(E)-6-(4-Chloro­phen­yl)-4-[(2-cyano-3-phenyl­all­yl)sulfan­yl]-2,2-difluoro-3-phenyl-1,3,2-oxaza­borinin-3-ium-2-uide

Li, M.; Wang, S.-W.; Wen, L.-R.

doi:10.1107/S1600536813007800

organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Page o648

https://doi.org/10.1107/S1600536813007800

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(E)-6-(4-Chlorophenyl)-4-[(2-cyano-3-phenylallyl)sulfanyl]-2,2-difluoro-3-phenyl-1,3,2-oxazaborinin-3-ium-2-uide

Ming Li,^a Shu-Wen Wang ^a and Li-Rong Wen ^a ^*

^aCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: wenlirong@qust.edu.cn

(Received 15 March 2013; accepted 21 March 2013; online 5 April 2013)

In the title compound, C₂₅H₁₈BClF₂N₂OS, the characteristic B—N and B—O bond lengths are 1.571 (3) and 1.458 (3) Å, respectively. The phenyl rings form dihedral angles of 83.1 (1) and 64.6 (1)° with the chlorophenyl ring. In the crystal, weak C—H⋯N, C—H⋯F, C—H⋯π and π–π interactions [centroid–centroid distances 3.877 (6) Å between the chlorophenyl rings of neighbouring molecules] held molecules together, forming ladders along the b axis.

Related literature

For background to thioacetanilides, see: Peruncheralathan et al. (2005 ); Li et al. (2010 ); Wu et al. (2009 ); Erten-Ela et al. (2008 ); Tokoro et al. (2010 ); Lu et al. (2002 ); Tsuboyama et al. (2003 ); Zhang et al. (2006 ). For the crystal structures of related compounds, see: Macedo et al. (2008 ).

Experimental

Crystal data

C₂₅H₁₈BClF₂N₂OS
M_r = 478.73
Monoclinic, P 2₁ /c
a = 9.6996 (19) Å
b = 16.290 (3) Å
c = 14.168 (3) Å
β = 98.71 (3)°
V = 2212.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 173 K
0.43 × 0.29 × 0.09 mm

Data collection

Rigaku MM007HF diffractometer with Saturn724+ CCD
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku/MSC, 2008 ) T_min = 0.685, T_max = 1.000
15558 measured reflections
5081 independent reflections
4491 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.120
S = 1.18
5081 reflections
298 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16A⋯F1ⁱ	0.99	2.35	3.184 (3)	141
C21—H21⋯N1ⁱⁱ	0.95	2.55	3.434 (4)	156
C15—H15⋯Cg1ⁱⁱⁱ	0.95	2.52	3.394 (5)	153
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z.

Data collection: CrystalClear-SM Expert (Rigaku/MSC, 2008); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813007800/cv5394sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813007800/cv5394Isup2.hkl

checkCIF report

Comment top

Thioacetanilides being novel enaminones (Peruncheralathan et al., 2005) with four active reaction sites show structural feature of highly polarized push-pull interaction C=C double bond (Li et al., 2010). BF₂ complexes, such as the Bodipy family, are most intriguing due to their outstanding optical properties, extraordinary chemical versatility, and variety of applications spanning from biolabeling (Wu et al., 2009) to solar cells (Erten-Ela et al., 2008) and nanoparticle engineering (Tokoro et al., 2010). Synthetic studies have been conducted on various phosphorescent materials with heavy metals such as iridium (Tsuboyama et al., 2003) and platinum (Lu et al., 2002) and on fluorescent boron complexes (Zhang et al., 2006). In order to explore the chemical reactivities of thioacetanilides, we obtained the title compound, (I).

In (I) (Fig. 1), the B1–N2 bond length (1.571 (3) Å) is more than 0.1 Å longer than the B1–O1 bond length (1.458 (3) Å) suggesting that the major resonance contribution to bonding is the alkoxy-imine form. All bond lengths and angles in (I) are normal and in a good agreement with those reported previously for related compounds (Macedo et al., 2008) The phenyl rings C10—C15 and C20—C25 form the dihedral angles of 83.1 (1) and 64.6 (1)°, respectively, with the chlorophenyl ring C1—C6.

