1-(5-Carboxy-pent-yl)-2,3,3-trimethyl-3H-indol-1-ium bromide monohydrate.

In the title compound, C(17)H(24)NO(2) (+)·Br(-)·H(2)O, the pentyl group chain in the cation extends nearly perpendicular [N-C-C-C = -64.4 (3)°] to the mean plane of the indole ring with the carboxyl end group twisted such that the dihedral angle between the mean planes of the indole and carb-oxy groups measures 43.2 (4)°. Both ions in the salt form inter-molecular hydrogen bonds (O-H⋯Br and O-H⋯O) with the water mol-ecule. As a result of the Br⋯H-O-H⋯Br inter-actions, a zigzag chain is formed in the c-axis direction. The crystal packing is influenced by the collective action of the O-H⋯O and O-H⋯Br inter-molecular inter-actions as well as π-π stacking inter-molecular inter-actions between adjacent benzyl rings of the indole group [centroid-centroid distance = 3.721 (13) Å] and inter-molecular C-H⋯π inter-actions between a methyl hydrogen and the benzyl ring of the indole group. The O-H⋯Br inter-actions form a distorted tetra-hedral array about the central Br atom. A MOPAC AM1 calculation provides support to these observations.

Related literature

For chemical and biological background, see: Zhu et al. (1994 ▶); Schwartz & Ulfelder (1992 ▶); Bengtsson et al. (2003 ▶); Hirons et al. (1994 ▶); Kurihara et al. (1977 ▶); Armitage & O’Brien (1992 ▶); Reers et al. (1991 ▶); Jung & Kim (2006 ▶); Menger & Pertusati (2008 ▶). A geometry optimized MOPAC AM1 computational calculation was performed using WebMO Pro (Schmidt & Polik, 2007 ▶).

Experimental

Crystal data

C17H24NO2 +·Br−·H2O

M = 372.30

Monoclinic,

a = 14.4528 (3) Å

b = 15.3367 (2) Å

c = 8.0810 (2) Å

β = 99.437 (2)°

V = 1766.98 (6) Å3

Z = 4

Cu Kα radiation

μ = 3.27 mm−1

T = 200 K

0.55 × 0.18 × 0.12 mm

Data collection

Oxford Diffraction Gemini R diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.296, T max = 0.676

13155 measured reflections

3504 independent reflections

3049 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.098

S = 1.06

3504 reflections

209 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.52 e Å−3

Δρmin = −0.43 e Å−3

Data collection: CrysAlis Pro (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049204/fl2265sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049204/fl2265Isup2.hkl

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

C17H24NO2+·Br−·H2O	F(000) = 776
Mr = 372.30	Dx = 1.399 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 8515 reflections
a = 14.4528 (3) Å	θ = 5.6–73.5°
b = 15.3367 (2) Å	µ = 3.27 mm−1
c = 8.0810 (2) Å	T = 200 K
β = 99.437 (2)°	Needle, colorless
V = 1766.98 (6) Å3	0.55 × 0.18 × 0.12 mm
Z = 4

Oxford Diffraction Gemini R diffractometer	3504 independent reflections
Radiation source: fine-focus sealed tube	3049 reflections with I > 2σ(I)
graphite	Rint = 0.033
Detector resolution: 10.5081 pixels mm-1	θmax = 73.7°, θmin = 5.8°
φ and ω scans	h = −17→15
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −18→19
Tmin = 0.296, Tmax = 0.676	l = −10→8
13155 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0518P)2 + 1.5238P] where P = (Fo2 + 2Fc2)/3
3504 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 0.52 e Å−3
3 restraints	Δρmin = −0.43 e Å−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.

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.

