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Acta Cryst. (2009). E65, o2175    [ doi:10.1107/S1600536809032024 ]

2-[2-(2-Pyridyl)ethyl]isoindolinium perchlorate

R. J. Butcher, Y. T. Tesema, T. B. Yisgedu and Y. Gultneh

Abstract top

In the title salt, C15H17N2+·ClO4-, the isoindoline N atom is protonated and an intramolecular N-H...N hydrogen bond occurs. In the crystal, N-H...O and numerous weak C-H...O interactions occur between the cation and anion. The O atoms of the perchlorate anion are disordered over four sets of sites with occupancies of 0.438 (4), 0.270 (9), 0.155 (8) and 0.138 (5).

Comment top

The stucture of the title compound, (I), is shown below. Dimensions are available in the archived CIF.

The crystal structure shows that the N atom of 2,3-dihydro-1H-isoindoline is protonated and involved in hydrogen bonding to the nearest pyridyl N atom (Table 1). The perchlorate ion O atoms are also involved in the hydrogen bonding with the isoindoline H atom. The amine H atom is also involved in hydrogen bonding to the perchlorate O atoms and there are extensive but weak interionic C—H···O interactions between the cation and anion (Table 1).

Related literature top

For further information on the synthesis, see: Bonnett et al. (1983); Meyers & Santiago (1995).

Experimental top

The neutral ligand 2-(2-pyridylethyl)-2,3-dihydro-1H-isoindole, was synthesized by reacting 2-(2-aminoethyl)pyridine and α,α'-dibromo-o-xylene in THF in the presence of triethylamine as a base and purified by column chromatography using modified literature methods of Bonnett et al. (1983) & Meyers et al. (1995). The perchlorate salt of the protonated ligand (1) was formed by addition of one equivalent of an aqueous solution of HClO4 to a solution of the neutral ligand in methanol and allowing the resulting solution to stand yielded pale pink needles of (I).

Refinement top

The perchlorate anion is disordered over four conformations with occupancy factors of 0.438 (4), 0.270 (9), 0.155 (8), and 0.138 (5). These were constrained to adopt a tetrahedral geometry. This disorder and its modelling resulted in 245 restraints. The H atoms were idealized with an N—H distance of 0.91Å and C—H distances were idealized at 0.93 (aromatic C—H), 0.96 (CH3), and 0.97 (CH2) Å and Uiso(H) = 1.2Ueq(C) (1.5Ueq(C) for the CH3 protons). Since a unique data set was collected there were no Friedel pairs and no attempt was made to establish the absolute sturcture.

