ClO4ÿ
Mr= 271.66 Monoclinic,P21=c
a= 8.527 (3) AÊ b= 16.174 (5) AÊ c= 8.753 (3) AÊ
= 100.878 (6)
V= 1185.5 (7) AÊ3
Z= 4
Dx= 1.522 Mg mÿ3 MoKradiation Cell parameters from 925
re¯ections
= 2.7±21.4
= 0.33 mmÿ1
T= 293 (2) K Plate, colorless 0.240.200.08 mm Data collection
Bruker SMART CCD area-detector diffractometer
'and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) Tmin= 0.866,Tmax= 0.970
4794 measured re¯ections
2033 independent re¯ections 1165 re¯ections withI> 2(I) Rint= 0.050
max= 25.0
h=ÿ10!7 k=ÿ14!19 l=ÿ10!10 Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.070
wR(F2) = 0.200
S= 1.02 2033 re¯ections
H-atom parameters constrained w= 1/[2(F
o2) + (0.1137P)2] whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001
max= 0.39 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
N1ÐC5 1.347 (6)
N1ÐC1 1.349 (6)
N2ÐC5 1.338 (6)
N2ÐC6 1.388 (6)
N3ÐC6 1.316 (6)
N3ÐC10 1.341 (6)
C5ÐN1ÐC1 121.9 (4)
C5ÐN2ÐC6 131.8 (4) C6ÐN3ÐC10 118.1 (4)
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
N1ÐH1A N3 0.86 1.96 2.623 (6) 133
N1ÐH1A O2i 0.86 2.47 3.149 (5) 137
N2ÐH2A O4 0.86 1.94 2.785 (6) 166
Symmetry code: (i) 1ÿx;1 2y;12ÿz.
Although all H atoms were visible in difference maps, they were ®nally placed at calculated positions (0.93 AÊ for aromatic CÐH and 0.86 AÊ for NÐH distances) and re®ned in the riding-model approx-imation, withUiso(H) = 1.2Ueq(C,N). Although we have tried many
times, the lamellar single crystals obtained were too thin for structure determination of better than modest precision. In the re®nement, a disorder model of the perchlorate anion was used (two constraint components for four O atoms of the perchlorate anion have occu-pancy factors of 0.564 and 0.436, respectively); however, the O atoms still exhibit slightly larger displacement ellipsoids than usual.
Data collection:SMART(Bruker, 1998); cell re®nement:SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication:SHELXL97.
The authors gratefully acknowledge ®nancial support from Tianjin University.
References
Brandenburg, K. & Berndt, M. (1999).DIAMOND. Version 2.1c. Crystal Impact GbR, Bonn, Germany.
Bruker (1998).SMART,SAINTandSHELXTL(Version 5.1). Bruker AXS, Madison, Wisconsin, USA.
Cotton, F. A., Daniels, L. M., Jordan, G. T. IV & Murillo, C. A. (1997).J. Am. Chem. Soc.119, 10377±10381.
Cotton, F. A., Daniels, L. M., Murillo, C. A. & Wang, X. P. (1998).Chem. Commun.pp. 39±40.
Desiraju, G. R. & Steiner, T. (1999).The Weak Hydrogen Bond in Structural Chemistry and Biology.Oxford University Press.