	x	y	z	Uiso*/Ueq
Br	0.168343 (18)	0.871933 (16)	0.50535 (3)	0.03689 (11)
O1	0.5587 (2)	0.7918 (2)	0.1347 (5)	0.0893 (10)
O2	0.42824 (18)	0.81569 (14)	0.2331 (4)	0.0661 (7)
H2O	0.3800	0.7873	0.2448	0.079*
O1W	0.28626 (17)	0.7310 (2)	0.3254 (3)	0.0707 (8)
H1W1	0.254 (3)	0.764 (3)	0.372 (5)	0.106*
H1W2	0.251 (3)	0.714 (3)	0.242 (4)	0.106*
N1	0.79026 (13)	0.52889 (12)	0.5047 (2)	0.0254 (4)
C1	0.76946 (16)	0.56100 (15)	0.6432 (3)	0.0279 (5)
C2	0.68861 (18)	0.53476 (18)	0.7221 (3)	0.0379 (6)
H2A	0.6566	0.4853	0.6607	0.057*
H2B	0.6449	0.5838	0.7192	0.057*
H2C	0.7106	0.5178	0.8389	0.057*
C3	0.84000 (16)	0.63015 (14)	0.7139 (3)	0.0268 (5)
C4	0.78975 (19)	0.71914 (16)	0.7114 (3)	0.0367 (6)
H4A	0.7579	0.7317	0.5972	0.055*
H4B	0.8359	0.7649	0.7478	0.055*
H4C	0.7435	0.7173	0.7875	0.055*
C5	0.88798 (19)	0.60805 (17)	0.8929 (3)	0.0348 (5)
H5A	0.9155	0.5496	0.8944	0.052*
H5B	0.8416	0.6097	0.9687	0.052*
H5C	0.9375	0.6508	0.9297	0.052*
C6	0.90648 (16)	0.62789 (13)	0.5885 (3)	0.0252 (4)
C7	0.98805 (16)	0.67357 (15)	0.5803 (3)	0.0301 (5)
H7A	1.0118	0.7148	0.6643	0.036*
C8	1.03446 (17)	0.65748 (16)	0.4452 (3)	0.0327 (5)
H8A	1.0904	0.6886	0.4369	0.039*
C9	1.00061 (17)	0.59686 (16)	0.3225 (3)	0.0318 (5)
H9A	1.0338	0.5873	0.2319	0.038*
C10	0.91882 (16)	0.54979 (15)	0.3296 (3)	0.0281 (5)
H10A	0.8952	0.5078	0.2470	0.034*
C11	0.87436 (15)	0.56811 (14)	0.4644 (3)	0.0246 (4)
C12	0.73635 (17)	0.46508 (15)	0.3907 (3)	0.0320 (5)
H12A	0.6940	0.4319	0.4522	0.038*
H12B	0.7800	0.4232	0.3508	0.038*
C13	0.67861 (17)	0.51091 (16)	0.2403 (3)	0.0339 (5)
H13A	0.7215	0.5454	0.1823	0.041*
H13B	0.6488	0.4661	0.1607	0.041*
C14	0.60247 (18)	0.57112 (19)	0.2847 (3)	0.0391 (6)
H14A	0.5631	0.5384	0.3527	0.047*
H14B	0.6323	0.6199	0.3540	0.047*
C15	0.5405 (2)	0.6079 (2)	0.1308 (4)	0.0553 (8)
H15A	0.5107	0.5590	0.0617	0.066*
H15B	0.5800	0.6403	0.0628	0.066*
C16	0.46391 (19)	0.66849 (18)	0.1732 (4)	0.0430 (6)
H16A	0.4067	0.6601	0.0888	0.052*
H16B	0.4486	0.6516	0.2838	0.052*
C17	0.4896 (2)	0.7628 (2)	0.1783 (4)	0.0492 (7)

	U11	U22	U33	U12	U13	U23
Br	0.04080 (17)	0.03133 (16)	0.03975 (18)	−0.00006 (10)	0.01018 (12)	0.00063 (10)
O1	0.0628 (16)	0.0726 (18)	0.136 (3)	−0.0271 (14)	0.0274 (17)	−0.0028 (18)
O2	0.0607 (14)	0.0372 (11)	0.097 (2)	0.0081 (10)	0.0028 (13)	−0.0153 (12)
O1W	0.0458 (12)	0.102 (2)	0.0635 (16)	0.0124 (13)	0.0056 (11)	−0.0374 (15)
N1	0.0266 (9)	0.0221 (8)	0.0263 (10)	−0.0014 (7)	0.0009 (7)	0.0013 (7)
C1	0.0300 (11)	0.0264 (11)	0.0259 (11)	0.0015 (9)	0.0005 (9)	0.0053 (9)
C2	0.0355 (13)	0.0415 (14)	0.0380 (14)	−0.0016 (10)	0.0105 (11)	0.0069 (11)
C3	0.0325 (11)	0.0237 (11)	0.0238 (11)	−0.0012 (8)	0.0033 (9)	−0.0004 (8)
C4	0.0450 (14)	0.0296 (12)	0.0366 (14)	0.0056 (10)	0.0100 (11)	−0.0002 (10)
C5	0.0439 (14)	0.0343 (12)	0.0244 (12)	−0.0008 (10)	0.0004 (10)	0.0014 (10)
C6	0.0317 (11)	0.0205 (10)	0.0225 (11)	0.0018 (8)	0.0015 (9)	0.0015 (8)
C7	0.0334 (11)	0.0232 (11)	0.0319 (13)	−0.0025 (9)	0.0003 (9)	0.0005 (9)
C8	0.0302 (11)	0.0282 (11)	0.0394 (14)	−0.0014 (9)	0.0051 (10)	0.0082 (10)
C9	0.0348 (12)	0.0313 (12)	0.0306 (13)	0.0075 (9)	0.0089 (10)	0.0065 (10)
C10	0.0347 (12)	0.0244 (11)	0.0239 (11)	0.0050 (9)	0.0010 (9)	0.0006 (9)
C11	0.0275 (10)	0.0210 (10)	0.0243 (11)	0.0008 (8)	0.0015 (8)	0.0045 (8)
C12	0.0327 (11)	0.0234 (11)	0.0374 (13)	−0.0030 (9)	−0.0020 (10)	−0.0040 (10)
C13	0.0330 (12)	0.0330 (12)	0.0332 (13)	0.0007 (9)	−0.0018 (10)	−0.0069 (10)
C14	0.0352 (13)	0.0426 (14)	0.0381 (14)	0.0067 (11)	0.0023 (11)	−0.0017 (11)
C15	0.0538 (18)	0.0570 (18)	0.0493 (18)	0.0244 (15)	−0.0087 (14)	−0.0133 (15)
C16	0.0363 (13)	0.0373 (14)	0.0526 (17)	0.0073 (11)	−0.0014 (12)	−0.0026 (12)
C17	0.0405 (15)	0.0418 (15)	0.062 (2)	−0.0031 (12)	−0.0019 (13)	−0.0028 (14)