Computing details top

Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS (Bruker, 1997); 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
[Figure 1] Fig. 1. The title compound showing the N—H···N bond (dashed bonds). Ellipsoids are drawn at the 20% probabilty level.
[Figure 2] Fig. 2. The packing arrangement viewed down the a axis showing the N—H···O and intermolecular C—H···O interactions (dashed bonds).
2-[2-(2-Pyridyl)ethyl]isoindolinium perchlorate top
Crystal data top
C15H17N2+·ClO4−F(000) = 680
Mr = 324.76Dx = 1.403 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 39 reflections
a = 7.7941 (9) Åθ = 5.1–12.5°
b = 11.7032 (19) ŵ = 0.27 mm−1
c = 16.850 (3) ÅT = 293 K
V = 1537.0 (4) Å3Needle, pale pink
Z = 40.5 × 0.2 × 0.08 mm
Data collection top
Bruker P4
diffractometer		1660 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
graphiteθmax = 27.5°, θmin = 2.4°
ω scansh = 0→10
Absorption correction: ψ scan
(North et al., 1968)		k = 0→15
Tmin = 0.241, Tmax = 0.265l = 0→21
2027 measured reflections3 standard reflections every 97 reflections
2001 independent reflections intensity decay: <2
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0626P)2 + 0.2989P]
where P = (Fo2 + 2Fc2)/3
2001 reflections(Δ/σ)max = 0.005
329 parametersΔρmax = 0.21 e Å−3
245 restraintsΔρmin = −0.15 e Å−3
Crystal data top
C15H17N2+·ClO4−V = 1537.0 (4) Å3
Mr = 324.76Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.7941 (9) ŵ = 0.27 mm−1
b = 11.7032 (19) ÅT = 293 K
c = 16.850 (3) Å0.5 × 0.2 × 0.08 mm
Data collection top
Bruker P4
diffractometer		1660 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.025
Tmin = 0.241, Tmax = 0.265θmax = 27.5°
2027 measured reflections3 standard reflections every 97 reflections
2001 independent reflections intensity decay: <2
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.120Δρmax = 0.21 e Å−3
S = 1.03Δρmin = −0.15 e Å−3
2001 reflectionsAbsolute structure: ?
329 parametersFlack parameter: ?
245 restraintsRogers parameter: ?
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
xyzUiso*/UeqOcc. (<1)
Cl−0.45920 (11)0.96522 (8)0.73473 (5)0.0643 (3)
O1−0.4598 (13)1.0879 (4)0.7432 (7)0.093 (3)0.438 (4)
O2−0.5971 (10)0.9347 (9)0.6824 (5)0.101 (3)0.438 (4)
O3−0.4861 (13)0.9137 (8)0.8101 (3)0.074 (2)0.438 (4)
O4−0.3007 (9)0.9305 (9)0.7017 (6)0.105 (3)0.438 (4)
O1A−0.497 (3)0.8798 (16)0.6772 (10)0.099 (5)0.155 (8)
O2A−0.2811 (10)0.9589 (19)0.7554 (14)0.100 (6)0.155 (8)
O3A−0.494 (3)1.0759 (10)0.7025 (15)0.103 (5)0.155 (8)
O4A−0.561 (3)0.948 (2)0.8038 (8)0.104 (5)0.155 (8)
O1B−0.466 (3)0.9618 (18)0.8191 (3)0.100 (6)0.138 (5)
O2B−0.404 (3)0.8561 (9)0.7054 (11)0.099 (5)0.138 (5)
O3B−0.341 (2)1.0506 (14)0.7094 (12)0.100 (4)0.138 (5)
O4B−0.6256 (14)0.9896 (18)0.7036 (13)0.104 (5)0.138 (5)
O1C−0.2804 (8)0.9697 (14)0.7176 (9)0.088 (4)0.270 (9)
O2C−0.5525 (18)0.9411 (15)0.6637 (6)0.111 (5)0.270 (9)
