Crystal structure of 3,9,9-trimethyl-2,3,3a,4,9,9a-hexa-hydro-1H-cyclo-penta[b]quinolin-4-ium chloride.

The title mol-ecular salt, C15H22N(+)·Cl(-), arose as an unexpected product of the reaction between aniline and melanol in the presence of HCl. The central heterocyclic ring has a half-chair conformation and the five-membered ring has an envelope conformation, with the C atom linked to the N atom as the flap. In the crystal, the ions are linked by N-H⋯Cl hydrogen bonds, generating chains propagating in the [100] direction. The crystal studied was a merohedral twin with a 0.64 (3):0.36 (3) domain ratio.

Related literature

For biological background, see: Szymański et al. (2012 ▸). For further synthetic details, see: Alaghaz et al. (2014 ▸).

Experimental

Crystal data

C15H22N+·Cl−

M = 251.78

Orthorhombic,

a = 7.0291 (5) Å

b = 10.3313 (8) Å

c = 18.9425 (14) Å

V = 1375.60 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 298 K

0.35 × 0.30 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

7372 measured reflections

3334 independent reflections

3013 reflections with I > 2σ(I)

R int = 0.028

Standard reflections: 0

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.123

S = 0.95

3334 reflections

165 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.23 e Å−3

Absolute structure: Flack x determined using 1165 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)

Absolute structure parameter: 0.36 (3)

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS7 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▸).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015011858/hb7450sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011858/hb7450Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015011858/hb7450Isup3.cml

Click here for additional data file.

ORTEP . DOI: 10.1107/S2056989015011858/hb7450fig1.tif

ORTEP diagram of the title compound drawn at 30% probability

Click here for additional data file.

. DOI: 10.1107/S2056989015011858/hb7450fig2.tif

Packing diagram of the mol­ecule viewed down ’b′ axis

CCDC reference: 1407884

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H22N+·Cl−	Dx = 1.216 Mg m−3
Mr = 251.78	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 7.0291 (5) Å	θ = 2.0–25°
b = 10.3313 (8) Å	µ = 0.26 mm−1
c = 18.9425 (14) Å	T = 298 K
V = 1375.60 (18) Å3	Block, colourless
Z = 4	0.35 × 0.30 × 0.30 mm
F(000) = 544

Oxford Diffraction Xcalibur Sapphire3 diffractometer	Rint = 0.028
ω scans	θmax = 28.5°, θmin = 2.2°
7372 measured reflections	h = −9→9
3334 independent reflections	k = −13→9
3013 reflections with I > 2σ(I)	l = −10→24

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.039	w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.123	(Δ/σ)max < 0.001
S = 0.95	Δρmax = 0.26 e Å−3
3334 reflections	Δρmin = −0.23 e Å−3
165 parameters	Absolute structure: Flack x determined using 1165 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.36 (3)

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.