O1—C17	1.198 (4)	C7—C8	1.394 (4)
O2—C17	1.330 (4)	C7—H7A	0.9500
O2—H2O	0.8400	C8—C9	1.389 (4)
O1W—H1W1	0.812 (19)	C8—H8A	0.9500
O1W—H1W2	0.817 (19)	C9—C10	1.394 (3)
N1—C1	1.302 (3)	C9—H9A	0.9500
N1—C11	1.440 (3)	C10—C11	1.381 (3)
N1—C12	1.476 (3)	C10—H10A	0.9500
C1—C2	1.476 (3)	C12—C13	1.528 (3)
C1—C3	1.516 (3)	C12—H12A	0.9900
C2—H2A	0.9800	C12—H12B	0.9900
C2—H2B	0.9800	C13—C14	1.524 (3)
C2—H2C	0.9800	C13—H13A	0.9900
C3—C6	1.507 (3)	C13—H13B	0.9900
C3—C5	1.536 (3)	C14—C15	1.518 (4)
C3—C4	1.545 (3)	C14—H14A	0.9900
C4—H4A	0.9800	C14—H14B	0.9900
C4—H4B	0.9800	C15—C16	1.526 (4)
C4—H4C	0.9800	C15—H15A	0.9900
C5—H5A	0.9800	C15—H15B	0.9900
C5—H5B	0.9800	C16—C17	1.493 (4)
C5—H5C	0.9800	C16—H16A	0.9900
C6—C11	1.382 (3)	C16—H16B	0.9900
C6—C7	1.382 (3)
C17—O2—H2O	109.5	C8—C9—H9A	119.4
H1W1—O1W—H1W2	104 (3)	C10—C9—H9A	119.4
C1—N1—C11	111.00 (19)	C11—C10—C9	115.8 (2)
C1—N1—C12	127.9 (2)	C11—C10—H10A	122.1
C11—N1—C12	120.96 (19)	C9—C10—H10A	122.1
N1—C1—C2	125.4 (2)	C10—C11—C6	124.3 (2)
N1—C1—C3	110.6 (2)	C10—C11—N1	127.7 (2)
C2—C1—C3	124.0 (2)	C6—C11—N1	108.0 (2)
C1—C2—H2A	109.5	N1—C12—C13	110.80 (19)
C1—C2—H2B	109.5	N1—C12—H12A	109.5
H2A—C2—H2B	109.5	C13—C12—H12A	109.5
C1—C2—H2C	109.5	N1—C12—H12B	109.5
H2A—C2—H2C	109.5	C13—C12—H12B	109.5
H2B—C2—H2C	109.5	H12A—C12—H12B	108.1
C6—C3—C1	101.18 (18)	C14—C13—C12	114.4 (2)
C6—C3—C5	112.9 (2)	C14—C13—H13A	108.7
C1—C3—C5	111.86 (19)	C12—C13—H13A	108.7
C6—C3—C4	111.20 (19)	C14—C13—H13B	108.7
C1—C3—C4	109.1 (2)	C12—C13—H13B	108.7
C5—C3—C4	110.3 (2)	H13A—C13—H13B	107.6
C3—C4—H4A	109.5	C15—C14—C13	112.6 (2)
C3—C4—H4B	109.5	C15—C14—H14A	109.1
H4A—C4—H4B	109.5	C13—C14—H14A	109.1
C3—C4—H4C	109.5	C15—C14—H14B	109.1
H4A—C4—H4C	109.5	C13—C14—H14B	109.1
H4B—C4—H4C	109.5	H14A—C14—H14B	107.8
C3—C5—H5A	109.5	C14—C15—C16	113.2 (3)
C3—C5—H5B	109.5	C14—C15—H15A	108.9
H5A—C5—H5B	109.5	C16—C15—H15A	108.9