O3C−0.492 (2)0.8776 (12)0.7918 (8)0.096 (4)0.270 (9)
O4C−0.5146 (19)1.0728 (8)0.7659 (10)0.111 (4)0.270 (9)
N1−0.0054 (4)0.8416 (2)0.61178 (17)0.0633 (7)
N2−0.0414 (3)0.7346 (2)0.75736 (15)0.0546 (6)
H2B−0.08050.79360.72720.065 (10)*
C1−0.0438 (5)0.9290 (3)0.5639 (2)0.0716 (9)
H1A−0.08600.99610.58610.084 (13)*
C2−0.0232 (5)0.9233 (4)0.4823 (2)0.0762 (10)
H2A−0.04680.98650.45070.114 (16)*
C30.0328 (5)0.8230 (4)0.4489 (2)0.0798 (11)
H3A0.04600.81670.39430.077 (11)*
C40.0691 (5)0.7319 (4)0.4976 (2)0.0702 (9)
H4A0.10590.66290.47620.086 (13)*
C50.0502 (5)0.7442 (3)0.57909 (19)0.0609 (8)
C60.0970 (5)0.6493 (3)0.6367 (2)0.0677 (9)
H6A0.20890.66580.65910.083 (13)*
H6B0.10620.57820.60740.073 (11)*
C7−0.0297 (5)0.6324 (3)0.7044 (2)0.0652 (8)
H7A−0.14220.61630.68250.069 (10)*
H7B0.00530.56680.73560.080 (11)*
C8−0.1673 (4)0.7187 (3)0.8247 (2)0.0626 (8)
H8A−0.28130.74390.80980.105 (15)*
H8B−0.17240.63950.84140.086 (12)*
C9−0.0935 (4)0.7931 (3)0.88894 (19)0.0552 (7)
C10−0.1673 (5)0.8278 (3)0.9602 (2)0.0690 (9)
H10A−0.27940.80760.97290.095 (14)*
C11−0.0696 (6)0.8932 (3)1.0117 (2)0.0743 (11)
H11A−0.11620.91561.06000.069 (10)*
C120.0928 (6)0.9252 (3)0.9930 (2)0.0721 (10)
H12A0.15470.97041.02820.112 (16)*
C130.1681 (5)0.8917 (3)0.9219 (2)0.0654 (8)
H13A0.27870.91460.90880.124 (19)*
C140.0738 (4)0.8232 (3)0.87123 (18)0.0546 (7)
C150.1273 (4)0.7717 (3)0.79305 (19)0.0612 (8)
H15A0.20320.70700.80090.064 (10)*
H15B0.18410.82770.75970.079 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0620 (5)0.0772 (5)0.0537 (4)−0.0053 (5)0.0037 (4)−0.0008 (4)
O10.083 (6)0.077 (4)0.121 (7)−0.012 (4)−0.002 (6)−0.003 (4)
O20.094 (6)0.146 (8)0.062 (4)−0.043 (5)−0.005 (4)−0.008 (5)
O30.082 (5)0.093 (6)0.047 (3)0.015 (5)0.017 (3)−0.004 (3)
O40.094 (5)0.110 (7)0.112 (6)0.028 (5)0.040 (5)0.003 (6)
O1A0.099 (10)0.117 (10)0.082 (8)−0.002 (9)−0.010 (8)−0.028 (8)
O2A0.084 (9)0.092 (10)0.126 (12)−0.007 (9)0.028 (10)0.011 (11)
O3A0.085 (9)0.111 (9)0.112 (11)0.031 (8)−0.016 (9)0.023 (9)
O4A0.096 (10)0.133 (11)0.085 (9)−0.003 (10)0.044 (8)−0.022 (9)
O1B0.100 (10)0.121 (12)0.079 (9)0.001 (11)0.015 (9)−0.017 (9)
O2B0.099 (10)0.102 (9)0.096 (9)0.012 (9)0.006 (9)−0.013 (8)
O3B0.087 (8)0.095 (8)0.120 (9)−0.014 (8)0.021 (8)0.002 (8)
O4B0.081 (9)0.128 (10)0.101 (10)0.022 (9)−0.013 (9)0.000 (9)
O1C0.078 (6)0.079 (7)0.107 (9)−0.010 (5)0.056 (6)−0.025 (7)
O2C0.123 (10)0.150 (9)0.059 (6)−0.021 (9)−0.013 (7)−0.010 (7)
O3C0.082 (7)0.107 (9)0.099 (8)0.007 (7)0.015 (7)0.016 (7)
O4C0.096 (8)0.117 (7)0.120 (8)0.039 (6)0.008 (7)−0.025 (7)
N10.0600 (17)0.0669 (17)0.0630 (15)0.0055 (13)−0.0045 (14)−0.0003 (13)
N20.0552 (14)0.0559 (13)0.0526 (13)0.0009 (12)−0.0042 (13)0.0014 (11)
C10.066 (2)0.069 (2)0.080 (2)−0.0005 (19)−0.004 (2)0.0048 (18)
C20.060 (2)0.091 (3)0.078 (2)−0.004 (2)0.0013 (19)0.026 (2)
C30.0581 (19)0.122 (3)0.0588 (19)0.006 (2)0.0058 (18)0.010 (2)
C40.061 (2)0.090 (2)0.0599 (18)0.0087 (19)−0.0008 (17)−0.0076 (18)