In the crystal, π-π interactions (centroid-to-centroid distances 3.877 (6) Å between the chlorophenyl rings of neighbouring molecules) and weak intermolecular C—H···N, C—H···F and C—H···π interactions (Table 1) held molecules together.

Related literature top

For background to thioacetanilides, see: Peruncheralathan et al. (2005); Li et al. (2010); Wu et al. (2009); Erten-Ela et al. (2008); Tokoro et al. (2010); Lu et al. (2002); Tsuboyama et al. (2003); Zhang et al. (2006). For the crystal structures of related compounds, see: Macedo et al. (2008).

Experimental top

A 25 ml volumetric flask was charged with 8 ml THF and 1.01 g (5 mmol) 2-cyano-1-phenylallyl acetate. Then 1.45 g (5 mmol) 3-(4-chlorophenyl)-3-oxo-N-phenylpropane thioamide and 0.09 g (3.75 mmol) sodium hydride were added. The mixture was stirred at room temperature for 4 h, and then 8 ml BF₃.Et₂O (10 mmol) was added with stirring for a further 4 h at room temperature. The reaction was monitored by TLC, and after TLC indicated the completion of the reaction, the solution was filtered, and the inorganic salts were removed. The solvent of the filtrate was removed with the aid of a rotary evaporator, and the residue was purified by column chromatography on silica gel, using petroleum ether/ethyl acetate (6:1) as eluent to provide the desired product yielding 2.01 g (84%) of pure BF2 complex, m.p. 462–463 K. Analytical data: IR (KBr, cm^-1): 3080, 2977, 2180, 1681, 1583, 1505, 850, 732, 699. ¹H-NMR (500 MHz, CDCl₃): δ (p.p.m.) 3.98 (2H, s), 6.26 (1H, s), 7.22 (1H, s), 7.32–7.33 (2H, d, J = 7.55 Hz), 7.40–7.49 (8H, m), 7.73–7.74 (2H, d, J = 7.65 Hz), 7.88–7.90 (2H, d, J = 4.28 Hz). Single crystals suitable for X-ray diffraction were obtained through slow evaporation of a solution of the pure title compound in ethanol.

Structure description top

For background to thioacetanilides, see: Peruncheralathan et al. (2005); Li et al. (2010); Wu et al. (2009); Erten-Ela et al. (2008); Tokoro et al. (2010); Lu et al. (2002); Tsuboyama et al. (2003); Zhang et al. (2006). For the crystal structures of related compounds, see: Macedo et al. (2008).

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku/MSC, 2008); cell refinement: CrystalClear-SM Expert (Rigaku/MSC, 2008); data reduction: CrystalClear-SM Expert (Rigaku/MSC, 2008); 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 (Sheldrick, 2008).

Figures top

Fig. 1. View of (I) showing the atomic numbering and 40% probability displacement ellipsoids.

(E)-6-(4-Chlorophenyl)-4-[(2-cyano-3-phenylallyl)sulfanyl]-2,2-difluoro-3-phenyl-1,3,2-oxazaborinin-3-ium-2-uide top

Crystal data top

C₂₅H₁₈BClF₂N₂OS	F(000) = 984
M_r = 478.73	D_x = 1.437 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7694 reflections
a = 9.6996 (19) Å	θ = 1.5–27.5°
b = 16.290 (3) Å	µ = 0.31 mm⁻¹
c = 14.168 (3) Å	T = 173 K
β = 98.71 (3)°	Plate, colourless
V = 2212.9 (8) Å³	0.43 × 0.29 × 0.09 mm
Z = 4

Data collection top

Rigaku MM007HF diffractometer with Saturn724+ CCD	5081 independent reflections
Radiation source: Rotating Anode	4491 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.052
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 2.1°
ω scans at fixed χ = 45°	h = −12→12
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku/MSC, 2008)	k = −20→21
T_min = 0.685, T_max = 1.000	l = −18→18
15558 measured reflections

Refinement top

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.18	w = 1/[σ²(F_o²) + (0.0312P)² + 1.2135P] where P = (F_o² + 2F_c²)/3
5081 reflections	(Δ/σ)_max = 0.001
298 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₅H₁₈BClF₂N₂OS	V = 2212.9 (8) Å³
M_r = 478.73	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.6996 (19) Å	µ = 0.31 mm⁻¹
b = 16.290 (3) Å	T = 173 K
c = 14.168 (3) Å	0.43 × 0.29 × 0.09 mm
β = 98.71 (3)°