Du, M. & Zhao, X. J. (2004a).Appl. Organomet. Chem.18, 93±94. Du, M. & Zhao, X. J. (2004b).Acta Cryst.C60, o54±o56. Du, M. & Zhao, X. J. (2004c).Acta Cryst.E60, o439±o441.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
Sheldrick, G. M. (2000).SADABS.University of GoÈttingen, Germany. Figure 1
supporting information
sup-1 Acta Cryst. (2004). E60, o645–o646
supporting information
Acta Cryst. (2004). E60, o645–o646 [https://doi.org/10.1107/S1600536804006300]
2-(2-Pyridylamino)pyridinium perchlorate displaying a one-dimensional
hydrogen-bonding supramolecular chain
Ya-Mei Guo, Zhi-Gang Geng and Xia Feng
(I)
Crystal data
C10H10N3+·ClO4− Mr = 271.66
Monoclinic, P21/c Hall symbol: -P_2ybc a = 8.527 (3) Å b = 16.174 (5) Å c = 8.753 (3) Å β = 100.878 (6)° V = 1185.5 (7) Å3 Z = 4
F(000) = 560 Dx = 1.522 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 925 reflections θ = 2.7–21.4°
µ = 0.33 mm−1 T = 293 K
Lamellar, colorless 0.24 × 0.20 × 0.08 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) Tmin = 0.866, Tmax = 0.970
4794 measured reflections 2033 independent reflections 1165 reflections with I > 2σ(I) Rint = 0.050
θmax = 25.0°, θmin = 2.4° h = −10→7
k = −14→19 l = −10→10
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.070 wR(F2) = 0.200 S = 1.02 2033 reflections 200 parameters 110 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.1137P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001
Special details
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)
x y z Uiso*/Ueq Occ. (<1)
N1 0.5632 (5) 0.4081 (2) 0.3345 (5) 0.0524 (11)
H1A 0.4741 0.4103 0.3668 0.063*
N2 0.5632 (5) 0.2676 (3) 0.3746 (5) 0.0619 (13)
H2A 0.6122 0.2219 0.3658 0.074*
N3 0.3454 (5) 0.3272 (3) 0.4496 (5) 0.0557 (12)
C1 0.6275 (7) 0.4786 (3) 0.2920 (6) 0.0597 (15)
H1 0.5759 0.5288 0.2987 0.072*
C2 0.7664 (7) 0.4766 (4) 0.2398 (6) 0.0657 (16)
H2 0.8109 0.5251 0.2098 0.079*
C3 0.8425 (7) 0.4010 (4) 0.2315 (7) 0.0660 (16)
H3 0.9389 0.3989 0.1964 0.079*
C4 0.7768 (7) 0.3307 (3) 0.2742 (6) 0.0590 (15)
H4 0.8271 0.2801 0.2675 0.071*
C5 0.6345 (6) 0.3342 (3) 0.3278 (6) 0.0448 (12)
C6 0.4247 (6) 0.2588 (3) 0.4348 (5) 0.0454 (12)
C7 0.3729 (6) 0.1816 (3) 0.4733 (6) 0.0535 (13)
H7 0.4309 0.1343 0.4601 0.064*
