Literature DB >> 24046713

rac-1-(5-Bromo-2-hy-droxy-phen-yl)-1-oxopropan-2-yl morpholine-4-carbo-dithio-ate.

Laura G Sarbu¹, Cristian G Hrib, Lucian M Birsa.

Abstract

In the racemic title compound, C14H16BrNO3S2, synthesized from the corresponding ω-bromo-propio-phenone, the dihedral angle between the plane of the phenol group and that of the planar section [maximum deviation = 0.040 (2) Å] of the morpholine-4-carbodi-thiol-ate moiety is 76.36 (10)°. A strong intra-molecular phenol O-H⋯O hydrogen bond if present in the mol-ecule. In the crystal, only weak C-H⋯S and C-H⋯O inter-actions are found.

Entities: CellLine Chemical Disease Gene

Year: 2013 PMID： 24046713 PMCID： PMC3770428 DOI： 10.1107/S1600536813017509

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For the synthesis and applications of dithiocarbamates, see: Buu-Hoi & Lavit (1955 ▶); WHO (1998 ▶). For applications of 1,3-dithiolium salts, see: Narita & Pittman (1976 ▶); Birsa & Asaftei (2008 ▶). For the structure of a related morpholine-4-carbodithioate, see: Bahrin et al. (2012 ▶).

Experimental

Crystal data

C14H16BrNO3S2 M = 390.31 Monoclinic, a = 11.182 (2) Å b = 19.660 (4) Å c = 7.4593 (15) Å β = 105.44 (3)° V = 1580.6 (5) Å3 Z = 4 Mo Kα radiation μ = 2.87 mm−1 T = 153 K 0.54 × 0.48 × 0.30 mm

Data collection

Stoe IPDS 2T area-detector diffractometer Absorption correction: for a sphere [modification of the interpolation procedure of Dwiggins (1975 ▶)] T min = 0.114, T max = 0.140 17019 measured reflections 4246 independent reflections 3807 reflections with I > 2σ(I) R int = 0.072

Refinement

R[F 2 > 2σ(F 2)] = 0.045 wR(F 2) = 0.102 S = 1.16 4246 reflections 195 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.71 e Å−3 Δρmin = −0.78 e Å−3 Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97. Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813017509/zs2265sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813017509/zs2265Isup2.hkl Click here for additional data file. Supplementary material file. DOI: 10.1107/S1600536813017509/zs2265Isup3.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₄H₁₆BrNO₃S₂	F(000) = 792
M_r = 390.31	D_x = 1.640 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 412–413 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.182 (2) Å	Cell parameters from 26120 reflections
b = 19.660 (4) Å	θ = 2.2–29.7°
c = 7.4593 (15) Å	µ = 2.87 mm⁻¹
β = 105.44 (3)°	T = 153 K
V = 1580.6 (5) Å³	Prism, colourless
Z = 4	0.54 × 0.48 × 0.30 mm

Stoe IPDS 2T area-detector diffractometer	4246 independent reflections
Radiation source: fine-focus sealed tube	3807 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
Detector resolution: 6.67 pixels mm^-1	θ_max = 29.2°, θ_min = 2.8°
rotation method scans	h = −15→13
Absorption correction: for a sphere [modification of the interpolation procedure of Dwiggins (1975)]	k = −25→26
T_min = 0.114, T_max = 0.140	l = −10→10
17019 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ²(F_o²) + (0.0355P)² + 1.2363P] where P = (F_o² + 2F_c²)/3
4246 reflections	(Δ/σ)_max = 0.001
195 parameters	Δρ_max = 0.71 e Å⁻³
0 restraints	Δρ_min = −0.78 e Å⁻³

Experimental. Absorption correction: interpolation using International Tables Vol C, Table 6.3.3.3 for values of muR in the range 0-2.5, and International Tables Vol. II, Table 5.3.6 B for µR in the range 2.6-10.0. The interpolation procedure (Dwiggins, 1975) was used with some modification.

