PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o423.
Published online 2009 January 31. doi:  10.1107/S1600536809003353
PMCID: PMC2968340

4-(4-Pyridylamino)pyridinium perchlorate

Abstract

In the title salt, C10H10N3 +·ClO4 , the 4-(4-pyridylamino)­pyridinium cations are linked into chains via N—H(...)N hydrogen bonding and into layers by C—H(...)π inter­actions [C(...)Cg = 3.3875 (19) Å]. Perchlorate ions are anchored to the layer motifs by N—H(...)O hydrogen bonding. The perchlorate anion was found to be disordered about a Cl—O axis, with two sites, each of equal occupancy, being resolved for the three remaining O atoms.

Related literature

For divalent metal adipate coordination polymers incorporating 4,4′-dipyridylamine as a ligand, see: Montney et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o423-scheme1.jpg

Experimental

Crystal data

  • C10H10N3 +·ClO4
  • M r = 271.66
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o423-efi1.jpg
  • a = 7.6254 (10) Å
  • b = 15.991 (2) Å
  • c = 9.8358 (13) Å
  • β = 101.913 (1)°
  • V = 1173.5 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.34 mm−1
  • T = 173 (2) K
  • 0.36 × 0.24 × 0.18 mm

Data collection

  • Bruker SMART 1K diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2007 [triangle]) T min = 0.907, T max = 0.941
  • 12615 measured reflections
  • 2728 independent reflections
  • 2165 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.096
  • S = 1.03
  • 2728 reflections
  • 196 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: SMART (Bruker, 2006 [triangle]); cell refinement: SAINT (Bruker, 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: CrystalMaker (Palmer, 2007 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003353/tk2362sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003353/tk2362Isup2.hkl

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

Acknowledgments

The authors gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work.

supplementary crystallographic information

Comment

The dipodal tethering ligand 4,4'-dipyridylamine (dpa) has proven beneficial for the construction of divalent metal adipate coordination polymers with novel topologies (Montney et al., 2007). In an attempt to probe the effect of alkyl group substitution on coordination polymer structure by using methyladipate, colourless crystals of the title salt (I) were obtained.

The asymmetric unit of (I) comprises a Hdpa+ cation and a perchlorate ion, with three of its O atoms disordered equally over two positions (Fig. 1). The Hdpa+ cations aggregate into supramolecular chains, aligned along [201] by means of N—H···N hydrogen bonding interactions between protonated and unprotonated pyridyl rings, Table 1. These chains are organized into layers (Fig. 2), oriented parallel to the ac-plane, and connected by C—H···π interactions between pyridyl rings in neighbouring Hdpa+ cations [C1—H1···Cg(N2,C6–C10)i = 2.82 Å, C1···Cgi = 3.3875 (19) Å with angle at H1 = 119° for i = -1+x, y, z]. Supramolecular interactions are optimized by the 33.77 (8)° torsion angle between the pyridyl rings. Perchlorate anions are anchored to the layer motifs by N—H···O hydrogen bonding; the layers stack along the b-direction (Fig. 3)

Experimental

All chemicals were obtained commercially. Cadmium perchlorate hydrate (20 mg, 0.064 mmol) and methyladipic acid (10 mg, 0.064 mmol) were dissolved in water (1.5 ml) in a glass vial. A 0.75 ml aliquot of a 1:1 water:ethanol mixture was carefully layered onto the aqueous solution, followed by an ethanolic solution (1.5 ml) of 4,4'-dipyridylamine (22 mg, 0.12 mmol). Colourless blocks of the title salt formed after 2 weeks.

Refinement

All H atoms bound to C atoms were placed in calculated positions, with C—H = 0.95 Å and refined in riding mode with Uiso = 1.2Ueq(C). The H atoms bound to N atoms were found via a Fourier difference map, restrained with N—H = 0.85 (2) Å, and refined with Uiso = 1.2Ueq(N). The perchlorate was disordered about a Cl—O axis with two sites, each of equal occupancy, being resolved for the three remaining O atoms. All atoms of the disordered model were refined anisotropcially.

Figures

Fig. 1.
The asymmetric unit of (I), showing 50% probability ellipsoids and atom numbering scheme. H atom positions are shown as grey sticks. Only one of the disordered set of perchlorate positions is shown. Colour code: green Cl, light blue N, red O, black C. ...
Fig. 2.
A layer of [C10H10N3]+ cations in (I). The N—H···N interactions are depicted as dashed lines.
Fig. 3.
Stacking diagram for (I), viewed slightly offset from the b-direction.