C8 0.2356 (7) 0.1765 (4) 0.5306 (7) 0.0672 (16)
H8 0.1985 0.1255 0.5577 0.081*
C9 0.1528 (7) 0.2472 (4) 0.5480 (7) 0.0693 (16)
H9 0.0590 0.2450 0.5876 0.083*
C10 0.2103 (7) 0.3213 (3) 0.5062 (7) 0.0615 (15)
H10 0.1534 0.3693 0.5176 0.074*
Cl1 0.79976 (15) 0.07711 (8) 0.25313 (15) 0.0535 (5)
O1 0.8893 (15) 0.1341 (6) 0.1885 (15) 0.118 (4) 0.564 (14)
O2 0.7529 (13) 0.0069 (6) 0.1559 (12) 0.089 (3) 0.564 (14)
O3 0.9093 (11) 0.0423 (7) 0.3879 (9) 0.124 (5) 0.564 (14)
O4 0.6739 (10) 0.1110 (6) 0.3156 (16) 0.102 (4) 0.564 (14)
O1′ 0.9058 (18) 0.1027 (11) 0.1479 (18) 0.133 (7) 0.436 (14)
O2′ 0.7787 (19) −0.0073 (5) 0.244 (2) 0.116 (6) 0.436 (14)
O3′ 0.877 (2) 0.1081 (14) 0.4022 (15) 0.234 (11) 0.436 (14)
supporting information
sup-3 Acta Cryst. (2004). E60, o645–o646
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
N1 0.048 (2) 0.052 (3) 0.060 (3) −0.001 (2) 0.018 (2) 0.001 (2)
N2 0.059 (3) 0.046 (3) 0.084 (3) 0.008 (2) 0.024 (3) −0.002 (2)
N3 0.052 (3) 0.049 (3) 0.069 (3) 0.002 (2) 0.017 (2) 0.002 (2)
C1 0.064 (4) 0.043 (3) 0.074 (4) 0.000 (3) 0.018 (3) 0.005 (3)
C2 0.064 (4) 0.056 (4) 0.080 (4) −0.009 (3) 0.023 (3) 0.011 (3)
C3 0.059 (3) 0.069 (4) 0.078 (4) −0.001 (3) 0.033 (3) −0.001 (3)
C4 0.063 (4) 0.046 (3) 0.074 (4) 0.008 (3) 0.027 (3) 0.003 (3)
C5 0.047 (3) 0.038 (3) 0.050 (3) −0.002 (2) 0.011 (2) 0.003 (2)
C6 0.042 (3) 0.047 (3) 0.047 (3) −0.005 (2) 0.009 (2) −0.004 (2)
C7 0.054 (3) 0.045 (3) 0.063 (3) −0.001 (3) 0.015 (3) −0.004 (2)
C8 0.074 (4) 0.054 (4) 0.075 (4) −0.019 (3) 0.020 (3) 0.004 (3)
C9 0.052 (3) 0.082 (5) 0.078 (4) −0.008 (3) 0.022 (3) −0.001 (3)
C10 0.056 (3) 0.056 (4) 0.075 (4) −0.001 (3) 0.019 (3) −0.008 (3)
Cl1 0.0494 (8) 0.0499 (8) 0.0611 (8) −0.0010 (7) 0.0102 (6) −0.0037 (7)
O1 0.140 (8) 0.080 (6) 0.155 (9) −0.028 (6) 0.084 (7) −0.009 (6)
O2 0.110 (7) 0.067 (6) 0.089 (6) 0.002 (5) 0.020 (5) −0.023 (5)
O3 0.116 (7) 0.162 (9) 0.092 (6) 0.045 (6) 0.017 (6) 0.006 (6)
O4 0.081 (5) 0.090 (6) 0.144 (9) 0.023 (5) 0.046 (6) −0.023 (6)
O1′ 0.133 (10) 0.135 (11) 0.145 (10) −0.005 (8) 0.066 (8) 0.019 (8)
O2′ 0.124 (9) 0.070 (7) 0.152 (11) −0.006 (6) 0.018 (9) 0.014 (7)
O3′ 0.244 (14) 0.219 (14) 0.223 (14) 0.003 (10) 0.005 (10) −0.005 (10)
O4′ 0.072 (6) 0.058 (6) 0.093 (8) 0.016 (4) 0.009 (5) −0.007 (5)