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	U_iso*/U_eq
N	0.7046 (2)	0.59260 (10)	−0.3669 (3)	0.0291 (4)
Br	0.94733 (3)	0.200387 (14)	0.15953 (5)	0.04007 (10)
S1	0.82823 (6)	0.55807 (3)	−0.03082 (8)	0.02727 (13)
S2	0.72078 (6)	0.45824 (3)	−0.33614 (9)	0.03161 (15)
O1	0.50712 (18)	0.37914 (11)	0.1313 (3)	0.0344 (4)
H1	0.525 (4)	0.416 (2)	0.120 (6)	0.059 (13)*
O2	0.63809 (17)	0.48119 (9)	0.0864 (3)	0.0316 (4)
O3	0.6883 (2)	0.70107 (9)	−0.6200 (3)	0.0378 (5)
C1	0.7188 (2)	0.36994 (12)	0.1107 (3)	0.0243 (4)
C2	0.6083 (2)	0.34177 (13)	0.1327 (3)	0.0269 (5)
C3	0.5990 (3)	0.27144 (14)	0.1556 (4)	0.0320 (5)
H3	0.5233	0.2522	0.1665	0.038*
C4	0.6994 (3)	0.23020 (13)	0.1624 (4)	0.0320 (5)
H4	0.6934	0.1826	0.1794	0.038*
C5	0.8095 (2)	0.25820 (12)	0.1445 (3)	0.0281 (5)
C6	0.8199 (2)	0.32679 (13)	0.1174 (3)	0.0269 (5)
H6	0.8955	0.3450	0.1031	0.032*
C7	0.7261 (2)	0.44422 (12)	0.0859 (3)	0.0246 (4)
C8	0.8494 (2)	0.47533 (12)	0.0777 (3)	0.0255 (4)
H8	0.8923	0.4444	0.0084	0.031*
C9	0.7432 (2)	0.53841 (11)	−0.2621 (3)	0.0238 (4)
C10	0.7202 (3)	0.66338 (12)	−0.3028 (4)	0.0359 (6)
H10A	0.7798	0.6655	−0.1782	0.043*
H10B	0.6397	0.6816	−0.2927	0.043*
C11	0.7672 (3)	0.70563 (12)	−0.4379 (4)	0.0311 (5)
H11A	0.7733	0.7537	−0.3972	0.037*
H11B	0.8513	0.6900	−0.4379	0.037*
C12	0.6805 (3)	0.63236 (14)	−0.6823 (4)	0.0393 (7)
H12A	0.7643	0.6159	−0.6817	0.047*
H12B	0.6274	0.6299	−0.8116	0.047*
C13	0.6270 (3)	0.58721 (13)	−0.5588 (4)	0.0353 (6)
H13A	0.5411	0.6015	−0.5652	0.042*
H13B	0.6249	0.5394	−0.6016	0.042*
C14	0.9305 (3)	0.48568 (15)	0.2771 (4)	0.0332 (5)
H14A	0.8848	0.5126	0.3476	0.050*
H14B	1.0067	0.5097	0.2740	0.050*
H14C	0.9517	0.4413	0.3372	0.050*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0470 (13)	0.0183 (9)	0.0238 (9)	−0.0032 (8)	0.0125 (9)	−0.0015 (7)
Br	0.03949 (16)	0.03294 (15)	0.04765 (17)	0.00946 (11)	0.01139 (12)	0.00128 (11)
S1	0.0348 (3)	0.0231 (3)	0.0248 (3)	−0.0061 (2)	0.0095 (2)	−0.0022 (2)
S2	0.0381 (3)	0.0189 (2)	0.0340 (3)	−0.0042 (2)	0.0029 (3)	−0.0027 (2)
O1	0.0267 (9)	0.0330 (10)	0.0462 (11)	−0.0017 (7)	0.0143 (8)	0.0047 (8)
O2	0.0280 (9)	0.0295 (9)	0.0393 (10)	0.0013 (7)	0.0127 (8)	0.0029 (7)
O3	0.0579 (13)	0.0268 (9)	0.0293 (9)	0.0021 (8)	0.0125 (9)	0.0056 (7)
C1	0.0268 (11)	0.0257 (10)	0.0202 (9)	−0.0017 (8)	0.0058 (8)	0.0018 (8)
C2	0.0256 (11)	0.0304 (11)	0.0241 (10)	−0.0029 (9)	0.0056 (9)	0.0017 (9)
C3	0.0311 (12)	0.0326 (12)	0.0329 (12)	−0.0058 (10)	0.0096 (10)	0.0015 (10)
C4	0.0391 (14)	0.0263 (11)	0.0300 (12)	−0.0037 (10)	0.0080 (11)	0.0019 (9)
C5	0.0326 (12)	0.0269 (11)	0.0242 (11)	0.0037 (9)	0.0063 (9)	0.0013 (9)
C6	0.0257 (11)	0.0294 (11)	0.0245 (10)	−0.0014 (9)	0.0049 (9)	−0.0002 (9)
C7	0.0247 (11)	0.0260 (10)	0.0232 (10)	−0.0024 (8)	0.0067 (8)	0.0014 (8)
C8	0.0254 (11)	0.0263 (10)	0.0256 (10)	−0.0020 (9)	0.0082 (9)	0.0013 (8)
C9	0.0271 (11)	0.0206 (9)	0.0263 (10)	−0.0040 (8)	0.0117 (9)	−0.0005 (8)
C10	0.0671 (19)	0.0182 (10)	0.0289 (12)	−0.0029 (11)	0.0240 (13)	0.0000 (9)
C11	0.0418 (14)	0.0247 (11)	0.0306 (12)	−0.0031 (10)	0.0161 (11)	−0.0006 (9)
C12	0.062 (2)	0.0291 (12)	0.0234 (11)	0.0014 (12)	0.0061 (12)	−0.0007 (9)
C13	0.0399 (14)	0.0272 (12)	0.0335 (13)	−0.0032 (10)	0.0006 (11)	0.0011 (10)
C14	0.0287 (12)	0.0398 (14)	0.0292 (11)	−0.0039 (10)	0.0044 (10)	0.0007 (10)

