2-(2-Quinol­yl)quinolinium nitrate

In the cation of the title compound, C₁₈H₁₃N₂⁺·NO₃⁻, the two bicyclic ring systems form a dihedral angle of 3.84 (4)°. The nitrate anion is disordered over two orientations in a 0.9:0.1 ratio. In the crystal structure, the cations form stacks along the a axis, with short inter­molecular contacts [C...C = 3.330 (3) and 3.345 (4) Å], and link to the anions via N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in solvent or counterion
• R factor = 0.057
• wR factor = 0.137
• Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT432_ALERT_2_B Short Inter X...Y Contact  C11    ..  O1'     ..       2.80 Ang.

Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N3
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      43.00 Perc.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C8     ..  O3'     ..       2.95 Ang.
PLAT704_ALERT_1_C Contact Calc    3.553(2), Rep    3.550(4), Dev..       1.50 Sigma
              C6   -C14     1.555   3.556

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In recent years, there has been considerable interest in proton transfer systems and their structures (Smith et al., 1999; Zafar et al., 2000; Rafizadeh et al., 2006; Yousefi et al., 2007). To our knowledge, there is only one proton-transfer system with 2,2'-biquinolinyl, such as [(biq.H)(I₂Cl₃)] [biq.H = 2-(2-quinolinyl)quinolinium], which was structurally characterized (Parlow & Hartl, 1979). Herewith we report the synthesis and crystal structure of the title compound, (I).

The asymmetric unit of (I) contains one cation and one anion (Fig. 1). In the cation, two bicycles form a dihedral angle of 3.84 (4)%. In the crystal structure, the cations form stacks along the a axis with short intermolecular contacts [C···C = 3.330 (3) and 3.345 (4)Å] linking the anions via N—H···O hydrogen bonds.

Related literature

For related literature, see: Smith et al. (1999); Zafar et al. (2000); Rafizadeh et al. (2006); Yousefi et al. (2007); Parlow & Hartl (1979).

S2. Experimental

For the preparation of the title compound, (I), a solution of 2,2'-biquinolinyl (0.20 g, 0.78 mmol) in HNO₃ 0.5 M (10 ml) was added to a solution of La(NO₃)₃.6H₂O, (0.11 g, 0.26 mmol) in water (5 ml) and the resulting yellow solution was stirred at 333 K for 2 h. Then, it was left to evaporate slowly at room temperature. The suitable crystals for X-ray diffraction experiment were obtained by methanol diffusion in a solution of yellow precipitated in DMSO after one week (yield 0.19 g, 76.2%, m.p 496–497 K).

S3. Refinement

C-bound H atoms were geometrically positioned (C-H 0.95 Å). The H atom of NH group was located on a difference Fourier map, but placed in idealized position (N-H 0.91 Å). All H atoms were refined in riding model approximation, with U_iso(H) = 1.2 U_eq of the parent atom. The NO₃ anion was treated as disordered between two orientations with the occupancies fixed to 0.9 and 0.1, respectively.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The content of asymmetric unit of (I) showing the atomic numbering and 50% probability displacement ellipsoids. Only major part of the disordered nitrate anion is shown.

2-(2-Quinolyl)quinolinium nitrate

Crystal data

C18H13N2^+·NO3^−	F(000) = 664
Mr = 319.31	Dx = 1.499 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 937 reflections
a = 6.9756 (6) Å	θ = 3–29°
b = 10.6408 (9) Å	µ = 0.11 mm^−1
c = 19.1226 (15) Å	T = 120 K
β = 94.399 (2)°	Block, yellow
V = 1415.2 (2) Å^3	0.45 × 0.30 × 0.25 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	2115 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 29.0°, θmin = 2.1°
ω scans	h = −9→9
15078 measured reflections	k = −14→14
3739 independent reflections	l = −25→26