Geometric parameters (Å, º)
N1—C5 1.347 (6) C6—C7 1.387 (7)
N1—C1 1.349 (6) C7—C8 1.361 (7)
N1—H1A 0.8600 C7—H7 0.9300
N2—C5 1.338 (6) C8—C9 1.367 (8)
N2—C6 1.388 (6) C8—H8 0.9300
N2—H2A 0.8600 C9—C10 1.371 (7)
N3—C6 1.316 (6) C9—H9 0.9300
N3—C10 1.341 (6) C10—H10 0.9300
C1—C2 1.348 (8) Cl1—O2′ 1.377 (9)
C1—H1 0.9300 Cl1—O1 1.384 (7)
C2—C3 1.393 (8) Cl1—O4 1.405 (6)
C2—H2 0.9300 Cl1—O2 1.430 (7)
C3—C4 1.352 (7) Cl1—O3′ 1.436 (10)
C3—H3 0.9300 Cl1—O4′ 1.444 (8)
C4—C5 1.383 (6) Cl1—O1′ 1.467 (9)
C4—H4 0.9300 Cl1—O3 1.471 (7)
C5—N1—C1 121.9 (4) C8—C9—C10 118.9 (5)
C5—N1—H1A 119.1 C8—C9—H9 120.5
C5—N2—C6 131.8 (4) N3—C10—C9 122.4 (5)
C5—N2—H2A 114.1 N3—C10—H10 118.8
C6—N2—H2A 114.1 C9—C10—H10 118.8
C6—N3—C10 118.1 (4) O2′—Cl1—O1 135.4 (8)
C2—C1—N1 120.1 (5) O2′—Cl1—O4 108.0 (8)
C2—C1—H1 119.9 O1—Cl1—O4 114.8 (6)
N1—C1—H1 119.9 O1—Cl1—O2 113.5 (6)
C1—C2—C3 119.2 (5) O4—Cl1—O2 113.2 (5)
C1—C2—H2 120.4 O2′—Cl1—O3′ 115.5 (8)
C3—C2—H2 120.4 O1—Cl1—O3′ 86.9 (10)
C4—C3—C2 120.2 (5) O4—Cl1—O3′ 76.2 (9)
C4—C3—H3 119.9 O2—Cl1—O3′ 147.9 (9)
C2—C3—H3 119.9 O2′—Cl1—O4′ 114.4 (7)
C3—C4—C5 119.7 (5) O1—Cl1—O4′ 90.7 (7)
C3—C4—H4 120.2 O2—Cl1—O4′ 95.8 (6)
C5—C4—H4 120.2 O3′—Cl1—O4′ 109.1 (8)
N2—C5—N1 117.7 (4) O2′—Cl1—O1′ 109.4 (8)
N2—C5—C4 123.3 (4) O4—Cl1—O1′ 137.8 (8)
N1—C5—C4 118.9 (4) O2—Cl1—O1′ 89.2 (8)
N3—C6—C7 122.7 (5) O3′—Cl1—O1′ 104.0 (9)
N3—C6—N2 116.2 (4) O4′—Cl1—O1′ 103.3 (7)
C7—C6—N2 121.1 (5) O2′—Cl1—O3 73.9 (7)
C8—C7—C6 118.7 (5) O1—Cl1—O3 105.5 (7)
C8—C7—H7 120.7 O4—Cl1—O3 104.7 (6)
C6—C7—H7 120.7 O2—Cl1—O3 103.7 (5)
C7—C8—C9 119.2 (5) O3′—Cl1—O3 45.0 (8)
C7—C8—H8 120.4 O4′—Cl1—O3 146.6 (6)
C9—C8—H8 120.4 O1′—Cl1—O3 103.8 (8)
C5—N1—C1—C2 0.5 (8) C10—N3—C6—C7 0.9 (7)
N1—C1—C2—C3 −0.4 (8) C10—N3—C6—N2 179.5 (4)
C1—C2—C3—C4 0.5 (9) C5—N2—C6—N3 0.3 (8)
C2—C3—C4—C5 −0.7 (8) C5—N2—C6—C7 179.0 (5)
C6—N2—C5—N1 −1.5 (8) N3—C6—C7—C8 −0.9 (8)
C6—N2—C5—C4 178.2 (5) N2—C6—C7—C8 −179.5 (5)
C1—N1—C5—N2 179.0 (4) C6—C7—C8—C9 0.2 (8)
C1—N1—C5—C4 −0.7 (7) C7—C8—C9—C10 0.4 (9)
C3—C4—C5—N2 −178.9 (5) C6—N3—C10—C9 −0.2 (8)
C3—C4—C5—N1 0.8 (7) C8—C9—C10—N3 −0.4 (9)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N1—H1A···N3 0.86 1.96 2.623 (6) 133
N1—H1A···O2i 0.86 2.47 3.149 (5) 137
N2—H2A···O4 0.86 1.94 2.785 (6) 166