	x	y	z	Uiso*/Ueq
Cl1	0.15461 (9)	0.64944 (6)	0.56931 (3)	0.0429 (2)
N1	0.4133 (3)	0.60045 (17)	0.43815 (9)	0.0287 (4)
C2	0.5014 (3)	0.4292 (2)	0.31431 (12)	0.0311 (5)
C3	0.6364 (3)	0.4629 (2)	0.37502 (12)	0.0306 (4)
H3	0.6958	0.5458	0.3630	0.037*
C4	0.3378 (3)	0.5258 (2)	0.31593 (10)	0.0282 (4)
C5	0.2938 (3)	0.6012 (2)	0.37467 (11)	0.0272 (4)
C6	0.5333 (3)	0.4825 (2)	0.44441 (11)	0.0284 (4)
H6	0.4519	0.4074	0.4539	0.034*
C7	0.1374 (3)	0.6827 (2)	0.37588 (13)	0.0360 (5)
H7	0.1104	0.7308	0.4162	0.043*
C8	0.0217 (3)	0.6927 (3)	0.31749 (14)	0.0409 (6)
H8	−0.0835	0.7473	0.3181	0.049*
C9	0.6887 (4)	0.4896 (2)	0.49987 (12)	0.0377 (5)
H9	0.7489	0.5750	0.4975	0.045*
C10	0.7987 (4)	0.3694 (3)	0.39459 (15)	0.0497 (7)
H10A	0.7630	0.2806	0.3844	0.060*
H10B	0.9133	0.3901	0.3684	0.060*
C11	0.2179 (3)	0.5383 (3)	0.25764 (12)	0.0375 (5)
H11	0.2427	0.4897	0.2173	0.045*
C12	0.0635 (3)	0.6210 (3)	0.25812 (14)	0.0420 (6)
H12	−0.0127	0.6283	0.2182	0.050*
C13	0.6117 (4)	0.4384 (3)	0.24472 (13)	0.0463 (6)
H13A	0.6450	0.5271	0.2359	0.070*
H13B	0.5338	0.4068	0.2068	0.070*
H13C	0.7254	0.3873	0.2479	0.070*
C14	0.6223 (4)	0.4657 (3)	0.57507 (13)	0.0518 (7)
H14A	0.5301	0.5300	0.5879	0.078*
H14B	0.7291	0.4707	0.6065	0.078*
H14C	0.5659	0.3813	0.5783	0.078*
C15	0.4183 (5)	0.2923 (2)	0.32124 (16)	0.0508 (7)
H15A	0.5201	0.2305	0.3240	0.076*
H15B	0.3407	0.2736	0.2808	0.076*
H15C	0.3423	0.2871	0.3632	0.076*
C16	0.8301 (5)	0.3879 (3)	0.47281 (15)	0.0598 (8)
H16A	0.9594	0.4165	0.4815	0.072*
H16B	0.8107	0.3066	0.4974	0.072*
H1A	0.334 (6)	0.613 (4)	0.4846 (18)	0.079 (11)*
H1B	0.490 (4)	0.673 (3)	0.4388 (16)	0.047 (8)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0449 (3)	0.0503 (3)	0.0335 (3)	0.0088 (3)	0.0067 (2)	0.0008 (3)
N1	0.0305 (8)	0.0319 (8)	0.0238 (9)	0.0006 (7)	−0.0019 (7)	−0.0030 (7)
C2	0.0361 (10)	0.0296 (10)	0.0275 (11)	0.0002 (8)	0.0007 (8)	−0.0042 (8)
C3	0.0310 (10)	0.0334 (10)	0.0275 (11)	0.0030 (8)	0.0009 (8)	−0.0018 (8)
C4	0.0277 (9)	0.0315 (9)	0.0255 (10)	−0.0056 (9)	0.0017 (8)	−0.0010 (8)
C5	0.0273 (9)	0.0319 (9)	0.0223 (10)	−0.0029 (7)	−0.0007 (7)	0.0001 (8)
C6	0.0324 (10)	0.0280 (9)	0.0247 (10)	0.0000 (8)	−0.0022 (7)	0.0014 (8)
C7	0.0354 (11)	0.0402 (11)	0.0324 (11)	0.0052 (9)	0.0016 (9)	−0.0012 (9)
C8	0.0300 (10)	0.0514 (14)	0.0412 (14)	0.0054 (10)	−0.0023 (9)	0.0065 (11)
C9	0.0411 (12)	0.0390 (11)	0.0330 (11)	0.0053 (10)	−0.0102 (9)	−0.0005 (10)
C10	0.0461 (13)	0.0571 (16)	0.0460 (15)	0.0197 (12)	−0.0060 (11)	−0.0060 (13)
C11	0.0375 (11)	0.0471 (13)	0.0278 (11)	−0.0064 (10)	−0.0034 (9)	−0.0041 (10)
C12	0.0338 (10)	0.0564 (15)	0.0358 (12)	−0.0054 (11)	−0.0087 (9)	0.0064 (11)
C13	0.0475 (14)	0.0614 (16)	0.0301 (12)	0.0111 (12)	0.0061 (10)	−0.0058 (12)
C14	0.0647 (17)	0.0607 (16)	0.0299 (13)	0.0123 (14)	−0.0096 (12)	0.0050 (12)
C15	0.0624 (16)	0.0310 (11)	0.0591 (19)	−0.0069 (12)	−0.0096 (14)	−0.0063 (12)
C16	0.0581 (16)	0.078 (2)	0.0430 (15)	0.0322 (17)	−0.0127 (13)	−0.0071 (15)

