2-(4-Bromo-phen-yl)-3,4-dihydro-isoquinolin-2-ium thio-cyanate hemihydrate.

In the title hemihydrated salt, C(15)H(13)BrN(+)·NCS(-)·0.5H(2)O, the two benzene rings are aligned at a dihedral angle of 46.9 (1)°. The six-membered heterocycle of the dihydro-isoquinoline unit adopts a half-chair conformation. The water mol-ecule and thio-cyanate ion are linked by O-H⋯N hydrogen bonds, generating a four-membered ring motif. In addition, C-H⋯O and C-H⋯S inter-actions link the components into a chain along the c axis. π-π inter-actions [centroid-centroid distance = 3.974 (2) Å] link the chains into sheets and further π-π [centroid-centroid distance = 3.746 (2) Å] and C-H⋯π inter-actions give rise to a three-dimensional nework.

Related literature

For the synthesis of the title compound, see: Ishii et al. (1985 ▶). For the biological activity of tetra­hydro­isoquinoline derivatives, see: Abe et al. (2005 ▶); Kamal et al. (2011 ▶); Lane et al. (2006 ▶); Liu et al. (2009) ▶; Storch et al. (2002) ▶; Jang et al. (2009) ▶.

Experimental

Crystal data

C15H13BrN+·NCS−·0.5H2O

M = 354.26

Triclinic,

a = 9.0211 (12) Å

b = 9.2685 (12) Å

c = 10.7284 (14) Å

α = 81.174 (2)°

β = 66.699 (1)°

γ = 68.368 (1)°

V = 765.81 (17) Å3

Z = 2

Mo Kα radiation

μ = 2.82 mm−1

T = 296 K

0.50 × 0.41 × 0.37 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.333, T max = 0.422

5705 measured reflections

2824 independent reflections

2262 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.100

S = 1.04

2824 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.54 e Å−3

Δρmin = −0.53 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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 datablock(s) global, I. DOI: 10.1107/S1600536811038542/ng5230sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038542/ng5230Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811038542/ng5230Isup3.cml

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

C15H13BrN+·CNS−·0.5H2O	Z = 2
Mr = 354.26	F(000) = 358
Triclinic, P1	Dx = 1.536 Mg m−3
a = 9.0211 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2685 (12) Å	Cell parameters from 2388 reflections
c = 10.7284 (14) Å	θ = 2.6–25.5°
α = 81.174 (2)°	µ = 2.82 mm−1
β = 66.699 (1)°	T = 296 K
γ = 68.368 (1)°	Block, yellow
V = 765.81 (17) Å3	0.50 × 0.41 × 0.37 mm

Bruker SMART APEXII CCD area-detector diffractometer	2824 independent reflections
Radiation source: fine-focus sealed tube	2262 reflections with I > 2σ(I)
graphite	Rint = 0.015
phi and ω scans	θmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.333, Tmax = 0.422	k = −11→11
5705 measured reflections	l = −12→12

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0542P)2 + 0.2978P] where P = (Fo2 + 2Fc2)/3
2824 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.53 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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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	Occ. (<1)
S1	0.93320 (15)	0.24168 (14)	0.06970 (15)	0.0945 (4)
N2	0.8517 (6)	0.1537 (4)	0.3422 (5)	0.0945 (12)
C16	0.8864 (5)	0.1895 (4)	0.2255 (6)	0.0872 (15)
O1	0.8821 (10)	−0.0376 (8)	0.5473 (7)	0.116 (2)	0.50
H1W	0.9000	0.0172	0.4752	0.174*	0.50
H2W	0.9526	−0.0671	0.5878	0.174*	0.50
C1	0.6164 (4)	0.7282 (3)	0.1329 (3)	0.0490 (7)
C2	0.5976 (4)	0.6630 (4)	0.0343 (3)	0.0606 (8)
H2	0.6783	0.5695	−0.0052	0.073*
C3	0.4598 (5)	0.7367 (5)	−0.0051 (3)	0.0662 (9)
H3	0.4470	0.6930	−0.0711	0.079*
C4	0.3401 (4)	0.8761 (4)	0.0538 (4)	0.0632 (9)
H4	0.2474	0.9260	0.0267	0.076*
C5	0.3568 (4)	0.9415 (4)	0.1519 (4)	0.0598 (8)
H5	0.2751	1.0350	0.1908	0.072*
C6	0.4943 (4)	0.8696 (3)	0.1936 (3)	0.0515 (7)
C7	0.5176 (4)	0.9260 (4)	0.3058 (4)	0.0660 (9)
H7A	0.4658	1.0382	0.3104	0.079*
H7B	0.4580	0.8836	0.3913	0.079*
C8	0.7013 (5)	0.8819 (4)	0.2877 (4)	0.0629 (9)
H8A	0.7538	0.9462	0.2169	0.076*
H8B	0.7081	0.9013	0.3713	0.076*
C9	0.7584 (4)	0.6529 (3)	0.1743 (3)	0.0491 (7)
H9	0.8271	0.5522	0.1445	0.059*
C10	0.9469 (4)	0.6359 (3)	0.2869 (3)	0.0449 (6)
C11	0.9916 (4)	0.4784 (3)	0.3128 (3)	0.0494 (7)
H11	0.9240	0.4245	0.3102	0.059*
C12	1.1367 (4)	0.4012 (3)	0.3427 (3)	0.0527 (7)
H12	1.1687	0.2947	0.3591	0.063*
C13	1.2341 (4)	0.4834 (4)	0.3479 (3)	0.0507 (7)
C14	1.1875 (4)	0.6411 (4)	0.3261 (3)	0.0606 (8)
H14	1.2528	0.6953	0.3324	0.073*
C15	1.0429 (4)	0.7188 (4)	0.2946 (3)	0.0581 (8)
H15	1.0108	0.8254	0.2787	0.070*
N1	0.7980 (3)	0.7159 (3)	0.2511 (2)	0.0453 (5)
Br1	1.43677 (4)	0.37833 (4)	0.38559 (4)	0.06978 (17)