C50.0543 (17)0.0722 (19)0.0561 (16)0.0054 (17)−0.0032 (16)−0.0035 (15)
C60.075 (2)0.070 (2)0.0584 (18)0.0152 (18)−0.0067 (18)−0.0095 (16)
C70.076 (2)0.0574 (17)0.0620 (17)0.0011 (17)−0.0066 (19)−0.0045 (14)
C80.0541 (18)0.0631 (19)0.071 (2)−0.0068 (16)0.0066 (16)0.0027 (16)
C90.0571 (18)0.0510 (15)0.0576 (17)0.0052 (14)0.0056 (14)0.0081 (14)
C100.070 (2)0.065 (2)0.072 (2)0.0034 (18)0.0226 (19)0.0092 (17)
C110.093 (3)0.075 (2)0.0546 (18)0.013 (2)0.015 (2)−0.0035 (17)
C120.081 (3)0.078 (2)0.0577 (18)0.0099 (19)−0.0069 (19)−0.0030 (18)
C130.0591 (19)0.076 (2)0.0605 (18)0.0006 (18)−0.0069 (16)−0.0013 (17)
C140.0525 (17)0.0614 (17)0.0499 (15)0.0047 (14)0.0009 (13)0.0068 (13)
C150.0502 (16)0.078 (2)0.0550 (16)−0.0031 (17)0.0003 (14)−0.0035 (16)
Geometric parameters (Å, °) top
Cl—O41.415 (4)C4—C51.389 (5)
Cl—O31.421 (4)C4—H4A0.9300
Cl—O4A1.423 (5)C5—C61.520 (5)
Cl—O1B1.424 (5)C6—C71.521 (5)
Cl—O1A1.424 (5)C6—H6A0.9700
Cl—O1C1.424 (5)C6—H6B0.9700
Cl—O3B1.424 (5)C7—H7A0.9700
Cl—O4B1.427 (5)C7—H7B0.9700
Cl—O3C1.428 (5)C8—C91.503 (5)
Cl—O2C1.429 (5)C8—H8A0.9700
Cl—O3A1.429 (5)C8—H8B0.9700
Cl—O4C1.431 (5)C9—C141.383 (5)
N1—C11.337 (4)C9—C101.392 (4)
N1—C51.338 (4)C10—C111.385 (5)
N2—C71.495 (4)C10—H10A0.9300
N2—C151.510 (4)C11—C121.357 (6)
N2—C81.512 (4)C11—H11A0.9300
N2—H2B0.9100C12—C131.390 (5)
C1—C21.385 (6)C12—H12A0.9300
C1—H1A0.9300C13—C141.382 (5)
C2—C31.374 (6)C13—H13A0.9300
C2—H2A0.9300C14—C151.508 (4)
C3—C41.373 (6)C15—H15A0.9700
C3—H3A0.9300C15—H15B0.9700
O4—Cl—O3111.0 (4)C7—C6—H6B108.6
O4A—Cl—O1A110.1 (5)H6A—C6—H6B107.6
O1B—Cl—O3B110.0 (5)N2—C7—C6112.5 (3)
O1B—Cl—O4B109.8 (5)N2—C7—H7A109.1
O3B—Cl—O4B109.7 (5)C6—C7—H7A109.1
O1C—Cl—O3C109.7 (4)N2—C7—H7B109.1
O1C—Cl—O2C109.6 (4)C6—C7—H7B109.1
O3C—Cl—O2C109.3 (4)H7A—C7—H7B107.8
O4A—Cl—O3A109.5 (4)C9—C8—N2102.8 (2)
O1A—Cl—O3A109.8 (4)C9—C8—H8A111.2
O1C—Cl—O4C109.7 (4)N2—C8—H8A111.2
O3C—Cl—O4C109.4 (4)C9—C8—H8B111.2
O2C—Cl—O4C109.1 (4)N2—C8—H8B111.2
C1—N1—C5118.4 (3)H8A—C8—H8B109.1
C7—N2—C15114.5 (3)C14—C9—C10120.1 (3)
C7—N2—C8112.9 (2)C14—C9—C8110.7 (3)
C15—N2—C8107.5 (2)C10—C9—C8129.2 (3)
C7—N2—H2B107.2C11—C10—C9118.3 (4)
C15—N2—H2B107.2C11—C10—H10A120.9
C8—N2—H2B107.2C9—C10—H10A120.9
N1—C1—C2122.4 (4)C12—C11—C10121.3 (4)
N1—C1—H1A118.8C12—C11—H11A119.3
C2—C1—H1A118.8C10—C11—H11A119.3
C3—C2—C1119.0 (4)C11—C12—C13121.0 (4)
C3—C2—H2A120.5C11—C12—H12A119.5
C1—C2—H2A120.5C13—C12—H12A119.5
C4—C3—C2119.0 (4)C14—C13—C12118.1 (4)
C4—C3—H3A120.5C14—C13—H13A120.9
C2—C3—H3A120.5C12—C13—H13A120.9
C3—C4—C5119.2 (4)C13—C14—C9121.0 (3)
C3—C4—H4A120.4C13—C14—C15128.6 (3)
C5—C4—H4A120.4C9—C14—C15110.3 (3)
N1—C5—C4122.0 (3)C14—C15—N2102.8 (3)
N1—C5—C6115.9 (3)C14—C15—H15A111.2
C4—C5—C6122.1 (3)N2—C15—H15A111.2
C5—C6—C7114.7 (3)C14—C15—H15B111.2
C5—C6—H6A108.6N2—C15—H15B111.2
C7—C6—H6A108.6H15A—C15—H15B109.1
C5—C6—H6B108.6
C5—N1—C1—C2−2.1 (6)N2—C8—C9—C10168.3 (3)
N1—C1—C2—C32.5 (6)C14—C9—C10—C110.5 (5)
C1—C2—C3—C4−1.0 (6)C8—C9—C10—C11177.3 (3)