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: mixed
wR(F^2) = 0.136	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0551P)^2 + 0.46P] where P = (Fo^2 + 2Fc^2)/3
3739 reflections	(Δ/σ)max < 0.001
229 parameters	Δρmax = 0.31 e Å^−3
3 restraints	Δρmin = −0.29 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.2846 (2)	0.12303 (14)	0.47447 (7)	0.0261 (3)
N2	0.21783 (19)	−0.05200 (13)	0.56913 (7)	0.0245 (3)
H2N	0.2249	0.0316	0.5802	0.029*
C1	0.3241 (2)	0.21681 (17)	0.42885 (9)	0.0265 (4)
C2	0.3386 (3)	0.34167 (17)	0.45393 (10)	0.0320 (4)
H2A	0.3180	0.3593	0.5015	0.038*
C3	0.3821 (3)	0.43694 (19)	0.41010 (10)	0.0352 (5)
H3A	0.3920	0.5205	0.4274	0.042*
C4	0.4124 (3)	0.4124 (2)	0.33902 (10)	0.0347 (5)
H4A	0.4448	0.4794	0.3093	0.042*
C5	0.3955 (3)	0.29307 (19)	0.31289 (10)	0.0329 (4)
H5A	0.4127	0.2780	0.2648	0.040*
C6	0.3524 (2)	0.19166 (18)	0.35718 (9)	0.0283 (4)
C7	0.3393 (3)	0.06604 (19)	0.33471 (9)	0.0319 (4)
H7A	0.3553	0.0460	0.2871	0.038*
C8	0.3037 (3)	−0.02721 (18)	0.38088 (9)	0.0307 (4)
H8A	0.2981	−0.1126	0.3663	0.037*
C9	0.2754 (2)	0.00614 (17)	0.45085 (9)	0.0243 (4)
C10	0.2313 (2)	−0.09095 (17)	0.50285 (9)	0.0249 (4)
C11	0.2028 (3)	−0.21806 (17)	0.48705 (10)	0.0309 (4)
H11A	0.2123	−0.2471	0.4405	0.037*
C12	0.1613 (3)	−0.30107 (17)	0.53859 (10)	0.0321 (4)
H12A	0.1413	−0.3873	0.5273	0.038*
C13	0.1480 (2)	−0.26001 (17)	0.60813 (9)	0.0272 (4)
C14	0.1044 (2)	−0.34060 (17)	0.66293 (10)	0.0313 (4)
H14A	0.0826	−0.4274	0.6539	0.038*
C15	0.0931 (3)	−0.29430 (18)	0.72935 (10)	0.0332 (4)
H15A	0.0621	−0.3492	0.7660	0.040*
C16	0.1272 (3)	−0.16592 (18)	0.74375 (10)	0.0326 (4)
H16A	0.1207	−0.1355	0.7902	0.039*
C17	0.1696 (2)	−0.08437 (17)	0.69156 (9)	0.0285 (4)
H17A	0.1928	0.0020	0.7015	0.034*
C18	0.1781 (2)	−0.13100 (17)	0.62339 (9)	0.0248 (4)
N3	0.2376 (3)	0.27946 (17)	0.62588 (8)	0.0385 (4)
O1	0.1506 (3)	0.17769 (16)	0.63037 (10)	0.0433 (5)	0.90
O2	0.1410 (3)	0.37683 (15)	0.60925 (9)	0.0502 (5)	0.90
O3	0.4157 (3)	0.2874 (2)	0.63555 (9)	0.0555 (5)	0.90
O1'	0.0850 (18)	0.2168 (18)	0.6230 (13)	0.060 (7)*	0.10
O2'	0.264 (3)	0.3897 (8)	0.6450 (11)	0.077 (6)*	0.10
O3'	0.3749 (19)	0.2024 (14)	0.6346 (9)	0.054 (4)*	0.10