	U11	U22	U33	U12	U13	U23
S1	0.0726 (7)	0.0938 (8)	0.1153 (9)	−0.0129 (6)	−0.0337 (6)	−0.0381 (7)
N2	0.128 (3)	0.070 (2)	0.126 (3)	−0.049 (2)	−0.083 (3)	0.028 (2)
C16	0.077 (3)	0.0439 (19)	0.169 (5)	−0.0073 (17)	−0.079 (3)	−0.017 (3)
O1	0.129 (6)	0.122 (5)	0.094 (4)	−0.048 (5)	−0.043 (4)	0.025 (4)
C1	0.0478 (16)	0.0527 (16)	0.0527 (17)	−0.0200 (13)	−0.0231 (13)	0.0025 (13)
C2	0.0553 (18)	0.071 (2)	0.0596 (19)	−0.0198 (16)	−0.0237 (16)	−0.0079 (16)
C3	0.063 (2)	0.093 (3)	0.0567 (19)	−0.035 (2)	−0.0304 (17)	0.0040 (18)
C4	0.0551 (19)	0.075 (2)	0.070 (2)	−0.0301 (18)	−0.0341 (17)	0.0235 (18)
C5	0.0534 (18)	0.0529 (17)	0.075 (2)	−0.0188 (14)	−0.0284 (16)	0.0091 (16)
C6	0.0513 (17)	0.0452 (16)	0.0610 (18)	−0.0181 (13)	−0.0249 (14)	0.0068 (13)
C7	0.063 (2)	0.0480 (17)	0.089 (3)	−0.0078 (15)	−0.0378 (19)	−0.0109 (17)
C8	0.072 (2)	0.0457 (17)	0.081 (2)	−0.0122 (15)	−0.0429 (19)	−0.0071 (15)
C9	0.0499 (16)	0.0464 (16)	0.0522 (17)	−0.0148 (13)	−0.0202 (14)	−0.0041 (13)
C10	0.0473 (15)	0.0500 (16)	0.0427 (15)	−0.0196 (13)	−0.0201 (12)	0.0019 (12)
C11	0.0534 (16)	0.0449 (16)	0.0541 (17)	−0.0156 (13)	−0.0229 (14)	−0.0059 (13)
C12	0.0562 (18)	0.0475 (16)	0.0515 (17)	−0.0120 (14)	−0.0203 (14)	−0.0055 (13)
C13	0.0446 (15)	0.0642 (19)	0.0420 (15)	−0.0158 (14)	−0.0181 (13)	0.0023 (13)
C14	0.064 (2)	0.069 (2)	0.069 (2)	−0.0383 (17)	−0.0360 (17)	0.0174 (16)
C15	0.066 (2)	0.0523 (17)	0.071 (2)	−0.0303 (15)	−0.0380 (17)	0.0173 (15)
N1	0.0501 (13)	0.0415 (12)	0.0505 (13)	−0.0173 (10)	−0.0235 (11)	0.0005 (10)
Br1	0.0550 (2)	0.0851 (3)	0.0708 (3)	−0.01661 (17)	−0.03359 (17)	0.00511 (18)