N1—C5	1.467 (3)	C9—C14	1.519 (3)
N1—C6	1.487 (3)	C9—C16	1.534 (4)
N1—H1A	1.05 (4)	C9—H9	0.9800
N1—H1B	0.93 (3)	C10—C16	1.510 (4)
C2—C4	1.523 (3)	C10—H10A	0.9700
C2—C3	1.531 (3)	C10—H10B	0.9700
C2—C13	1.532 (3)	C11—C12	1.381 (3)
C2—C15	1.536 (3)	C11—H11	0.9300
C3—C6	1.515 (3)	C12—H12	0.9300
C3—C10	1.540 (3)	C13—H13A	0.9600
C3—H3	0.9800	C13—H13B	0.9600
C4—C5	1.393 (3)	C13—H13C	0.9600
C4—C11	1.395 (3)	C14—H14A	0.9600
C5—C7	1.386 (3)	C14—H14B	0.9600
C6—C9	1.518 (3)	C14—H14C	0.9600
C6—H6	0.9800	C15—H15A	0.9600
C7—C8	1.376 (3)	C15—H15B	0.9600
C7—H7	0.9300	C15—H15C	0.9600
C8—C12	1.378 (4)	C16—H16A	0.9700
C8—H8	0.9300	C16—H16B	0.9700
C5—N1—C6	113.23 (16)	C6—C9—H9	108.8
C5—N1—H1A	112 (2)	C14—C9—H9	108.8
C6—N1—H1A	110 (2)	C16—C9—H9	108.8
C5—N1—H1B	109.9 (18)	C16—C10—C3	105.4 (2)
C6—N1—H1B	109.6 (18)	C16—C10—H10A	110.7
H1A—N1—H1B	102 (3)	C3—C10—H10A	110.7
C4—C2—C3	107.70 (17)	C16—C10—H10B	110.7
C4—C2—C13	111.01 (19)	C3—C10—H10B	110.7
C3—C2—C13	108.59 (19)	H10A—C10—H10B	108.8
C4—C2—C15	108.32 (18)	C12—C11—C4	121.8 (2)
C3—C2—C15	112.4 (2)	C12—C11—H11	119.1
C13—C2—C15	108.9 (2)	C4—C11—H11	119.1
C6—C3—C2	112.69 (18)	C8—C12—C11	120.3 (2)
C6—C3—C10	103.27 (18)	C8—C12—H12	119.8
C2—C3—C10	119.81 (19)	C11—C12—H12	119.8
C6—C3—H3	106.8	C2—C13—H13A	109.5
C2—C3—H3	106.8	C2—C13—H13B	109.5
C10—C3—H3	106.8	H13A—C13—H13B	109.5
C5—C4—C11	116.5 (2)	C2—C13—H13C	109.5
C5—C4—C2	123.37 (19)	H13A—C13—H13C	109.5
C11—C4—C2	120.08 (19)	H13B—C13—H13C	109.5
C7—C5—C4	122.0 (2)	C9—C14—H14A	109.5
C7—C5—N1	116.36 (19)	C9—C14—H14B	109.5
C4—C5—N1	121.67 (18)	H14A—C14—H14B	109.5
N1—C6—C3	108.17 (16)	C9—C14—H14C	109.5
N1—C6—C9	115.09 (18)	H14A—C14—H14C	109.5
C3—C6—C9	105.22 (18)	H14B—C14—H14C	109.5
N1—C6—H6	109.4	C2—C15—H15A	109.5
C3—C6—H6	109.4	C2—C15—H15B	109.5
C9—C6—H6	109.4	H15A—C15—H15B	109.5
C8—C7—C5	120.1 (2)	C2—C15—H15C	109.5
C8—C7—H7	120.0	H15A—C15—H15C	109.5
C5—C7—H7	120.0	H15B—C15—H15C	109.5
C7—C8—C12	119.3 (2)	C10—C16—C9	108.7 (2)
C7—C8—H8	120.3	C10—C16—H16A	110.0
C12—C8—H8	120.3	C9—C16—H16A	110.0
C6—C9—C14	114.8 (2)	C10—C16—H16B	110.0
C6—C9—C16	101.64 (19)	C9—C16—H16B	110.0
C14—C9—C16	113.6 (2)	H16A—C16—H16B	108.3
C4—C2—C3—C6	48.4 (2)	C2—C3—C6—N1	−66.8 (2)
C13—C2—C3—C6	168.67 (19)	C10—C3—C6—N1	162.49 (19)
C15—C2—C3—C6	−70.8 (2)	C2—C3—C6—C9	169.71 (19)
C4—C2—C3—C10	170.1 (2)	C10—C3—C6—C9	39.0 (2)
C13—C2—C3—C10	−69.6 (3)	C4—C5—C7—C8	−1.1 (3)
C15—C2—C3—C10	50.9 (3)	N1—C5—C7—C8	177.7 (2)
C3—C2—C4—C5	−17.9 (3)	C5—C7—C8—C12	0.0 (4)
C13—C2—C4—C5	−136.7 (2)	N1—C6—C9—C14	79.9 (3)
C15—C2—C4—C5	103.8 (2)	C3—C6—C9—C14	−161.2 (2)
C3—C2—C4—C11	164.75 (19)	N1—C6—C9—C16	−157.0 (2)
C13—C2—C4—C11	46.0 (3)	C3—C6—C9—C16	−38.0 (2)
C15—C2—C4—C11	−73.5 (3)	C6—C3—C10—C16	−23.7 (3)
C11—C4—C5—C7	1.2 (3)	C2—C3—C10—C16	−150.0 (3)
C2—C4—C5—C7	−176.2 (2)	C5—C4—C11—C12	−0.1 (3)
C11—C4—C5—N1	−177.55 (19)	C2—C4—C11—C12	177.3 (2)
C2—C4—C5—N1	5.1 (3)	C7—C8—C12—C11	1.1 (4)
C6—N1—C5—C7	159.69 (19)	C4—C11—C12—C8	−1.0 (4)
C6—N1—C5—C4	−21.5 (3)	C3—C10—C16—C9	0.4 (3)
C5—N1—C6—C3	50.1 (2)	C6—C9—C16—C10	22.9 (3)
C5—N1—C6—C9	167.43 (18)	C14—C9—C16—C10	146.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	1.05 (4)	2.07 (4)	3.1201 (19)	173 (3)
N1—H1B···Cl1i	0.93 (3)	2.17 (3)	3.0943 (19)	174 (3)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1ACl1	1.05(4)	2.07(4)	3.1201(19)	173(3)
N1H1BCl1i	0.93(3)	2.17(3)	3.0943(19)	174(3)

Symmetry code: (i) .