1-[1-(4-Bromo-phen-yl)ethyl-idene]-4-(2,4-dimeth-oxy-phen-yl)thio-semicarbazide.

In the title compound, C(17)H(18)BrN(3)O(2)S, the dihedral angle between the aromatic rings is 9.15 (17)°. A bifurcated intra-molecular N-H⋯(N,O) hydrogen bond generates two S(5) rings and a weak intra-molecular C-H⋯S inter-action completes an S(6) ring motif. In the crystal, inversion dimers linked by pairs of N-H⋯S hydrogen bonds generate R(2) (2)(8) loops and weak C-H⋯S and C-H⋯π inter-actions are also present.

Related literature

For the pharmacological applications of thio­semicarbazones see: Beraldo & Gambino (2004 ▶); Pervez et al. (2008 ▶, 2010a ▶,b ▶). For related structures, see: Jian et al. (2005 ▶); Martínez et al. (2006 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C17H18BrN3O2S

M = 408.31

Monoclinic,

a = 5.8390 (2) Å

b = 30.3335 (11) Å

c = 9.9423 (4) Å

β = 94.910 (2)°

V = 1754.49 (11) Å3

Z = 4

Mo Kα radiation

μ = 2.48 mm−1

T = 296 K

0.25 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.642, T max = 0.652

17115 measured reflections

4346 independent reflections

2654 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.100

S = 1.01

4346 reflections

220 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810022622/hb5499sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810022622/hb5499Isup2.hkl

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

C17H18BrN3O2S	F(000) = 832
Mr = 408.31	Dx = 1.546 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2654 reflections
a = 5.8390 (2) Å	θ = 2.2–28.3°
b = 30.3335 (11) Å	µ = 2.48 mm−1
c = 9.9423 (4) Å	T = 296 K
β = 94.910 (2)°	Prism, colorless
V = 1754.49 (11) Å3	0.25 × 0.22 × 0.20 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	4346 independent reflections
Radiation source: fine-focus sealed tube	2654 reflections with I > 2σ(I)
graphite	Rint = 0.044
Detector resolution: 7.5 pixels mm-1	θmax = 28.3°, θmin = 2.2°
ω scans	h = −4→7
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −40→40
Tmin = 0.642, Tmax = 0.652	l = −13→13
17115 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0413P)2 + 0.4088P] where P = (Fo2 + 2Fc2)/3
4346 reflections	(Δ/σ)max = 0.001
220 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
Br1	1.68144 (7)	0.28876 (1)	0.66065 (3)	0.0846 (1)
S1	0.69373 (12)	0.00989 (2)	0.87217 (7)	0.0577 (2)
O1	0.7242 (3)	0.14610 (6)	0.55058 (18)	0.0598 (7)
O2	0.0390 (3)	0.09126 (7)	0.3147 (2)	0.0710 (8)
N1	0.7530 (3)	0.08160 (7)	0.7192 (2)	0.0504 (7)
N2	1.0174 (3)	0.06989 (7)	0.8946 (2)	0.0490 (7)
N3	1.1192 (3)	0.10729 (7)	0.8520 (2)	0.0465 (7)
C1	0.5629 (4)	0.08091 (8)	0.6222 (2)	0.0453 (8)
C2	0.3956 (5)	0.04927 (10)	0.6085 (3)	0.0684 (11)
C3	0.2178 (5)	0.05173 (10)	0.5075 (3)	0.0707 (11)
C4	0.2059 (4)	0.08609 (9)	0.4186 (3)	0.0536 (9)
C5	0.3721 (4)	0.11870 (9)	0.4316 (3)	0.0519 (9)
C6	0.5493 (4)	0.11606 (8)	0.5315 (2)	0.0449 (8)
C7	0.7459 (5)	0.17845 (10)	0.4497 (3)	0.0718 (11)
C8	−0.1278 (5)	0.05715 (11)	0.2945 (3)	0.0714 (11)
C9	0.8214 (4)	0.05526 (8)	0.8225 (2)	0.0426 (8)
C10	1.2991 (4)	0.12299 (8)	0.9180 (2)	0.0413 (8)
C11	1.3922 (4)	0.16334 (8)	0.8596 (2)	0.0397 (7)
C12	1.2659 (4)	0.18592 (9)	0.7571 (3)	0.0522 (9)
C13	1.3493 (5)	0.22333 (9)	0.7001 (3)	0.0585 (10)
C14	1.5632 (4)	0.23844 (9)	0.7440 (3)	0.0511 (9)
C15	1.6935 (5)	0.21732 (9)	0.8453 (3)	0.0560 (10)
C16	1.6074 (4)	0.17997 (9)	0.9025 (3)	0.0508 (9)
C17	1.4082 (5)	0.10312 (9)	1.0456 (3)	0.0565 (9)
H1	0.84389	0.10350	0.71009	0.0605*
H2	0.40157	0.02564	0.66831	0.0820*
H2A	1.07456	0.05588	0.96481	0.0587*
H3	0.10583	0.02985	0.50022	0.0849*
H5	0.36375	0.14251	0.37241	0.0623*
H7A	0.61321	0.19727	0.44397	0.1075*
H7B	0.75783	0.16426	0.36429	0.1075*
H7C	0.88133	0.19576	0.47252	0.1075*
H8A	−0.21919	0.05609	0.37027	0.1075*
H8B	−0.05148	0.02938	0.28602	0.1075*
H8C	−0.22514	0.06296	0.21373	0.1075*
H12	1.12106	0.17552	0.72613	0.0626*
H13	1.26085	0.23820	0.63226	0.0701*
H15	1.83820	0.22799	0.87536	0.0672*
H16	1.69579	0.16564	0.97145	0.0610*
H17A	1.48971	0.07685	1.02462	0.0848*
H17B	1.29134	0.09589	1.10418	0.0848*
H17C	1.51361	0.12388	1.08973	0.0848*