N—C9	1.324 (3)	C4—H4	0.9500
N—C10	1.467 (3)	C5—C6	1.373 (3)
N—C13	1.467 (3)	C6—H6	0.9500
Br—C5	1.894 (3)	C7—C8	1.524 (3)
S1—C9	1.776 (2)	C8—C14	1.536 (3)
S1—C8	1.804 (2)	C8—H8	1.0000
S2—C9	1.667 (2)	C10—C11	1.504 (3)
O1—C2	1.346 (3)	C10—H10A	0.9900
O1—H1	0.77 (4)	C10—H10B	0.9900
O2—C7	1.224 (3)	C11—H11A	0.9900
O3—C11	1.412 (3)	C11—H11B	0.9900
O3—C12	1.424 (3)	C12—C13	1.512 (4)
C1—C6	1.403 (3)	C12—H12A	0.9900
C1—C2	1.404 (3)	C12—H12B	0.9900
C1—C7	1.477 (3)	C13—H13A	0.9900
C2—C3	1.400 (4)	C13—H13B	0.9900
C3—C4	1.375 (4)	C14—H14A	0.9800
C3—H3	0.9500	C14—H14B	0.9800
C4—C5	1.387 (4)	C14—H14C	0.9800

C9—N—C10	125.4 (2)	N—C9—S2	124.63 (19)
C9—N—C13	122.2 (2)	N—C9—S1	113.86 (17)
C10—N—C13	112.0 (2)	S2—C9—S1	121.47 (14)
C9—S1—C8	102.22 (11)	N—C10—C11	109.7 (2)
C2—O1—H1	106 (3)	N—C10—H10A	109.7
C11—O3—C12	110.0 (2)	C11—C10—H10A	109.7
C6—C1—C2	118.9 (2)	N—C10—H10B	109.7
C6—C1—C7	122.1 (2)	C11—C10—H10B	109.7
C2—C1—C7	118.9 (2)	H10A—C10—H10B	108.2
O1—C2—C3	116.8 (2)	O3—C11—C10	111.7 (2)
O1—C2—C1	123.2 (2)	O3—C11—H11A	109.3
C3—C2—C1	120.0 (2)	C10—C11—H11A	109.3
C4—C3—C2	120.0 (2)	O3—C11—H11B	109.3
C4—C3—H3	120.0	C10—C11—H11B	109.3
C2—C3—H3	120.0	H11A—C11—H11B	107.9
C3—C4—C5	120.0 (2)	O3—C12—C13	111.0 (2)
C3—C4—H4	120.0	O3—C12—H12A	109.4
C5—C4—H4	120.0	C13—C12—H12A	109.4
C6—C5—C4	121.1 (2)	O3—C12—H12B	109.4
C6—C5—Br	119.9 (2)	C13—C12—H12B	109.4
C4—C5—Br	119.03 (19)	H12A—C12—H12B	108.0
C5—C6—C1	120.0 (2)	N—C13—C12	109.0 (2)
C5—C6—H6	120.0	N—C13—H13A	109.9
C1—C6—H6	120.0	C12—C13—H13A	109.9
O2—C7—C1	121.1 (2)	N—C13—H13B	109.9
O2—C7—C8	119.9 (2)	C12—C13—H13B	109.9
C1—C7—C8	118.8 (2)	H13A—C13—H13B	108.3
C7—C8—C14	108.8 (2)	C8—C14—H14A	109.5
C7—C8—S1	111.58 (17)	C8—C14—H14B	109.5