C2—C3—C4—C5−0.8 (6)C9—C10—C11—C121.4 (6)
C1—N1—C5—C40.2 (6)C10—C11—C12—C13−1.2 (6)
C1—N1—C5—C6178.2 (3)C11—C12—C13—C14−0.9 (5)
C3—C4—C5—N11.2 (6)C12—C13—C14—C92.8 (5)
C3—C4—C5—C6−176.7 (4)C12—C13—C14—C15−177.3 (3)
N1—C5—C6—C743.7 (5)C10—C9—C14—C13−2.6 (5)
C4—C5—C6—C7−138.3 (4)C8—C9—C14—C13−180.0 (3)
C15—N2—C7—C6−56.6 (4)C10—C9—C14—C15177.5 (3)
C8—N2—C7—C6179.9 (3)C8—C9—C14—C150.1 (4)
C5—C6—C7—N2−63.2 (4)C13—C14—C15—N2−165.4 (3)
C7—N2—C8—C9150.7 (3)C9—C14—C15—N214.4 (4)
C15—N2—C8—C923.4 (3)C7—N2—C15—C14−149.7 (3)
N2—C8—C9—C14−14.6 (3)C8—N2—C15—C14−23.4 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N10.912.112.769 (4)129
N2—H2B···O40.912.393.197 (9)148
N2—H2B···O2A0.912.533.222 (19)133
N2—H2B···O1C0.912.593.390 (16)147
C2—H2A···O1Bi0.932.303.062 (11)139
C3—H3A···O1Aii0.932.623.193 (10)121
C7—H7B···O2Aiii0.972.503.232 (16)132
C8—H8A···O30.972.553.383 (10)144
C8—H8A···O2B0.972.393.168 (19)136
C8—H8A···O3C0.972.293.189 (17)154
C8—H8B···O4Biv0.972.483.167 (17)128
C11—H11A···O3Av0.932.553.27 (2)135
C11—H11A···O3Bv0.932.573.47 (2)162
C13—H13A···O3vi0.932.483.299 (9)148
C13—H13A···O4Avi0.932.202.976 (8)140
C13—H13A···O1Bvi0.932.563.44 (2)158
C13—H13A···O3Cvi0.932.703.444 (17)138
C15—H15A···O1iii0.972.553.423 (9)150
C15—H15B···O2vi0.972.483.425 (10)163
C15—H15B···O4Avi0.972.553.194 (19)124
Symmetry codes: (i) −x−1/2, −y+2, z−1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) −x, y−1/2, −z+3/2; (iv) −x−1, y−1/2, −z+3/2; (v) −x−1/2, −y+2, z+1/2; (vi) x+1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N10.912.112.769 (4)129
N2—H2B···O40.912.393.197 (9)148
N2—H2B···O2A0.912.533.222 (19)133
N2—H2B···O1C0.912.593.390 (16)147
C2—H2A···O1Bi0.932.303.062 (11)139
C3—H3A···O1Aii0.932.623.193 (10)121
C7—H7B···O2Aiii0.972.503.232 (16)132
C8—H8A···O30.972.553.383 (10)144
C8—H8A···O2B0.972.393.168 (19)136
C8—H8A···O3C0.972.293.189 (17)154
C8—H8B···O4Biv0.972.483.167 (17)128
C11—H11A···O3Av0.932.553.27 (2)135
C11—H11A···O3Bv0.932.573.47 (2)162
C13—H13A···O3vi0.932.483.299 (9)148
C13—H13A···O4Avi0.932.202.976 (8)140
C13—H13A···O1Bvi0.932.563.44 (2)158
C13—H13A···O3Cvi0.932.703.444 (17)138
C15—H15A···O1iii0.972.553.423 (9)150
C15—H15B···O2vi0.972.483.425 (10)163
C15—H15B···O4Avi0.972.553.194 (19)124
Symmetry codes: (i) −x−1/2, −y+2, z−1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) −x, y−1/2, −z+3/2; (iv) −x−1, y−1/2, −z+3/2; (v) −x−1/2, −y+2, z+1/2; (vi) x+1, y, z.
Acknowledgements top

RJB wishes to acknowledge the Laboratory for the Structure of Matter at the Naval Research Laboratory for access to their diffractometers.

references
References top

Bonnett, R., North, S. A., Newton, R. F. & Scopes, D. I. C. (1983). Tetrahedron, 39, 1401–1405.

Bruker (1997). XSCANS. Bruker AXS Inc., Madison, Wisconsin, USA.

Meyers, A. I. & Santiago, B. (1995). Tetrahedron Lett. 36, 5877–5880.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.