	U11	U22	U33	U12	U13	U23
Br1	0.1088 (3)	0.0700 (2)	0.0736 (2)	−0.0456 (2)	0.0001 (2)	0.0106 (2)
S1	0.0585 (4)	0.0489 (4)	0.0642 (4)	−0.0114 (3)	−0.0030 (3)	0.0194 (3)
O1	0.0677 (12)	0.0508 (11)	0.0587 (12)	−0.0148 (9)	−0.0080 (9)	0.0172 (9)
O2	0.0668 (12)	0.0697 (14)	0.0712 (13)	0.0015 (11)	−0.0242 (10)	0.0076 (11)
N1	0.0543 (12)	0.0453 (12)	0.0496 (12)	−0.0150 (10)	−0.0074 (10)	0.0128 (10)
N2	0.0522 (12)	0.0458 (12)	0.0470 (12)	−0.0095 (10)	−0.0066 (10)	0.0129 (10)
N3	0.0493 (12)	0.0431 (12)	0.0464 (12)	−0.0070 (9)	−0.0005 (10)	0.0087 (9)
C1	0.0483 (14)	0.0439 (14)	0.0429 (13)	−0.0044 (11)	−0.0008 (11)	0.0061 (11)
C2	0.077 (2)	0.0571 (18)	0.0670 (19)	−0.0215 (15)	−0.0181 (16)	0.0215 (15)
C3	0.0721 (19)	0.063 (2)	0.072 (2)	−0.0253 (16)	−0.0223 (16)	0.0155 (16)
C4	0.0529 (16)	0.0520 (16)	0.0540 (16)	0.0031 (12)	−0.0056 (13)	−0.0032 (13)
C5	0.0644 (17)	0.0443 (14)	0.0462 (15)	0.0062 (12)	−0.0006 (13)	0.0072 (11)
C6	0.0517 (15)	0.0390 (13)	0.0442 (14)	−0.0022 (11)	0.0051 (12)	0.0012 (10)
C7	0.090 (2)	0.0543 (19)	0.070 (2)	−0.0172 (16)	0.0010 (17)	0.0197 (15)
C8	0.0591 (18)	0.076 (2)	0.075 (2)	0.0018 (16)	−0.0180 (15)	−0.0104 (17)
C9	0.0461 (14)	0.0407 (13)	0.0412 (13)	−0.0013 (10)	0.0043 (11)	0.0027 (10)
C10	0.0435 (14)	0.0416 (13)	0.0384 (13)	0.0037 (10)	0.0018 (11)	−0.0006 (10)
C11	0.0417 (13)	0.0388 (13)	0.0384 (12)	−0.0005 (10)	0.0025 (10)	−0.0044 (10)
C12	0.0475 (15)	0.0506 (15)	0.0572 (16)	−0.0094 (12)	−0.0030 (12)	0.0095 (13)
C13	0.0617 (18)	0.0552 (17)	0.0567 (17)	−0.0082 (13)	−0.0053 (14)	0.0109 (13)
C14	0.0603 (16)	0.0469 (15)	0.0465 (15)	−0.0135 (12)	0.0075 (13)	−0.0047 (12)
C15	0.0539 (16)	0.0591 (18)	0.0544 (16)	−0.0181 (13)	0.0004 (13)	−0.0090 (13)
C16	0.0507 (15)	0.0525 (16)	0.0480 (14)	−0.0024 (12)	−0.0029 (12)	0.0005 (12)
C17	0.0650 (17)	0.0505 (16)	0.0515 (16)	−0.0036 (13)	−0.0099 (13)	0.0063 (12)