C14—C8—S1	106.75 (17)	H14A—C14—H14B	109.5
C7—C8—H8	109.9	C8—C14—H14C	109.5
C14—C8—H8	109.9	H14A—C14—H14C	109.5
S1—C8—H8	109.9	H14B—C14—H14C	109.5

C6—C1—C2—O1	178.9 (2)	O2—C7—C8—S1	−25.7 (3)
C7—C1—C2—O1	0.4 (3)	C1—C7—C8—S1	159.95 (17)
C6—C1—C2—C3	−1.8 (3)	C9—S1—C8—C7	−65.12 (19)
C7—C1—C2—C3	179.7 (2)	C9—S1—C8—C14	176.19 (17)
O1—C2—C3—C4	−178.6 (2)	C10—N—C9—S2	178.1 (2)
C1—C2—C3—C4	2.1 (4)	C13—N—C9—S2	5.6 (4)
C2—C3—C4—C5	−0.7 (4)	C10—N—C9—S1	−4.1 (3)
C3—C4—C5—C6	−0.9 (4)	C13—N—C9—S1	−176.5 (2)
C3—C4—C5—Br	178.7 (2)	C8—S1—C9—N	173.43 (19)
C4—C5—C6—C1	1.2 (4)	C8—S1—C9—S2	−8.64 (18)
Br—C5—C6—C1	−178.47 (18)	C9—N—C10—C11	133.4 (3)
C2—C1—C6—C5	0.2 (3)	C13—N—C10—C11	−53.5 (3)
C7—C1—C6—C5	178.6 (2)	C12—O3—C11—C10	−60.2 (3)
C6—C1—C7—O2	−177.6 (2)	N—C10—C11—O3	56.1 (3)
C2—C1—C7—O2	0.8 (3)	C11—O3—C12—C13	61.1 (3)
C6—C1—C7—C8	−3.3 (3)	C9—N—C13—C12	−132.4 (3)
C2—C1—C7—C8	175.1 (2)	C10—N—C13—C12	54.3 (3)
O2—C7—C8—C14	91.8 (3)	O3—C12—C13—N	−57.7 (3)
C1—C7—C8—C14	−82.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.76 (4)	1.86 (4)	2.558 (3)	151 (5)
C4—H4···S2ⁱ	0.95	2.79	3.712 (3)	164
C3—H3···O3ⁱⁱ	0.95	2.51	3.443 (4)	168
C12—H12B···O1ⁱⁱⁱ	0.99	2.46	3.454 (4)	178

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.76 (4)	1.86 (4)	2.558 (3)	151 (5)
C4—H4⋯S2ⁱ	0.95	2.79	3.712 (3)	164
C3—H3⋯O3ⁱⁱ	0.95	2.51	3.443 (4)	168
C12—H12B⋯O1ⁱⁱⁱ	0.99	2.46	3.454 (4)	178

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

2 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Tricyclic flavonoids with 1,3-dithiolium substructure.

Authors: Lucian G Bahrin; Peter G Jones; Henning Hopf
Journal: Beilstein J Org Chem Date: 2012-11-16 Impact factor: 2.883

2 in total