Crystal data

C10H10N3+·ClO4F(000) = 560
Mr = 271.66Dx = 1.538 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 12615 reflections
a = 7.6254 (10) Åθ = 2.5–28.3°
b = 15.991 (2) ŵ = 0.34 mm1
c = 9.8358 (13) ÅT = 173 K
β = 101.913 (1)°Block, colourless
V = 1173.5 (3) Å30.36 × 0.24 × 0.18 mm
Z = 4

Data collection

Bruker SMART 1K diffractometer2728 independent reflections
Radiation source: fine-focus sealed tube2165 reflections with I > 2σ(I)
graphiteRint = 0.039
ω scansθmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)h = −9→9
Tmin = 0.907, Tmax = 0.941k = −20→20
12615 measured reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0377P)2 + 0.7438P] where P = (Fo2 + 2Fc2)/3
2728 reflections(Δ/σ)max < 0.001
196 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = −0.32 e Å3

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)

xyzUiso*/UeqOcc. (<1)
Cl10.21340 (6)0.43473 (3)0.70621 (5)0.03353 (14)
O20.2109 (9)0.5174 (3)0.6429 (5)0.0405 (12)0.50
O30.3562 (15)0.4011 (7)0.6502 (10)0.057 (2)0.50
O40.2567 (7)0.4511 (3)0.8496 (4)0.0676 (13)0.50
O2A0.2135 (9)0.4032 (7)0.8406 (6)0.169 (4)0.50
O3A0.2109 (10)0.5200 (5)0.6966 (10)0.124 (4)0.50
O4A0.3645 (17)0.3918 (7)0.6858 (13)0.095 (4)0.50
O10.0503 (2)0.39806 (10)0.6382 (2)0.0597 (5)
N10.0749 (2)0.35317 (10)0.28489 (16)0.0309 (3)
H1N−0.011 (3)0.3422 (13)0.325 (2)0.037*
N20.52241 (19)0.38493 (9)0.11764 (16)0.0280 (3)
H2N0.579 (3)0.4301 (13)0.141 (2)0.034*
N30.8017 (2)0.22960 (10)−0.10972 (16)0.0318 (3)
C10.1057 (2)0.29873 (11)0.18885 (19)0.0309 (4)
H10.02530.25340.16280.037*
C20.2499 (2)0.30704 (11)0.12757 (19)0.0287 (4)
H20.26790.26870.05790.034*
C30.3713 (2)0.37270 (10)0.16845 (17)0.0245 (3)
C40.3305 (2)0.43069 (11)0.26600 (18)0.0290 (4)
H40.40600.47770.29260.035*
C50.1831 (2)0.41920 (12)0.32180 (19)0.0321 (4)
H50.15650.45830.38750.039*
C60.6948 (2)0.19706 (12)−0.03119 (19)0.0296 (4)
H60.68560.1379−0.02750.036*
C70.7192 (2)0.36562 (11)−0.04063 (19)0.0303 (4)
H70.73120.4246−0.04610.036*
C80.6077 (2)0.33074 (10)0.04003 (17)0.0247 (3)
C90.5971 (2)0.24396 (11)0.04488 (18)0.0272 (4)
H90.52400.21750.09950.033*
C100.8118 (2)0.31334 (12)−0.11227 (19)0.0335 (4)
H100.88730.3381−0.16670.040*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0299 (2)0.0328 (2)0.0376 (3)0.00006 (18)0.00622 (17)−0.00398 (18)
O20.049 (2)0.022 (2)0.055 (2)−0.0091 (17)0.0214 (18)0.0102 (17)
O30.044 (4)0.071 (5)0.065 (3)0.011 (3)0.034 (3)−0.009 (2)
O40.107 (4)0.063 (3)0.0306 (18)−0.023 (2)0.010 (2)−0.0062 (17)
O2A0.115 (5)0.327 (12)0.050 (3)−0.121 (7)−0.018 (3)0.064 (5)
O3A0.037 (3)0.037 (3)0.279 (11)0.005 (2)−0.006 (5)−0.067 (5)
O4A0.047 (4)0.045 (3)0.183 (11)0.022 (3)−0.002 (5)−0.033 (6)
O10.0370 (8)0.0382 (8)0.0990 (14)−0.0130 (7)0.0028 (8)−0.0019 (9)
N10.0262 (7)0.0354 (8)0.0359 (8)0.0032 (6)0.0175 (6)0.0061 (7)
N20.0236 (7)0.0258 (7)0.0379 (8)−0.0042 (6)0.0140 (6)−0.0066 (6)
N30.0298 (8)0.0373 (9)0.0313 (8)0.0015 (6)0.0133 (6)−0.0035 (6)
C10.0249 (8)0.0270 (9)0.0427 (10)0.0002 (7)0.0112 (8)0.0035 (8)
C20.0255 (8)0.0281 (9)0.0350 (9)0.0008 (7)0.0115 (7)−0.0041 (7)
C30.0222 (8)0.0256 (8)0.0271 (8)0.0029 (6)0.0084 (6)0.0030 (7)
C40.0269 (8)0.0273 (9)0.0339 (9)0.0007 (7)0.0091 (7)−0.0042 (7)
C50.0304 (9)0.0366 (10)0.0316 (9)0.0079 (8)0.0114 (7)−0.0014 (8)
C60.0256 (8)0.0289 (9)0.0357 (9)−0.0009 (7)0.0095 (7)−0.0036 (7)
C70.0286 (9)0.0290 (9)0.0360 (9)−0.0008 (7)0.0129 (7)0.0030 (7)
C80.0199 (7)0.0298 (9)0.0252 (8)0.0001 (6)0.0067 (6)−0.0025 (7)
C90.0227 (8)0.0293 (9)0.0323 (9)−0.0021 (7)0.0118 (7)0.0007 (7)
C100.0311 (9)0.0410 (11)0.0331 (9)−0.0016 (8)0.0175 (8)0.0015 (8)