Br1—C14	1.895 (3)	C11—C12	1.387 (4)
S1—C9	1.660 (2)	C12—C13	1.376 (4)
O1—C6	1.370 (3)	C13—C14	1.366 (4)
O1—C7	1.417 (3)	C14—C15	1.368 (4)
O2—C4	1.367 (3)	C15—C16	1.382 (4)
O2—C8	1.423 (4)	C2—H2	0.9300
N1—C1	1.407 (3)	C3—H3	0.9300
N1—C9	1.335 (3)	C5—H5	0.9300
N2—N3	1.365 (3)	C7—H7A	0.9600
N2—C9	1.371 (3)	C7—H7B	0.9600
N3—C10	1.282 (3)	C7—H7C	0.9600
N1—H1	0.8600	C8—H8A	0.9600
N2—H2A	0.8600	C8—H8B	0.9600
C1—C2	1.368 (4)	C8—H8C	0.9600
C1—C6	1.394 (3)	C12—H12	0.9300
C2—C3	1.383 (4)	C13—H13	0.9300
C3—C4	1.365 (4)	C15—H15	0.9300
C4—C5	1.384 (4)	C16—H16	0.9300
C5—C6	1.374 (3)	C17—H17A	0.9600
C10—C11	1.478 (3)	C17—H17B	0.9600
C10—C17	1.497 (4)	C17—H17C	0.9600
C11—C16	1.387 (3)
C6—O1—C7	118.27 (19)	C14—C15—C16	119.2 (3)
C4—O2—C8	117.3 (2)	C11—C16—C15	121.6 (3)
C1—N1—C9	133.2 (2)	C1—C2—H2	119.00
N3—N2—C9	118.23 (19)	C3—C2—H2	119.00
N2—N3—C10	120.6 (2)	C2—C3—H3	120.00
C9—N1—H1	113.00	C4—C3—H3	120.00
C1—N1—H1	113.00	C4—C5—H5	120.00
N3—N2—H2A	121.00	C6—C5—H5	120.00
C9—N2—H2A	121.00	O1—C7—H7A	109.00
C2—C1—C6	118.1 (2)	O1—C7—H7B	109.00
N1—C1—C6	115.5 (2)	O1—C7—H7C	109.00
N1—C1—C2	126.4 (2)	H7A—C7—H7B	109.00
C1—C2—C3	121.3 (3)	H7A—C7—H7C	109.00
C2—C3—C4	120.3 (3)	H7B—C7—H7C	109.00
O2—C4—C3	124.8 (2)	O2—C8—H8A	109.00
O2—C4—C5	115.9 (2)	O2—C8—H8B	109.00
C3—C4—C5	119.3 (3)	O2—C8—H8C	109.00
C4—C5—C6	120.3 (3)	H8A—C8—H8B	109.00
O1—C6—C5	124.6 (2)	H8A—C8—H8C	109.00
C1—C6—C5	120.7 (2)	H8B—C8—H8C	109.00
O1—C6—C1	114.75 (19)	C11—C12—H12	119.00
S1—C9—N1	127.77 (18)	C13—C12—H12	119.00
S1—C9—N2	119.25 (17)	C12—C13—H13	120.00
N1—C9—N2	112.9 (2)	C14—C13—H13	120.00
C11—C10—C17	121.5 (2)	C14—C15—H15	120.00
N3—C10—C11	114.80 (19)	C16—C15—H15	120.00
N3—C10—C17	123.7 (2)	C11—C16—H16	119.00
C10—C11—C16	122.3 (2)	C15—C16—H16	119.00
C12—C11—C16	117.2 (2)	C10—C17—H17A	109.00