Data collection top

Rigaku MM007HF diffractometer with Saturn724+ CCD	5081 independent reflections
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku/MSC, 2008)	4491 reflections with I > 2σ(I)
T_min = 0.685, T_max = 1.000	R_int = 0.052
15558 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.18	Δρ_max = 0.31 e Å⁻³
5081 reflections	Δρ_min = −0.23 e Å⁻³
298 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	1.18430 (6)	0.47712 (4)	1.29061 (4)	0.03843 (16)
S1	0.47463 (6)	0.63647 (4)	0.79190 (4)	0.03476 (16)
F1	0.61480 (16)	0.34159 (9)	0.78320 (10)	0.0494 (4)
F2	0.46844 (15)	0.35602 (9)	0.89236 (12)	0.0531 (4)
O1	0.69166 (16)	0.40858 (9)	0.92380 (11)	0.0328 (4)
N1	0.7666 (3)	0.74393 (18)	0.69117 (18)	0.0609 (7)
N2	0.51593 (17)	0.47557 (11)	0.80301 (12)	0.0262 (4)
C1	1.0468 (2)	0.47953 (14)	1.19668 (15)	0.0274 (5)
C2	1.0082 (2)	0.55340 (14)	1.15244 (16)	0.0304 (5)
H2	1.0558	0.6027	1.1730	0.036*
C3	0.8982 (2)	0.55382 (13)	1.07731 (16)	0.0292 (5)
H3	0.8696	0.6041	1.0465	0.035*
C4	0.8293 (2)	0.48155 (13)	1.04648 (15)	0.0250 (4)
C5	0.8714 (2)	0.40787 (13)	1.09205 (16)	0.0292 (5)
H5	0.8256	0.3582	1.0709	0.035*
C6	0.9795 (2)	0.40674 (14)	1.16804 (16)	0.0299 (5)
H6	1.0071	0.3568	1.2000	0.036*
C7	0.7153 (2)	0.48088 (13)	0.96488 (15)	0.0248 (4)
C8	0.6431 (2)	0.54917 (13)	0.93219 (15)	0.0275 (5)
H8	0.6567	0.5989	0.9674	0.033*
C9	0.5476 (2)	0.54684 (13)	0.84604 (15)	0.0261 (4)
C10	0.4192 (2)	0.47173 (13)	0.71416 (15)	0.0264 (4)
C11	0.4659 (2)	0.44916 (14)	0.63062 (15)	0.0299 (5)
H11	0.5618	0.4376	0.6303	0.036*
C12	0.3708 (2)	0.44347 (14)	0.54681 (16)	0.0332 (5)
H12	0.4020	0.4278	0.4890	0.040*
C13	0.2318 (2)	0.46038 (15)	0.54715 (17)	0.0353 (5)
H13	0.1674	0.4568	0.4897	0.042*
C14	0.1866 (2)	0.48238 (16)	0.63088 (17)	0.0371 (6)
H14	0.0907	0.4944	0.6309	0.044*
C15	0.2795 (2)	0.48729 (15)	0.71564 (17)	0.0351 (5)
H15	0.2475	0.5012	0.7737	0.042*
C16	0.5544 (2)	0.71958 (13)	0.86749 (16)	0.0305 (5)
H16A	0.4994	0.7701	0.8507	0.037*
H16B	0.5464	0.7061	0.9346	0.037*
C17	0.7407 (2)	0.74202 (16)	0.76730 (19)	0.0392 (6)
C18	0.7058 (2)	0.73849 (13)	0.86224 (16)	0.0290 (5)
C19	0.7974 (2)	0.75408 (13)	0.94089 (17)	0.0298 (5)
H19	0.7598	0.7497	0.9988	0.036*
C20	0.9453 (2)	0.77676 (13)	0.95341 (18)	0.0331 (5)
C21	1.0184 (3)	0.77306 (15)	1.04606 (19)	0.0399 (6)
H21	0.9705	0.7581	1.0972	0.048*
C22	1.1595 (3)	0.79076 (17)	1.0647 (2)	0.0497 (7)
H22	1.2079	0.7870	1.1281	0.060*
C23	1.2294 (3)	0.81371 (17)	0.9917 (3)	0.0549 (8)
H23	1.3263	0.8257	1.0045	0.066*
C24	1.1594 (3)	0.81935 (16)	0.8998 (2)	0.0525 (8)
H24	1.2083	0.8351	0.8494	0.063*
C25	1.0182 (3)	0.80214 (15)	0.8805 (2)	0.0412 (6)
H25	0.9703	0.8076	0.8172	0.049*
B1	0.5719 (3)	0.39255 (16)	0.85061 (19)	0.0319 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0282 (3)	0.0561 (4)	0.0277 (3)	0.0032 (2)	−0.0063 (2)	−0.0049 (3)
S1	0.0339 (3)	0.0328 (3)	0.0334 (3)	0.0042 (2)	−0.0084 (2)	0.0026 (2)
F1	0.0668 (10)	0.0414 (8)	0.0339 (8)	0.0178 (7)	−0.0125 (7)	−0.0125 (6)
F2	0.0451 (9)	0.0497 (9)	0.0622 (11)	−0.0141 (7)	0.0003 (7)	0.0157 (8)
O1	0.0389 (9)	0.0252 (8)	0.0294 (9)	0.0015 (7)	−0.0102 (7)	−0.0042 (6)
N1	0.0547 (15)	0.090 (2)	0.0404 (15)	0.0242 (14)	0.0130 (11)	0.0166 (13)
N2	0.0249 (9)	0.0321 (10)	0.0201 (9)	−0.0005 (7)	−0.0013 (7)	−0.0020 (7)
C1	0.0232 (10)	0.0402 (12)	0.0181 (11)	0.0031 (9)	0.0005 (8)	−0.0029 (9)
C2	0.0307 (11)	0.0330 (12)	0.0266 (12)	−0.0051 (9)	0.0020 (9)	−0.0050 (9)
C3	0.0328 (11)	0.0278 (11)	0.0256 (12)	−0.0010 (9)	−0.0003 (9)	−0.0007 (9)
C4	0.0265 (10)	0.0281 (11)	0.0197 (11)	0.0020 (8)	0.0014 (8)	−0.0020 (8)
C5	0.0317 (11)	0.0278 (11)	0.0266 (12)	0.0011 (9)	−0.0004 (8)	−0.0011 (9)
C6	0.0325 (11)	0.0287 (11)	0.0265 (12)	0.0060 (9)	−0.0014 (9)	−0.0004 (9)
C7	0.0277 (10)	0.0263 (11)	0.0202 (11)	−0.0026 (8)	0.0029 (8)	−0.0011 (8)
C8	0.0294 (11)	0.0279 (11)	0.0229 (11)	0.0006 (9)	−0.0029 (8)	−0.0035 (8)
C9	0.0246 (10)	0.0308 (11)	0.0222 (11)	−0.0003 (8)	0.0011 (8)	−0.0006 (8)
C10	0.0266 (10)	0.0297 (11)	0.0214 (11)	−0.0042 (9)	−0.0011 (8)	0.0017 (8)
C11	0.0271 (11)	0.0366 (12)	0.0251 (12)	−0.0038 (9)	0.0014 (8)	−0.0026 (9)
C12	0.0390 (12)	0.0392 (13)	0.0210 (12)	−0.0095 (10)	0.0036 (9)	−0.0018 (9)
C13	0.0352 (12)	0.0430 (14)	0.0245 (12)	−0.0097 (10)	−0.0061 (9)	0.0050 (10)
C14	0.0254 (11)	0.0512 (15)	0.0326 (13)	−0.0026 (10)	−0.0020 (9)	0.0011 (11)
C15	0.0278 (11)	0.0507 (15)	0.0267 (13)	−0.0038 (10)	0.0035 (9)	−0.0049 (10)
C16	0.0297 (11)	0.0288 (11)	0.0317 (13)	0.0074 (9)	0.0002 (9)	0.0004 (9)
C17	0.0345 (12)	0.0473 (15)	0.0353 (15)	0.0106 (11)	0.0041 (10)	0.0065 (11)
C18	0.0318 (11)	0.0246 (10)	0.0311 (12)	0.0071 (9)	0.0066 (9)	0.0030 (9)
C19	0.0331 (11)	0.0248 (11)	0.0317 (13)	0.0024 (9)	0.0058 (9)	0.0010 (9)
C20	0.0330 (11)	0.0214 (10)	0.0449 (15)	0.0013 (9)	0.0061 (10)	0.0002 (10)
C21	0.0380 (13)	0.0353 (13)	0.0452 (16)	−0.0021 (10)	0.0029 (11)	−0.0054 (11)
C22	0.0386 (14)	0.0444 (15)	0.0616 (19)	−0.0029 (12)	−0.0067 (12)	−0.0058 (13)
C23	0.0334 (13)	0.0383 (15)	0.092 (3)	−0.0078 (12)	0.0072 (14)	−0.0011 (15)
C24	0.0411 (14)	0.0341 (14)	0.086 (2)	−0.0042 (12)	0.0215 (15)	0.0109 (14)
C25	0.0397 (13)	0.0314 (13)	0.0536 (17)	0.0016 (10)	0.0105 (11)	0.0096 (11)
B1	0.0342 (13)	0.0305 (13)	0.0284 (14)	−0.0032 (11)	−0.0040 (10)	−0.0041 (10)

Geometric parameters (Å, º) top

Cl1—C1	1.736 (2)	C11—C12	1.392 (3)
S1—C9	1.748 (2)	C11—H11	0.9500
S1—C16	1.824 (2)	C12—C13	1.377 (3)
F1—B1	1.376 (3)	C12—H12	0.9500
F2—B1	1.375 (3)	C13—C14	1.373 (3)
O1—C7	1.318 (2)	C13—H13	0.9500
O1—B1	1.458 (3)	C14—C15	1.391 (3)
N1—C17	1.144 (3)	C14—H14	0.9500
N2—C9	1.326 (3)	C15—H15	0.9500
N2—C10	1.453 (3)	C16—C18	1.513 (3)
N2—B1	1.571 (3)	C16—H16A	0.9900
C1—C2	1.382 (3)	C16—H16B	0.9900
C1—C6	1.384 (3)	C17—C18	1.437 (3)
C2—C3	1.388 (3)	C18—C19	1.340 (3)
C2—H2	0.9500	C19—C20	1.466 (3)
C3—C4	1.391 (3)	C19—H19	0.9500
C3—H3	0.9500	C20—C21	1.396 (3)
C4—C5	1.394 (3)	C20—C25	1.400 (3)
C4—C7	1.474 (3)	C21—C22	1.384 (3)
C5—C6	1.385 (3)	C21—H21	0.9500
C5—H5	0.9500	C22—C23	1.372 (4)
C6—H6	0.9500	C22—H22	0.9500
C7—C8	1.358 (3)	C23—C24	1.377 (4)
C8—C9	1.417 (3)	C23—H23	0.9500
C8—H8	0.9500	C24—C25	1.384 (4)
C10—C11	1.380 (3)	C24—H24	0.9500
C10—C15	1.381 (3)	C25—H25	0.9500

C9—S1—C16	104.75 (10)	C13—C14—C15	120.7 (2)
C7—O1—B1	122.73 (17)	C13—C14—H14	119.6
C9—N2—C10	120.69 (18)	C15—C14—H14	119.6
C9—N2—B1	121.04 (17)	C10—C15—C14	119.0 (2)
C10—N2—B1	118.08 (17)	C10—C15—H15	120.5
C2—C1—C6	121.98 (19)	C14—C15—H15	120.5
C2—C1—Cl1	119.43 (17)	C18—C16—S1	116.79 (16)
C6—C1—Cl1	118.60 (17)	C18—C16—H16A	108.1
C1—C2—C3	118.4 (2)	S1—C16—H16A	108.1
C1—C2—H2	120.8	C18—C16—H16B	108.1
C3—C2—H2	120.8	S1—C16—H16B	108.1
C2—C3—C4	120.9 (2)	H16A—C16—H16B	107.3
C2—C3—H3	119.6	N1—C17—C18	178.8 (3)
C4—C3—H3	119.6	C19—C18—C17	123.4 (2)
C3—C4—C5	119.35 (19)	C19—C18—C16	121.6 (2)
C3—C4—C7	121.36 (19)	C17—C18—C16	115.0 (2)
C5—C4—C7	119.27 (19)	C18—C19—C20	131.4 (2)
C6—C5—C4	120.4 (2)	C18—C19—H19	114.3
C6—C5—H5	119.8	C20—C19—H19	114.3
C4—C5—H5	119.8	C21—C20—C25	117.7 (2)
C1—C6—C5	119.0 (2)	C21—C20—C19	116.8 (2)
C1—C6—H6	120.5	C25—C20—C19	125.4 (2)
C5—C6—H6	120.5	C22—C21—C20	121.2 (3)
O1—C7—C8	122.33 (19)	C22—C21—H21	119.4
O1—C7—C4	114.39 (18)	C20—C21—H21	119.4
C8—C7—C4	123.25 (19)	C23—C22—C21	120.0 (3)
C7—C8—C9	120.5 (2)	C23—C22—H22	120.0
C7—C8—H8	119.7	C21—C22—H22	120.0
C9—C8—H8	119.7	C22—C23—C24	120.1 (3)
N2—C9—C8	119.69 (19)	C22—C23—H23	119.9
N2—C9—S1	118.65 (15)	C24—C23—H23	119.9
C8—C9—S1	121.61 (16)	C23—C24—C25	120.3 (3)
C11—C10—C15	120.8 (2)	C23—C24—H24	119.9
C11—C10—N2	120.13 (19)	C25—C24—H24	119.9
C15—C10—N2	119.0 (2)	C24—C25—C20	120.7 (3)
C10—C11—C12	119.2 (2)	C24—C25—H25	119.7
C10—C11—H11	120.4	C20—C25—H25	119.7
C12—C11—H11	120.4	F2—B1—F1	110.8 (2)
C13—C12—C11	120.4 (2)	F2—B1—O1	109.0 (2)
C13—C12—H12	119.8	F1—B1—O1	108.0 (2)
C11—C12—H12	119.8	F2—B1—N2	109.24 (19)
C14—C13—C12	119.8 (2)	F1—B1—N2	110.0 (2)
C14—C13—H13	120.1	O1—B1—N2	109.71 (18)
C12—C13—H13	120.1

C6—C1—C2—C3	0.2 (3)	C10—C11—C12—C13	0.2 (3)
Cl1—C1—C2—C3	179.82 (17)	C11—C12—C13—C14	−0.5 (4)
C1—C2—C3—C4	−0.7 (3)	C12—C13—C14—C15	−0.4 (4)
C2—C3—C4—C5	0.2 (3)	C11—C10—C15—C14	−2.0 (4)
C2—C3—C4—C7	−178.1 (2)	N2—C10—C15—C14	−179.0 (2)
C3—C4—C5—C6	0.8 (3)	C13—C14—C15—C10	1.6 (4)
C7—C4—C5—C6	179.1 (2)	C9—S1—C16—C18	72.85 (18)
C2—C1—C6—C5	0.8 (3)	N1—C17—C18—C19	157 (14)
Cl1—C1—C6—C5	−178.86 (17)	N1—C17—C18—C16	−26 (14)
C4—C5—C6—C1	−1.3 (3)	S1—C16—C18—C19	−137.62 (19)
B1—O1—C7—C8	−10.5 (3)	S1—C16—C18—C17	45.1 (2)
B1—O1—C7—C4	171.5 (2)	C17—C18—C19—C20	−0.2 (4)
C3—C4—C7—O1	158.4 (2)	C16—C18—C19—C20	−177.3 (2)
C5—C4—C7—O1	−19.9 (3)	C18—C19—C20—C21	−167.7 (2)
C3—C4—C7—C8	−19.6 (3)	C18—C19—C20—C25	12.7 (4)
C5—C4—C7—C8	162.2 (2)	C25—C20—C21—C22	−2.5 (4)
O1—C7—C8—C9	−6.2 (3)	C19—C20—C21—C22	177.9 (2)
C4—C7—C8—C9	171.6 (2)	C20—C21—C22—C23	1.1 (4)
C10—N2—C9—C8	−179.45 (19)	C21—C22—C23—C24	0.1 (4)
B1—N2—C9—C8	5.6 (3)	C22—C23—C24—C25	0.2 (4)
C10—N2—C9—S1	−1.9 (3)	C23—C24—C25—C20	−1.7 (4)
B1—N2—C9—S1	−176.82 (16)	C21—C20—C25—C24	2.8 (4)
C7—C8—C9—N2	8.1 (3)	C19—C20—C25—C24	−177.7 (2)
C7—C8—C9—S1	−169.38 (17)	C7—O1—B1—F2	−97.9 (2)
C16—S1—C9—N2	−175.52 (17)	C7—O1—B1—F1	141.6 (2)
C16—S1—C9—C8	2.0 (2)	C7—O1—B1—N2	21.6 (3)
C9—N2—C10—C11	112.8 (2)	C9—N2—B1—F2	100.3 (2)
B1—N2—C10—C11	−72.1 (3)	C10—N2—B1—F2	−74.8 (3)
C9—N2—C10—C15	−70.1 (3)	C9—N2—B1—F1	−137.9 (2)
B1—N2—C10—C15	105.0 (2)	C10—N2—B1—F1	47.0 (3)
C15—C10—C11—C12	1.1 (3)	C9—N2—B1—O1	−19.2 (3)
N2—C10—C11—C12	178.1 (2)	C10—N2—B1—O1	165.75 (18)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16A···F1ⁱ	0.99	2.35	3.184 (3)	141
C21—H21···N1ⁱⁱ	0.95	2.55	3.434 (4)	156
C15—H15···Cg1ⁱⁱⁱ	0.95	2.52	3.394 (5)	153

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+3/2, z+1/2; (iii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₂₅H₁₈BClF₂N₂OS
M_r	478.73
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	9.6996 (19), 16.290 (3), 14.168 (3)
β (°)	98.71 (3)
V (Å³)	2212.9 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.43 × 0.29 × 0.09

Data collection
Diffractometer	Rigaku MM007HF diffractometer with Saturn724+ CCD
Absorption correction	Multi-scan (CrystalClear-SM Expert; Rigaku/MSC, 2008)
T_min, T_max	0.685, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15558, 5081, 4491
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.120, 1.18
No. of reflections	5081
No. of parameters	298
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.23

Computer programs: CrystalClear-SM Expert (Rigaku/MSC, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16A···F1ⁱ	0.99	2.35	3.184 (3)	140.8
C21—H21···N1ⁱⁱ	0.95	2.55	3.434 (4)	155.6
C15—H15···Cg1ⁱⁱⁱ	0.95	2.52	3.394 (5)	153.0

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+3/2, z+1/2; (iii) −x+1, −y+1, −z.

References

Erten-Ela, S., Yilmaz, D., Icli, B., Dede, Y., Icli, S. & Akkaya, U. E. (2008). Org. Lett. 10, 3299–3320. Web of Science PubMed CAS Google Scholar
Li, M., Hou, Y. L., Wen, L. R. & Gong, F. M. (2010). J. Org. Chem. 75, 8522–8532. Web of Science CSD CrossRef CAS PubMed Google Scholar
Lu, W., Mi, B. X., Chan, M. C. W., Hui, Z., Zhu, N., Lee, S. T. & Che, C. M. (2002). Chem. Commun. pp. 206–207. Web of Science CSD CrossRef Google Scholar
Macedo, F. P., Gwengo, C., Lindeman, S. V., Smith, M. D. & Gardinier, J. R. (2008). Eur. J. Inorg. Chem. pp. 3200–3211. Web of Science CSD CrossRef Google Scholar
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Rigaku/MSC (2008). CrystalClear-SM Expert. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tokoro, Y., Nagai, A. & Chujo, Y. (2010). Tetrahedron Lett. 51, 3451–3454. Web of Science CrossRef CAS Google Scholar
Tsuboyama, A., Iwawaki, H., Iwawaki, H., Furugori, M., Mukaide, T., Kamatani, J., Igawa, S., Moriyama, T., Miura, S., Takiguchi, T., Okada, S., Hoshino, M. & Ueno, K. (2003). J. Am. Chem. Soc. 125, 12971–12979. Web of Science CSD CrossRef PubMed CAS Google Scholar
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Volume 69| Part 5| May 2013| Page o648

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(E)-6-(4-Chloro­phen­yl)-4-[(2-cyano-3-phenyl­all­yl)sulfan­yl]-2,2-di­fluoro-3-phenyl-1,3,2-oxaza­borinin-3-ium-2-uide

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Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

(E)-6-(4-Chlorophenyl)-4-[(2-cyano-3-phenylallyl)sulfanyl]-2,2-difluoro-3-phenyl-1,3,2-oxazaborinin-3-ium-2-uide