C3—C5—H5C	109.5	C14—C15—H15B	108.9
H5A—C5—H5C	109.5	C16—C15—H15B	108.9
H5B—C5—H5C	109.5	H15A—C15—H15B	107.7
C11—C6—C7	119.3 (2)	C17—C16—C15	114.2 (3)
C11—C6—C3	109.15 (19)	C17—C16—H16A	108.7
C7—C6—C3	131.6 (2)	C15—C16—H16A	108.7
C6—C7—C8	118.1 (2)	C17—C16—H16B	108.7
C6—C7—H7A	120.9	C15—C16—H16B	108.7
C8—C7—H7A	120.9	H16A—C16—H16B	107.6
C9—C8—C7	121.3 (2)	O1—C17—O2	120.4 (3)
C9—C8—H8A	119.4	O1—C17—C16	124.5 (3)
C7—C8—H8A	119.4	O2—C17—C16	115.1 (3)
C8—C9—C10	121.3 (2)
C11—N1—C1—C2	−179.2 (2)	C8—C9—C10—C11	0.5 (3)
C12—N1—C1—C2	4.5 (4)	C9—C10—C11—C6	−0.7 (3)
C11—N1—C1—C3	1.0 (2)	C9—C10—C11—N1	−179.0 (2)
C12—N1—C1—C3	−175.3 (2)	C7—C6—C11—C10	0.2 (3)
N1—C1—C3—C6	−1.7 (2)	C3—C6—C11—C10	−180.0 (2)
C2—C1—C3—C6	178.4 (2)	C7—C6—C11—N1	178.82 (19)
N1—C1—C3—C5	−122.2 (2)	C3—C6—C11—N1	−1.4 (2)
C2—C1—C3—C5	58.0 (3)	C1—N1—C11—C10	178.8 (2)
N1—C1—C3—C4	115.6 (2)	C12—N1—C11—C10	−4.6 (3)
C2—C1—C3—C4	−64.3 (3)	C1—N1—C11—C6	0.3 (2)
C1—C3—C6—C11	1.9 (2)	C12—N1—C11—C6	176.90 (19)
C5—C3—C6—C11	121.6 (2)	C1—N1—C12—C13	99.2 (3)
C4—C3—C6—C11	−113.9 (2)	C11—N1—C12—C13	−76.8 (3)
C1—C3—C6—C7	−178.4 (2)	N1—C12—C13—C14	−64.4 (3)
C5—C3—C6—C7	−58.7 (3)	C12—C13—C14—C15	−174.0 (2)
C4—C3—C6—C7	65.8 (3)	C13—C14—C15—C16	−179.9 (3)
C11—C6—C7—C8	0.4 (3)	C14—C15—C16—C17	94.4 (4)
C3—C6—C7—C8	−179.3 (2)	C15—C16—C17—O1	8.5 (5)
C6—C7—C8—C9	−0.5 (4)	C15—C16—C17—O2	−172.8 (3)
C7—C8—C9—C10	0.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O1W	0.84	1.82	2.637 (4)	166
O1W—H1W1···Br	0.81 (2)	2.43 (2)	3.240 (2)	175 (5)
O1W—H1W2···Bri	0.82 (2)	2.47 (2)	3.262 (3)	165 (5)
C4—H4B···Cg2ii	0.99	2.88	3.828 (3)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O1W	0.84	1.82	2.637 (4)	166
O1W—H1W1⋯Br	0.812 (19)	2.431 (19)	3.240 (2)	175 (5)
O1W—H1W2⋯Bri	0.817 (19)	2.47 (2)	3.262 (3)	165 (5)
C4—H4B⋯Cg2i2	0.99	2.88	3.828 (3)	162

Symmetry code: (i) ; (ii) . Cg2 is the centroid of the C6–C11 ring.