C10—C11—C12	120.5 (2)	C10—C17—H17B	109.00
C11—C12—C13	121.7 (2)	C10—C17—H17C	109.00
C12—C13—C14	119.4 (3)	H17A—C17—H17B	109.00
Br1—C14—C13	119.2 (2)	H17A—C17—H17C	109.00
C13—C14—C15	120.9 (3)	H17B—C17—H17C	110.00
Br1—C14—C15	119.90 (19)
C7—O1—C6—C1	169.2 (2)	C2—C3—C4—O2	179.3 (3)
C7—O1—C6—C5	−10.1 (3)	C2—C3—C4—C5	−0.8 (4)
C8—O2—C4—C3	−3.1 (4)	O2—C4—C5—C6	−178.9 (2)
C8—O2—C4—C5	176.9 (2)	C3—C4—C5—C6	1.1 (4)
C9—N1—C1—C2	−2.8 (4)	C4—C5—C6—O1	178.5 (2)
C9—N1—C1—C6	178.0 (2)	C4—C5—C6—C1	−0.8 (4)
C1—N1—C9—S1	0.2 (4)	N3—C10—C11—C12	11.5 (3)
C1—N1—C9—N2	−177.7 (2)	N3—C10—C11—C16	−167.7 (2)
C9—N2—N3—C10	178.1 (2)	C17—C10—C11—C12	−167.6 (2)
N3—N2—C9—S1	−179.91 (16)	C17—C10—C11—C16	13.1 (4)
N3—N2—C9—N1	−1.8 (3)	C10—C11—C12—C13	−179.4 (2)
N2—N3—C10—C11	179.44 (19)	C16—C11—C12—C13	−0.1 (4)
N2—N3—C10—C17	−1.4 (3)	C10—C11—C16—C15	178.9 (2)
N1—C1—C2—C3	−179.0 (3)	C12—C11—C16—C15	−0.3 (4)
C6—C1—C2—C3	0.2 (4)	C11—C12—C13—C14	0.9 (4)
N1—C1—C6—O1	0.1 (3)	C12—C13—C14—Br1	177.8 (2)
N1—C1—C6—C5	179.5 (2)	C12—C13—C14—C15	−1.2 (4)
C2—C1—C6—O1	−179.3 (2)	Br1—C14—C15—C16	−178.2 (2)
C2—C1—C6—C5	0.2 (4)	C13—C14—C15—C16	0.7 (4)
C1—C2—C3—C4	0.1 (4)	C14—C15—C16—C11	0.1 (4)

Cg1 is the centroid of C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	2.12	2.573 (3)	113
N1—H1···N3	0.86	2.05	2.538 (3)	115
N2—H2A···S1i	0.86	2.84	3.662 (2)	161
C2—H2···S1	0.93	2.58	3.248 (3)	129
C17—H17A···S1ii	0.96	2.86	3.774 (3)	161
C8—H8A···Cg1iii	0.96	2.98	3.860 (3)	153

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	2.12	2.573 (3)	113
N1—H1⋯N3	0.86	2.05	2.538 (3)	115
N2—H2A⋯S1i	0.86	2.84	3.662 (2)	161
C2—H2⋯S1	0.93	2.58	3.248 (3)	129
C17—H17A⋯S1ii	0.96	2.86	3.774 (3)	161
C8—H8A⋯Cg1iii	0.96	2.98	3.860 (3)	153

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