S1—C16	1.597 (6)	C7—H7B	0.9700
N2—C16	1.189 (6)	C8—N1	1.486 (4)
N2—O1	2.642 (8)	C8—H8A	0.9700
O1—H1W	0.8500	C8—H8B	0.9700
O1—H2W	0.8500	C9—N1	1.297 (4)
C1—C2	1.388 (4)	C9—H9	0.9300
C1—C6	1.409 (4)	C10—C11	1.379 (4)
C1—C9	1.422 (4)	C10—C15	1.384 (4)
C2—C3	1.376 (5)	C10—N1	1.444 (3)
C2—H2	0.9300	C11—C12	1.379 (4)
C3—C4	1.385 (5)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.379 (4)
C4—C5	1.374 (5)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.373 (4)
C5—C6	1.386 (4)	C13—Br1	1.899 (3)
C5—H5	0.9300	C14—C15	1.384 (4)
C6—C7	1.497 (5)	C14—H14	0.9300
C7—C8	1.490 (5)	C15—H15	0.9300
C7—H7A	0.9700
C16—N2—O1	154.6 (4)	N1—C8—H8A	109.2
N2—C16—S1	178.6 (4)	C7—C8—H8A	109.2
N2—O1—H1W	14.7	N1—C8—H8B	109.2
N2—O1—H2W	134.1	C7—C8—H8B	109.2
H1W—O1—H2W	120.7	H8A—C8—H8B	107.9
C2—C1—C6	120.3 (3)	N1—C9—C1	124.0 (3)
C2—C1—C9	120.5 (3)	N1—C9—H9	118.0
C6—C1—C9	119.2 (3)	C1—C9—H9	118.0
C3—C2—C1	120.1 (3)	C11—C10—C15	120.9 (3)
C3—C2—H2	120.0	C11—C10—N1	119.8 (2)
C1—C2—H2	120.0	C15—C10—N1	119.4 (2)
C2—C3—C4	119.7 (3)	C12—C11—C10	119.8 (3)
C2—C3—H3	120.1	C12—C11—H11	120.1
C4—C3—H3	120.1	C10—C11—H11	120.1
C5—C4—C3	120.8 (3)	C11—C12—C13	119.3 (3)
C5—C4—H4	119.6	C11—C12—H12	120.4
C3—C4—H4	119.6	C13—C12—H12	120.4
C4—C5—C6	120.6 (3)	C14—C13—C12	121.2 (3)
C4—C5—H5	119.7	C14—C13—Br1	118.9 (2)
C6—C5—H5	119.7	C12—C13—Br1	119.9 (2)
C5—C6—C1	118.5 (3)	C13—C14—C15	119.7 (3)
C5—C6—C7	124.6 (3)	C13—C14—H14	120.2
C1—C6—C7	116.8 (3)	C15—C14—H14	120.2
C8—C7—C6	113.0 (3)	C10—C15—C14	119.2 (3)
C8—C7—H7A	109.0	C10—C15—H15	120.4
C6—C7—H7A	109.0	C14—C15—H15	120.4
C8—C7—H7B	109.0	C9—N1—C10	121.8 (2)
C6—C7—H7B	109.0	C9—N1—C8	118.7 (2)
H7A—C7—H7B	107.8	C10—N1—C8	118.9 (2)
N1—C8—C7	111.9 (3)
O1—N2—C16—S1	−134 (17)	N1—C10—C11—C12	177.9 (3)
C6—C1—C2—C3	0.3 (5)	C10—C11—C12—C13	0.8 (4)
C9—C1—C2—C3	179.9 (3)	C11—C12—C13—C14	1.0 (5)
C1—C2—C3—C4	0.1 (5)	C11—C12—C13—Br1	−178.8 (2)
C2—C3—C4—C5	−0.4 (5)	C12—C13—C14—C15	−1.8 (5)
C3—C4—C5—C6	0.3 (5)	Br1—C13—C14—C15	178.1 (3)
C4—C5—C6—C1	0.1 (5)	C11—C10—C15—C14	1.3 (5)
C4—C5—C6—C7	−175.8 (3)	N1—C10—C15—C14	−178.6 (3)
C2—C1—C6—C5	−0.4 (4)	C13—C14—C15—C10	0.6 (5)
C9—C1—C6—C5	179.9 (3)	C1—C9—N1—C10	−178.1 (3)
C2—C1—C6—C7	175.8 (3)	C1—C9—N1—C8	−6.4 (4)
C9—C1—C6—C7	−3.8 (4)	C11—C10—N1—C9	−37.9 (4)
C5—C6—C7—C8	−151.8 (3)	C15—C10—N1—C9	142.1 (3)
C1—C6—C7—C8	32.3 (4)	C11—C10—N1—C8	150.5 (3)
C6—C7—C8—N1	−46.7 (4)	C15—C10—N1—C8	−29.6 (4)
C2—C1—C9—N1	170.0 (3)	C7—C8—N1—C9	35.1 (4)
C6—C1—C9—N1	−10.3 (4)	C7—C8—N1—C10	−152.9 (3)
C15—C10—C11—C12	−2.0 (4)

Cg2 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···N2	0.85	1.83	2.642 (8)	159.
O1—H2W···N2i	0.85	2.04	2.879 (9)	171.
C5—H5···O1ii	0.93	2.60	3.133 (8)	117
C9—H9···S1	0.93	2.81	3.709 (3)	162
C12—H12···O1i	0.93	2.57	3.438 (8)	156
C14—H14···Cg2iii	0.93	2.87	3.447 (4)	121

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯N2	0.85	1.83	2.642 (8)	159
O1—H2W⋯N2i	0.85	2.04	2.879 (9)	171
C5—H5⋯O1ii	0.93	2.60	3.133 (8)	117
C9—H9⋯S1	0.93	2.81	3.709 (3)	162
C12—H12⋯O1i	0.93	2.57	3.438 (8)	156
C14—H14⋯Cg2iii	0.93	2.87	3.447 (4)	121

Symmetry codes: (i) ; (ii) ; (iii) .