Geometric parameters (Å, °)

Cl1—O3A1.366 (7)C1—H10.9500
Cl1—O4A1.391 (11)C2—C31.402 (2)
Cl1—O41.405 (4)C2—H20.9500
Cl1—O11.4125 (15)C3—C41.414 (2)
Cl1—O2A1.414 (5)C4—C51.362 (2)
Cl1—O31.423 (8)C4—H40.9500
Cl1—O21.459 (5)C5—H50.9500
N1—C11.341 (2)C6—C91.381 (2)
N1—C51.343 (2)C6—H60.9500
N1—H1N0.85 (2)C7—C101.378 (2)
N2—C31.362 (2)C7—C81.394 (2)
N2—C81.400 (2)C7—H70.9500
N2—H2N0.85 (2)C8—C91.391 (2)
N3—C61.338 (2)C9—H90.9500
N3—C101.342 (2)C10—H100.9500
C1—C21.366 (2)
O3A—Cl1—O4A118.9 (6)N2—C3—C2124.10 (15)
O3A—Cl1—O1112.5 (3)N2—C3—C4118.42 (16)
O4A—Cl1—O1113.7 (5)C2—C3—C4117.46 (15)
O4—Cl1—O1123.6 (2)C5—C4—C3120.02 (17)
O3A—Cl1—O2A114.7 (6)C5—C4—H4120.0
O4A—Cl1—O2A96.8 (7)C3—C4—H4120.0
O1—Cl1—O2A97.2 (2)N1—C5—C4120.63 (17)
O4—Cl1—O3114.8 (5)N1—C5—H5119.7
O1—Cl1—O3109.2 (5)C4—C5—H5119.7
O4—Cl1—O2103.9 (3)N3—C6—C9124.21 (17)
O1—Cl1—O2103.9 (3)N3—C6—H6117.9
O3—Cl1—O296.9 (5)C9—C6—H6117.9
C1—N1—C5120.91 (15)C10—C7—C8119.04 (16)
C1—N1—H1N117.0 (14)C10—C7—H7120.5
C5—N1—H1N121.9 (14)C8—C7—H7120.5
C3—N2—C8129.38 (15)C9—C8—C7117.72 (15)
C3—N2—H2N116.3 (14)C9—C8—N2124.18 (15)
C8—N2—H2N114.1 (14)C7—C8—N2117.97 (15)
C6—N3—C10116.29 (15)C6—C9—C8118.78 (15)
N1—C1—C2121.48 (17)C6—C9—H9120.6
N1—C1—H1119.3C8—C9—H9120.6
C2—C1—H1119.3N3—C10—C7123.95 (16)
C1—C2—C3119.35 (16)N3—C10—H10118.0
C1—C2—H2120.3C7—C10—H10118.0
C3—C2—H2120.3
C5—N1—C1—C21.6 (3)C10—N3—C6—C90.1 (3)
N1—C1—C2—C31.7 (3)C10—C7—C8—C90.6 (3)
C8—N2—C3—C2−13.5 (3)C10—C7—C8—N2176.70 (16)
C8—N2—C3—C4168.15 (17)C3—N2—C8—C9−26.6 (3)
C1—C2—C3—N2177.63 (17)C3—N2—C8—C7157.57 (18)
C1—C2—C3—C4−4.0 (3)N3—C6—C9—C80.5 (3)
N2—C3—C4—C5−178.24 (16)C7—C8—C9—C6−0.8 (3)
C2—C3—C4—C53.3 (3)N2—C8—C9—C6−176.68 (16)
C1—N1—C5—C4−2.4 (3)C6—N3—C10—C7−0.4 (3)
C3—C4—C5—N1−0.2 (3)C8—C7—C10—N30.0 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···N3i0.85 (2)2.04 (2)2.839 (2)157 (2)
N2—H2N···O3Aii0.85 (2)2.17 (2)2.873 (8)140.2 (18)
N2—H2N···O4ii0.85 (2)2.27 (2)3.098 (5)166.1 (19)

Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2362).

References

  • Bruker (2006). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Montney, M. R., Mallika Krishnan, S., Supkowski, R. M. & LaDuca, R. L. (2007). Inorg. Chem.46, 7362–7370. [PubMed]
  • Palmer, D. (2007). CrystalMaker CrystalMaker Software, Bicester, Oxfordshire, England.
  • Sheldrick, G. M. (2007). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography