Crystal structure of triphenylphosphonium-meth-yl-enetrifluoroborate.

The title compound, C19H17BF3P {alternative name: triphen-yl[(tri-fluoro-boran-yl)meth-yl]phosphanium}, was formed by the reaction of tri-phenyl-phosphine with potassium iodo-methyl-tri-fluoro-borate. The mol-ecule features a nearly staggered conformation along the P-C bond and a less than staggered conformation along the C-B bond. In the crystal, weak C-H⋯F hydrogen bonds between the meta-phenyl C-H groups and the tri-fluoro-borate B-F groups form chains of R22(16) rings along [100]. These chains are are further stabilized by weak C-H⋯π inter-actions. A weak intra-molecular C-H⋯F hydrogen bond is also observed.

Chemical context

Alkyl­tri­phenyl­phospho­nium (Ph3PRX) salts are widely used as precursors in the preparation of phospho­rus ylides for Wittig-type olefination (Julia, 1985 ▸). Such olefination reactions continue to be one of the most important means of alkene generation. Potassium organotri­fluoro­borates (KRBF3) are common substrates used in Suzuki–Miyaura coupling as stable boronic acid precursors. Additionally, they may be used to produce organodihaloboranes (RBX 2) (Darses & Genet, 2008 ▸). Seyferth & Grim (1961 ▸) showed that reaction of tri­phenyl­phosphine­methyl­ene ylide (Ph3PCH2 −) with boron trifluoride di­ethyl­etherate (BF3-OEt2) yields triphen­yl[(tri­fluoro­boran­yl)meth­yl]phosphonium (Ph3PCH2BF3). We have synthesized Ph3PCH2BF3 via an alternate route, by reacting tri­phenyl­phosphine (PPh3) with potassium iodo­methyl­tri­fluoro­borate (ICH2BF3K) in 45% yield.

There are many examples of zwitterionic organotri­fluoro­borates containing ammonium moieties, but very few containing phospho­nium groups have been reported (see Database survey). Phospho­nium tri­fluoro­borates have been shown to enhance the hydrolytic stability of the RBF3 moiety (Wade et al., 2010 ▸.) In this context we synthesized Ph3PCH2BF3 and report herein its crystal structure.

Structural commentary

The mol­ecular structure of the title compound is shown in Fig. 1 ▸. A weak intra­molecular C—H⋯F hydrogen bond forms an S(7) ring (Table 1 ▸). The mol­ecule features a nearly anti conformation along the P1—C1 bond [B1—C1—P1—C8 torsion angle = 172.4 (2)°] and a less staggered conformation along the C1—B1 bond [F2—B1—C1—P1 torsion angle = 158.3 (2)°].

Figure 1

The mol­ecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯F1i	0.95 (3)	2.44 (2)	3.293 (4)	149.7 (17)
C12—H12⋯F1ii	0.96 (3)	2.37 (3)	3.084 (3)	131 (2)
C19—H19⋯F1	0.97 (2)	2.43 (2)	3.263 (3)	143.9 (18)
C11—H11⋯Cg ii	0.89 (3)	2.77 (3)	3.639 (3)	165 (2)

Symmetry codes: (i) ; (ii) .

The B-F bond lengths fall within normal ranges for organotri­fluoro­borate compounds. The methyl­ene C—P bond length [1.787 (4) Å] and the C—B bond length [1.636 (4) Å] also fall within the normal range for similar compounds (Allen et al., 1987 ▸). In terms of the surrounding angles, the B and P atoms appear to be sp hybridized. The methyl­ene carbon is predominantly sp hybridized, but has a distorted tetra­hedral geometry with a P1—C1—B1 angle of 119.7 (2)°.

Supra­molecular features

In the crystal, two weak C—H⋯F hydrogen bonds between the meta hydrogen atoms on the tri­phenyl­phospho­nium rings and the tri­fluoro­borate moiety (Table 1 ▸) fall within the range of distances observed in other tri­phenyl­phospho­nium tri­fluoro­borates (Wade et al., 2010 ▸) and form chains of (16) rings along the [100] axis (Fig. 2 ▸). These chains are further stabilized by herringbone edge-to-face weak C—H⋯π inter­actions (Fig. 3 ▸).

Figure 2

Part of the crystal structure, showing weak C—H⋯F hydrogen bonds as dashed lines.

Figure 3

Part of the crystal structure, showing weak C—H⋯π inter­actions along [100] as dashed lines. Only the H atoms involved in these inter­actions are shown.

Database survey

A search of the Cambridge Structural Database (Version 5.37, update February 2017; Groom et al., 2016 ▸) for phospho­nium-containing tri­fluoro­borates yielded only five structures: FUYDIN (Wade et al., 2010 ▸), OZOJOD (Gott et al., 2011 ▸), PUXWEL (Piskunov et al., 2010 ▸), ZEKLEI (Li et al., 2012 ▸) and ZEKLOS (Zibo et al., 2012 ▸).

Synthesis and crystallization

Potassium iodo­methyl­tri­fluoro­borate (1.00 g, 4.04 mmol) and tri­phenyl­phosphine (1.11 g, 4.23 mmol) were combined in a pressure flask containing a stir bar under nitro­gen, and anhydrous THF (25.0 mL) was added. The flask was sealed and heated to 343 K for 18 h. The reaction was cooled to room temperature and the solvent was removed in vacuo. The residue was washed with Et2O (3 x 10 mL) and the resulting solid was dissolved in a minimal amount of acetone and the product was precipitated with water and collected by filtration, to afford a white solid (0.63 g, 1.82 mmol, 45%.) X-ray quality crystals were grown by slow diffusion of pentane into a solution of the title compound dissolved in di­chloro­methane.

1H NMR (500 MHz, CDCl3) δ (ppm): 7.66 (m, 9H), 7.56 (m, 6H), 2.07 (br d, 2H, J = 15 Hz). 13C NMR (126 MHz, CDCl3) δ (ppm): 133.7 (d, J = 3 Hz), 133.5 (d, J = 10 Hz), 129.6 (d, J = 12 Hz) 123.2 (d, J = 87 Hz) (C—B not observed). 11B NMR (160 MHz, CDCl3) δ (ppm): 2.49 (q, J = 47 Hz). 19F NMR (470 MHz, CDCl3) δ (ppm): −138.9 (q, J = 37 Hz). FTIR (ATR, cm−1): 3070, 2960, 1587, 1484, 1438, 1146, 1104, 1025, 994, 969, 824, 754, 725, 691, 511, 497.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms were refined independently with isotropic displacement parameters.

Table 2

Experimental details

Crystal data
Chemical formula	C19H17BF3P
M r	344.10
Crystal system, space group	Triclinic, P
Temperature (K)	173
a, b, c (Å)	9.514 (2), 9.870 (3), 9.883 (3)
α, β, γ (°)	64.609 (6), 87.539 (7), 86.660 (7)
V (Å3)	836.8 (4)
Z	2
Radiation type	Mo Kα
μ (mm−1)	0.19
Crystal size (mm)	0.13 × 0.07 × 0.01
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 ▸)
T min, T max	0.925, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11811, 2953, 2090
R int	0.061
(sin θ/λ)max (Å−1)	0.595
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.041, 0.094, 1.02
No. of reflections	2953
No. of parameters	285
H-atom treatment	All H-atom parameters refined
Δρmax, Δρmin (e Å−3)	0.26, −0.29

Computer programs: APEX2 and SAINT (Bruker, 2012 ▸), SHELXS97 and SHELXTL (Sheldrick 2008 ▸) and SHELXL2013 (Sheldrick 2015 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017009884/lh5846sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017009884/lh5846Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017009884/lh5846Isup3.cml

CCDC reference: 1560028

Additional supporting information: crystallographic information; 3D view; checkCIF report

C19H17BF3P	Z = 2
Mr = 344.10	F(000) = 356
Triclinic, P1	Dx = 1.366 Mg m−3
a = 9.514 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.870 (3) Å	Cell parameters from 2126 reflections
c = 9.883 (3) Å	θ = 2.3–23.9°
α = 64.609 (6)°	µ = 0.19 mm−1
β = 87.539 (7)°	T = 173 K
γ = 86.660 (7)°	Plate, colorless
V = 836.8 (4) Å3	0.13 × 0.07 × 0.01 mm

Bruker APEXII CCD diffractometer	2090 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.061
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −11→11
Tmin = 0.925, Tmax = 1.000	k = −10→11
11811 measured reflections	l = −11→11
2953 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041	All H-atom parameters refined
wR(F2) = 0.094	w = 1/[σ2(Fo2) + (0.0458P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2953 reflections	Δρmax = 0.26 e Å−3
285 parameters	Δρmin = −0.29 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
P1	0.88100 (6)	0.18041 (7)	0.68950 (7)	0.01697 (18)
B1	0.6884 (3)	0.2752 (3)	0.8793 (3)	0.0230 (7)
F1	0.58103 (14)	0.26765 (16)	0.79007 (15)	0.0321 (4)
F2	0.66153 (16)	0.40289 (16)	0.90564 (16)	0.0385 (4)
F3	0.68558 (16)	0.14803 (16)	1.01567 (15)	0.0381 (4)
C1	0.8421 (3)	0.2870 (3)	0.7950 (3)	0.0208 (6)
C2	0.7769 (2)	0.2468 (2)	0.5241 (2)	0.0159 (5)
C3	0.7246 (3)	0.3952 (3)	0.4576 (3)	0.0244 (6)
C4	0.6496 (3)	0.4457 (3)	0.3269 (3)	0.0290 (6)
C5	0.6268 (3)	0.3508 (3)	0.2611 (3)	0.0260 (6)
C6	0.6785 (3)	0.2042 (3)	0.3260 (3)	0.0270 (6)
C7	0.7526 (3)	0.1511 (3)	0.4578 (3)	0.0227 (6)
C8	1.0645 (2)	0.1992 (2)	0.6332 (2)	0.0177 (5)
C9	1.1081 (3)	0.2542 (3)	0.4834 (3)	0.0208 (6)
C10	1.2509 (3)	0.2685 (3)	0.4467 (3)	0.0271 (6)
C11	1.3487 (3)	0.2274 (3)	0.5571 (3)	0.0282 (6)
C12	1.3064 (3)	0.1730 (3)	0.7066 (3)	0.0249 (6)
C13	1.1648 (2)	0.1596 (3)	0.7452 (3)	0.0224 (6)
C14	0.8521 (2)	−0.0170 (3)	0.7952 (2)	0.0175 (5)
C15	0.9617 (3)	−0.1247 (3)	0.8201 (3)	0.0221 (6)
C16	0.9361 (3)	−0.2760 (3)	0.8966 (3)	0.0276 (6)
C17	0.8011 (3)	−0.3208 (3)	0.9478 (3)	0.0296 (6)
C18	0.6919 (3)	−0.2144 (3)	0.9237 (3)	0.0293 (6)
C19	0.7161 (3)	−0.0636 (3)	0.8475 (3)	0.0234 (6)
H1A	0.860 (3)	0.389 (3)	0.727 (3)	0.034 (8)*
H1B	0.913 (3)	0.256 (3)	0.864 (3)	0.036 (8)*
H3	0.736 (3)	0.457 (3)	0.510 (3)	0.048 (8)*
H4	0.616 (2)	0.547 (3)	0.282 (2)	0.024 (7)*
H5	0.578 (2)	0.385 (3)	0.171 (3)	0.029 (7)*
H6	0.662 (3)	0.139 (3)	0.281 (3)	0.032 (7)*
H7	0.785 (2)	0.043 (3)	0.508 (2)	0.022 (6)*
H9	1.043 (2)	0.282 (2)	0.404 (2)	0.019 (6)*
H10	1.279 (2)	0.310 (3)	0.342 (3)	0.030 (7)*
H11	1.441 (3)	0.233 (3)	0.535 (3)	0.028 (7)*
H12	1.374 (3)	0.148 (3)	0.784 (3)	0.039 (8)*
H13	1.135 (2)	0.119 (2)	0.851 (3)	0.024 (6)*
H15	1.055 (2)	−0.099 (2)	0.789 (2)	0.020 (6)*
H16	1.014 (3)	−0.352 (3)	0.915 (3)	0.036 (7)*
H17	0.785 (3)	−0.429 (3)	1.000 (3)	0.042 (8)*
H18	0.603 (3)	−0.246 (3)	0.958 (3)	0.032 (7)*
H19	0.639 (2)	0.011 (3)	0.829 (2)	0.023 (6)*

	U11	U22	U33	U12	U13	U23
P1	0.0150 (3)	0.0181 (4)	0.0176 (3)	−0.0004 (2)	−0.0011 (2)	−0.0073 (3)
B1	0.0240 (16)	0.0278 (18)	0.0209 (15)	0.0002 (13)	−0.0003 (12)	−0.0141 (13)
F1	0.0175 (7)	0.0438 (10)	0.0395 (9)	0.0008 (6)	−0.0033 (6)	−0.0220 (8)
F2	0.0425 (9)	0.0369 (10)	0.0466 (10)	−0.0011 (7)	0.0079 (7)	−0.0287 (8)
F3	0.0475 (10)	0.0350 (9)	0.0237 (8)	0.0007 (7)	0.0056 (7)	−0.0058 (7)
C1	0.0199 (13)	0.0252 (16)	0.0203 (13)	−0.0003 (11)	−0.0050 (11)	−0.0123 (12)
C2	0.0132 (12)	0.0185 (14)	0.0163 (12)	−0.0006 (10)	0.0006 (9)	−0.0078 (10)
C3	0.0286 (14)	0.0200 (15)	0.0252 (13)	−0.0005 (11)	−0.0048 (11)	−0.0100 (12)
C4	0.0344 (16)	0.0198 (16)	0.0270 (14)	0.0022 (12)	−0.0058 (12)	−0.0044 (12)
C5	0.0255 (14)	0.0309 (17)	0.0167 (13)	−0.0010 (12)	−0.0047 (11)	−0.0051 (12)
C6	0.0273 (14)	0.0368 (17)	0.0250 (14)	−0.0013 (12)	−0.0035 (11)	−0.0205 (13)
C7	0.0283 (14)	0.0198 (15)	0.0220 (13)	0.0021 (11)	−0.0040 (11)	−0.0108 (12)
C8	0.0173 (12)	0.0140 (13)	0.0212 (12)	−0.0012 (10)	−0.0003 (10)	−0.0069 (10)
C9	0.0215 (13)	0.0191 (14)	0.0224 (13)	−0.0003 (10)	−0.0006 (11)	−0.0093 (11)
C10	0.0301 (15)	0.0254 (16)	0.0269 (15)	−0.0053 (12)	0.0085 (12)	−0.0124 (12)
C11	0.0174 (14)	0.0246 (16)	0.0433 (17)	−0.0053 (11)	0.0070 (13)	−0.0153 (13)
C12	0.0182 (14)	0.0222 (15)	0.0332 (15)	−0.0034 (11)	−0.0032 (12)	−0.0102 (12)
C13	0.0190 (13)	0.0228 (14)	0.0221 (13)	−0.0027 (10)	0.0001 (11)	−0.0063 (11)
C14	0.0188 (12)	0.0195 (14)	0.0152 (12)	−0.0023 (10)	−0.0021 (9)	−0.0081 (10)
C15	0.0210 (14)	0.0238 (15)	0.0205 (13)	−0.0042 (11)	−0.0007 (11)	−0.0082 (11)
C16	0.0343 (16)	0.0196 (15)	0.0277 (14)	0.0022 (12)	−0.0050 (12)	−0.0091 (12)
C17	0.0448 (18)	0.0187 (16)	0.0238 (14)	−0.0086 (13)	0.0007 (12)	−0.0070 (12)
C18	0.0292 (16)	0.0316 (17)	0.0293 (15)	−0.0142 (13)	0.0073 (12)	−0.0145 (13)
C19	0.0192 (13)	0.0257 (15)	0.0264 (14)	−0.0030 (12)	0.0012 (11)	−0.0120 (12)

P1—C1	1.787 (2)	C8—C13	1.401 (3)
P1—C2	1.796 (2)	C9—C10	1.390 (3)
P1—C8	1.805 (2)	C9—H9	0.96 (2)
P1—C14	1.804 (2)	C10—C11	1.373 (4)
B1—F3	1.394 (3)	C10—H10	0.96 (2)
B1—F2	1.400 (3)	C11—C12	1.388 (4)
B1—F1	1.404 (3)	C11—H11	0.89 (2)
B1—C1	1.636 (4)	C12—C13	1.383 (3)
C1—H1A	0.96 (3)	C12—H12	0.95 (3)
C1—H1B	0.92 (3)	C13—H13	0.99 (2)
C2—C3	1.394 (3)	C14—C15	1.395 (3)
C2—C7	1.395 (3)	C14—C19	1.401 (3)
C3—C4	1.383 (3)	C15—C16	1.385 (3)
C3—H3	0.97 (3)	C15—H15	0.94 (2)
C4—C5	1.380 (4)	C16—C17	1.385 (4)
C4—H4	0.95 (2)	C16—H16	0.99 (3)
C5—C6	1.377 (4)	C17—C18	1.385 (4)
C5—H5	0.94 (2)	C17—H17	0.99 (3)
C6—C7	1.385 (3)	C18—C19	1.378 (3)
C6—H6	0.95 (2)	C18—H18	0.92 (3)
C7—H7	1.00 (2)	C19—H19	0.97 (2)
C8—C9	1.394 (3)
C1—P1—C2	111.67 (12)	C9—C8—C13	119.8 (2)
C1—P1—C8	108.25 (11)	C9—C8—P1	122.17 (18)
C2—P1—C8	108.48 (10)	C13—C8—P1	118.04 (17)
C1—P1—C14	113.04 (12)	C10—C9—C8	119.6 (2)
C2—P1—C14	107.54 (10)	C10—C9—H9	117.9 (13)
C8—P1—C14	107.70 (11)	C8—C9—H9	122.5 (13)
F3—B1—F2	109.0 (2)	C11—C10—C9	120.4 (2)
F3—B1—F1	108.4 (2)	C11—C10—H10	121.1 (14)
F2—B1—F1	108.5 (2)	C9—C10—H10	118.5 (14)
F3—B1—C1	110.9 (2)	C10—C11—C12	120.6 (2)
F2—B1—C1	109.1 (2)	C10—C11—H11	121.3 (15)
F1—B1—C1	110.84 (19)	C12—C11—H11	118.1 (15)
B1—C1—P1	119.66 (17)	C13—C12—C11	119.9 (2)
B1—C1—H1A	111.2 (15)	C13—C12—H12	119.0 (15)
P1—C1—H1A	105.1 (15)	C11—C12—H12	121.1 (15)
B1—C1—H1B	110.3 (16)	C12—C13—C8	119.8 (2)
P1—C1—H1B	103.3 (16)	C12—C13—H13	120.1 (13)
H1A—C1—H1B	106 (2)	C8—C13—H13	120.1 (13)
C3—C2—C7	119.4 (2)	C15—C14—C19	119.2 (2)
C3—C2—P1	120.63 (17)	C15—C14—P1	121.19 (17)
C7—C2—P1	119.90 (17)	C19—C14—P1	119.50 (18)
C4—C3—C2	119.7 (2)	C16—C15—C14	120.3 (2)
C4—C3—H3	122.1 (16)	C16—C15—H15	117.2 (14)
C2—C3—H3	118.0 (16)	C14—C15—H15	122.5 (14)
C5—C4—C3	120.6 (3)	C17—C16—C15	120.0 (3)
C5—C4—H4	120.7 (14)	C17—C16—H16	120.0 (15)
C3—C4—H4	118.7 (14)	C15—C16—H16	120.0 (15)
C6—C5—C4	120.0 (2)	C16—C17—C18	120.1 (3)
C6—C5—H5	118.9 (15)	C16—C17—H17	118.8 (15)
C4—C5—H5	121.1 (15)	C18—C17—H17	121.2 (15)
C5—C6—C7	120.3 (2)	C19—C18—C17	120.4 (3)
C5—C6—H6	119.8 (15)	C19—C18—H18	120.3 (16)
C7—C6—H6	119.9 (15)	C17—C18—H18	119.2 (16)
C6—C7—C2	120.0 (2)	C18—C19—C14	120.0 (2)
C6—C7—H7	120.3 (13)	C18—C19—H19	120.6 (13)
C2—C7—H7	119.6 (13)	C14—C19—H19	119.4 (13)
F3—B1—C1—P1	81.6 (2)	C2—P1—C8—C13	177.28 (18)
F2—B1—C1—P1	−158.33 (17)	C14—P1—C8—C13	−66.6 (2)
F1—B1—C1—P1	−38.9 (3)	C13—C8—C9—C10	0.4 (3)
C2—P1—C1—B1	68.2 (2)	P1—C8—C9—C10	178.94 (18)
C8—P1—C1—B1	−172.42 (19)	C8—C9—C10—C11	0.6 (4)
C14—P1—C1—B1	−53.2 (2)	C9—C10—C11—C12	−0.8 (4)
C1—P1—C2—C3	25.8 (2)	C10—C11—C12—C13	0.1 (4)
C8—P1—C2—C3	−93.4 (2)	C11—C12—C13—C8	0.8 (4)
C14—P1—C2—C3	150.38 (18)	C9—C8—C13—C12	−1.1 (3)
C1—P1—C2—C7	−156.73 (19)	P1—C8—C13—C12	−179.71 (19)
C8—P1—C2—C7	84.1 (2)	C1—P1—C14—C15	−119.9 (2)
C14—P1—C2—C7	−32.2 (2)	C2—P1—C14—C15	116.40 (19)
C7—C2—C3—C4	−0.1 (4)	C8—P1—C14—C15	−0.3 (2)
P1—C2—C3—C4	177.32 (19)	C1—P1—C14—C19	63.0 (2)
C2—C3—C4—C5	−0.3 (4)	C2—P1—C14—C19	−60.7 (2)
C3—C4—C5—C6	0.2 (4)	C8—P1—C14—C19	−177.42 (18)
C4—C5—C6—C7	0.5 (4)	C19—C14—C15—C16	−0.4 (3)
C5—C6—C7—C2	−1.0 (4)	P1—C14—C15—C16	−177.49 (18)
C3—C2—C7—C6	0.8 (4)	C14—C15—C16—C17	0.4 (4)
P1—C2—C7—C6	−176.70 (18)	C15—C16—C17—C18	−0.5 (4)
C1—P1—C8—C9	−122.6 (2)	C16—C17—C18—C19	0.6 (4)
C2—P1—C8—C9	−1.3 (2)	C17—C18—C19—C14	−0.6 (4)
C14—P1—C8—C9	114.8 (2)	C15—C14—C19—C18	0.5 (3)
C1—P1—C8—C13	55.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···F1i	0.95 (3)	2.44 (2)	3.293 (4)	149.7 (17)
C12—H12···F1ii	0.96 (3)	2.37 (3)	3.084 (3)	131 (2)
C19—H19···F1	0.97 (2)	2.43 (2)	3.263 (3)	143.9 (18)
C11—H11···Cgii	0.89 (3)	2.77 (3)	3.639 (3)	165 (2)