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0253 (8)	0.0271 (8)	0.0258 (8)	0.0003 (6)	0.0022 (6)	0.0036 (6)
N2	0.0255 (8)	0.0229 (7)	0.0249 (8)	0.0000 (6)	0.0011 (6)	−0.0003 (6)
C1	0.0239 (9)	0.0306 (10)	0.0249 (9)	0.0021 (7)	0.0017 (7)	0.0031 (8)
C2	0.0371 (11)	0.0314 (10)	0.0280 (10)	0.0010 (8)	0.0063 (8)	0.0017 (8)
C3	0.0368 (11)	0.0306 (10)	0.0384 (11)	0.0008 (8)	0.0044 (9)	0.0054 (8)
C4	0.0289 (10)	0.0431 (12)	0.0323 (10)	0.0004 (8)	0.0027 (8)	0.0144 (9)
C5	0.0274 (10)	0.0473 (12)	0.0239 (9)	0.0000 (9)	0.0010 (7)	0.0069 (8)
C6	0.0214 (9)	0.0393 (11)	0.0243 (9)	0.0021 (8)	0.0014 (7)	0.0027 (8)
C7	0.0286 (10)	0.0442 (12)	0.0230 (9)	−0.0017 (8)	0.0035 (7)	−0.0013 (8)
C8	0.0329 (10)	0.0318 (10)	0.0273 (10)	−0.0010 (8)	0.0029 (8)	−0.0046 (8)
C9	0.0214 (8)	0.0288 (9)	0.0226 (8)	0.0006 (7)	0.0001 (7)	−0.0005 (7)
C10	0.0203 (8)	0.0292 (10)	0.0251 (9)	0.0016 (7)	0.0013 (7)	−0.0017 (7)
C11	0.0332 (10)	0.0299 (10)	0.0295 (10)	0.0002 (8)	0.0026 (8)	−0.0047 (8)
C12	0.0310 (10)	0.0240 (9)	0.0412 (11)	−0.0010 (8)	0.0029 (8)	−0.0041 (8)
C13	0.0215 (9)	0.0282 (9)	0.0319 (10)	0.0015 (7)	0.0027 (7)	0.0018 (8)
C14	0.0280 (10)	0.0241 (9)	0.0417 (11)	−0.0014 (7)	0.0024 (8)	0.0046 (8)
C15	0.0290 (10)	0.0336 (10)	0.0375 (11)	−0.0009 (8)	0.0053 (8)	0.0118 (8)
C16	0.0339 (10)	0.0364 (11)	0.0278 (10)	0.0036 (8)	0.0048 (8)	0.0024 (8)
C17	0.0287 (10)	0.0288 (9)	0.0282 (9)	0.0013 (8)	0.0027 (7)	−0.0003 (8)
C18	0.0203 (8)	0.0258 (9)	0.0283 (9)	0.0016 (7)	0.0017 (7)	0.0036 (7)
N3	0.0534 (11)	0.0360 (10)	0.0272 (9)	−0.0011 (9)	0.0102 (8)	−0.0040 (7)
O1	0.0697 (12)	0.0249 (9)	0.0380 (10)	−0.0089 (10)	0.0211 (9)	−0.0020 (8)
O2	0.0790 (13)	0.0276 (9)	0.0460 (10)	0.0114 (9)	0.0186 (9)	0.0005 (7)
O3	0.0514 (12)	0.0705 (14)	0.0440 (11)	−0.0145 (10)	0.0011 (8)	0.0099 (9)

Geometric parameters (Å, º)

N1—C9	1.323 (2)	C10—C11	1.397 (3)
N1—C1	1.367 (2)	C11—C12	1.371 (3)
N2—C10	1.344 (2)	C11—H11A	0.9500
N2—C18	1.380 (2)	C12—C13	1.410 (3)
N2—H2N	0.910	C12—H12A	0.9500
C1—C2	1.413 (3)	C13—C14	1.405 (2)
C1—C6	1.425 (2)	C13—C18	1.416 (3)
C2—C3	1.364 (3)	C14—C15	1.370 (3)
C2—H2A	0.9500	C14—H14A	0.9500
C3—C4	1.416 (3)	C15—C16	1.410 (3)
C3—H3A	0.9500	C15—H15A	0.9500
C4—C5	1.366 (3)	C16—C17	1.372 (3)
C4—H4A	0.9500	C16—H16A	0.9500
C5—C6	1.418 (3)	C17—C18	1.400 (2)
C5—H5A	0.9500	C17—H17A	0.9500
C6—C7	1.405 (3)	N3—O2'	1.239 (5)
C7—C8	1.364 (3)	N3—O3	1.245 (2)
C7—H7A	0.9500	N3—O1	1.247 (2)
C8—C9	1.413 (2)	N3—O1'	1.253 (5)
C8—H8A	0.9500	N3—O3'	1.263 (5)
C9—C10	1.483 (2)	N3—O2	1.263 (2)
N1···C18^i	3.606 (3)	C6···C14^i	3.550 (4)
N1···C10^ii	3.388 (3)	C18···C6^ii	3.330 (3)
C1···C13^i	3.345 (4)
C9—N1—C1	118.36 (15)	N2—C10—C9	116.81 (15)
C10—N2—C18	123.64 (15)	C11—C10—C9	124.27 (16)
C10—N2—H2N	120.8	C12—C11—C10	120.19 (17)
C18—N2—H2N	115.4	C12—C11—H11A	119.9
N1—C1—C2	118.83 (16)	C10—C11—H11A	119.9
N1—C1—C6	121.75 (16)	C11—C12—C13	120.75 (17)
C2—C1—C6	119.42 (16)	C11—C12—H12A	119.6
C3—C2—C1	120.24 (17)	C13—C12—H12A	119.6
C3—C2—H2A	119.9	C14—C13—C12	123.24 (17)
C1—C2—H2A	119.9	C14—C13—C18	118.36 (17)
C2—C3—C4	120.60 (19)	C12—C13—C18	118.40 (16)
C2—C3—H3A	119.7	C15—C14—C13	120.20 (17)
C4—C3—H3A	119.7	C15—C14—H14A	119.9
C5—C4—C3	120.51 (18)	C13—C14—H14A	119.9
C5—C4—H4A	119.7	C14—C15—C16	120.56 (17)
C3—C4—H4A	119.7	C14—C15—H15A	119.7
C4—C5—C6	120.33 (17)	C16—C15—H15A	119.7
C4—C5—H5A	119.8	C17—C16—C15	120.89 (18)
C6—C5—H5A	119.8	C17—C16—H16A	119.6
C7—C6—C5	123.57 (17)	C15—C16—H16A	119.6
C7—C6—C1	117.54 (16)	C16—C17—C18	118.69 (17)
C5—C6—C1	118.88 (17)	C16—C17—H17A	120.7
C8—C7—C6	120.34 (17)	C18—C17—H17A	120.7
C8—C7—H7A	119.8	N2—C18—C17	120.62 (16)
C6—C7—H7A	119.8	N2—C18—C13	118.09 (16)
C7—C8—C9	118.43 (17)	C17—C18—C13	121.29 (16)
C7—C8—H8A	120.8	O3—N3—O1	122.3 (2)
C9—C8—H8A	120.8	O2'—N3—O1'	128.7 (14)
N1—C9—C8	123.57 (16)	O2'—N3—O3'	118.7 (14)
N1—C9—C10	115.67 (15)	O1'—N3—O3'	107.1 (13)
C8—C9—C10	120.77 (16)	O3—N3—O2	119.2 (2)
N2—C10—C11	118.92 (16)	O1—N3—O2	118.5 (2)
C9—N1—C1—C2	−178.56 (16)	N1—C9—C10—N2	−4.2 (2)
C9—N1—C1—C6	0.9 (2)	C8—C9—C10—N2	176.18 (15)
N1—C1—C2—C3	178.55 (17)	N1—C9—C10—C11	175.52 (16)
C6—C1—C2—C3	−1.0 (3)	C8—C9—C10—C11	−4.1 (3)
C1—C2—C3—C4	0.3 (3)	N2—C10—C11—C12	0.2 (3)
C2—C3—C4—C5	1.1 (3)	C9—C10—C11—C12	−179.57 (16)
C3—C4—C5—C6	−1.7 (3)	C10—C11—C12—C13	−0.4 (3)
C4—C5—C6—C7	−177.72 (18)	C11—C12—C13—C14	179.46 (17)
C4—C5—C6—C1	1.0 (3)	C11—C12—C13—C18	0.2 (3)
N1—C1—C6—C7	−0.3 (3)	C12—C13—C14—C15	−179.80 (17)
C2—C1—C6—C7	179.14 (16)	C18—C13—C14—C15	−0.5 (3)
N1—C1—C6—C5	−179.15 (16)	C13—C14—C15—C16	−0.7 (3)
C2—C1—C6—C5	0.3 (3)	C14—C15—C16—C17	0.9 (3)
C5—C6—C7—C8	177.74 (17)	C15—C16—C17—C18	0.1 (3)
C1—C6—C7—C8	−1.0 (3)	C10—N2—C18—C17	178.81 (15)
C6—C7—C8—C9	1.7 (3)	C10—N2—C18—C13	−0.6 (2)
C1—N1—C9—C8	−0.2 (2)	C16—C17—C18—N2	179.18 (16)
C1—N1—C9—C10	−179.75 (15)	C16—C17—C18—C13	−1.4 (3)
C7—C8—C9—N1	−1.1 (3)	C14—C13—C18—N2	−178.98 (15)
C7—C8—C9—C10	178.41 (16)	C12—C13—C18—N2	0.3 (2)
C18—N2—C10—C11	0.4 (2)	C14—C13—C18—C17	1.6 (2)
C18—N2—C10—C9	−179.86 (14)	C12—C13—C18—C17	−179.08 (16)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1	0.91	1.92	2.766 (2)	153