[4-(Methoxy-carbon-yl)benz-yl]triphenyl-phospho-nium bromide hemihydrate.

In the crystal structure of the title compound, C(27)H(24)O(2)P(+)·Br(-)·0.5H(2)O, there are inter-molecular O-H⋯Br hydrogen bonds between the H atoms of the water of crystallization and the bromide anions. The three phenyl rings of the triphenyl-phosphonium moiety are at angles of 59.73 (15), 79.15 (14) and 82.81 (17)° with the C/P/C planes.

Related literature

For related literature, see: Ahmed et al. (1996 ▶); Harcken & Martin (2001 ▶); Kojima et al. (2002 ▶); McDonald & Campbell (1959 ▶); Nassar et al. (2004 ▶); Phillips et al. (2002 ▶); Tanaka et al. (2003 ▶); Wittig & Schöllkopf (1954 ▶).

Experimental

Crystal data

C27H24O2P+·Br−·0.5H2O

M = 500.35

Monoclinic,

a = 21.017 (8) Å

b = 14.045 (5) Å

c = 19.868 (7) Å

β = 126.107 (4)°

V = 4738 (3) Å3

Z = 8

Mo Kα radiation

μ = 1.83 mm−1

T = 123 (2) K

0.40 × 0.31 × 0.22 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer

Absorption correction: integration (ABSCOR; Higashi, 1999 ▶) T min = 0.404, T max = 0.520

18847 measured reflections

5425 independent reflections

5022 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.079

S = 1.15

5425 reflections

290 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −0.53 e Å−3

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001 ▶); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2004 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97 and TEXSAN.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808000184/hg2361sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808000184/hg2361Isup2.hkl

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

C27H24O2P+·Br–·0.5H2O	F000 = 2056
Mr = 500.35	Dx = 1.403 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71070 Å
Hall symbol: -C 2yc	Cell parameters from 7012 reflections
a = 21.017 (8) Å	θ = 3.1–27.5º
b = 14.045 (5) Å	µ = 1.83 mm−1
c = 19.868 (7) Å	T = 123 (2) K
β = 126.107 (4)º	Block, colorless
V = 4738 (3) Å3	0.40 × 0.31 × 0.22 mm
Z = 8

Rigaku/MSC Mercury CCD diffractometer	5022 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.038
T = 123(2) K	θmax = 27.5º
ω scans	θmin = 3.2º
Absorption correction: integration(ABSCOR; Higashi, 1999)	h = −27→25
Tmin = 0.404, Tmax = 0.520	k = −18→17
18847 measured reflections	l = −18→25
5425 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.079	w = 1/[σ2(Fo2) + (0.0133P)2 + 10.1118P] where P = (Fo2 + 2Fc2)/3
S = 1.15	(Δ/σ)max = 0.001
5425 reflections	Δρmax = 0.51 e Å−3
290 parameters	Δρmin = −0.53 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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	Uiso*/Ueq
P1	0.31029 (3)	0.44471 (4)	0.32117 (3)	0.01545 (12)
C1	0.41411 (12)	0.41713 (15)	0.38823 (13)	0.0174 (4)
H1A	0.4424	0.4655	0.3789	0.021*
H1B	0.4324	0.4234	0.4468	0.021*
C2	0.43759 (12)	0.32001 (16)	0.37752 (12)	0.0181 (4)
C3	0.42000 (13)	0.23839 (16)	0.40364 (13)	0.0206 (5)
H3	0.3909	0.2438	0.4261	0.025*
C4	0.44456 (13)	0.14960 (17)	0.39714 (14)	0.0222 (5)
H4	0.4314	0.0945	0.4143	0.027*
C5	0.48845 (12)	0.14061 (16)	0.36557 (13)	0.0205 (5)
C6	0.50870 (13)	0.22217 (18)	0.34252 (14)	0.0249 (5)
H6	0.5408	0.2170	0.3235	0.030*
C7	0.48255 (13)	0.31103 (18)	0.34700 (14)	0.0241 (5)
H7	0.4953	0.3660	0.3292	0.029*
C8	0.51658 (13)	0.04628 (18)	0.35787 (14)	0.0260 (5)
O1	0.56546 (10)	0.03619 (14)	0.34485 (11)	0.0341 (4)
O2	0.48183 (10)	−0.02626 (12)	0.36867 (12)	0.0343 (4)
C9	0.50683 (18)	−0.1213 (2)	0.3647 (2)	0.0495 (8)
H9A	0.4922	−0.1329	0.3085	0.074*
H9B	0.4811	−0.1685	0.3776	0.074*
H9C	0.5641	−0.1266	0.4052	0.074*
C10	0.27533 (12)	0.45605 (15)	0.21423 (13)	0.0167 (4)
C11	0.19410 (13)	0.45949 (17)	0.15136 (13)	0.0217 (5)
H11	0.1578	0.4523	0.1648	0.026*
C12	0.16704 (14)	0.47353 (17)	0.06923 (14)	0.0252 (5)
H12	0.1120	0.4762	0.0265	0.030*
C13	0.21980 (14)	0.48367 (16)	0.04915 (14)	0.0240 (5)
H13	0.2008	0.4929	−0.0072	0.029*
C14	0.30000 (14)	0.48039 (17)	0.11111 (14)	0.0243 (5)
H14	0.3361	0.4875	0.0974	0.029*
C15	0.32787 (13)	0.46655 (16)	0.19402 (13)	0.0212 (5)
H15	0.3830	0.4643	0.2366	0.025*
C16	0.29724 (13)	0.55555 (15)	0.35705 (13)	0.0182 (4)
C17	0.22172 (14)	0.58176 (18)	0.33081 (17)	0.0311 (6)
H17	0.1780	0.5419	0.2939	0.037*
C18	0.21096 (16)	0.66619 (19)	0.35887 (18)	0.0363 (6)
H18	0.1596	0.6842	0.3409	0.044*
C19	0.27431 (15)	0.72433 (17)	0.41278 (15)	0.0280 (5)
H19	0.2665	0.7816	0.4325	0.034*
C20	0.34886 (14)	0.69949 (17)	0.43800 (14)	0.0253 (5)
H20	0.3921	0.7402	0.4744	0.030*
C21	0.36103 (13)	0.61531 (17)	0.41050 (13)	0.0221 (5)
H21	0.4124	0.5984	0.4279	0.027*
C22	0.25177 (12)	0.35735 (15)	0.32766 (13)	0.0171 (4)
C23	0.24544 (13)	0.36231 (17)	0.39383 (14)	0.0223 (5)
H23	0.2734	0.4097	0.4356	0.027*
C24	0.19816 (14)	0.29762 (18)	0.39790 (15)	0.0265 (5)
H24	0.1933	0.3011	0.4424	0.032*
C25	0.15793 (14)	0.22790 (18)	0.33766 (16)	0.0281 (5)
H25	0.1248	0.1846	0.3404	0.034*
C26	0.16576 (15)	0.22106 (18)	0.27322 (16)	0.0287 (5)
H26	0.1388	0.1725	0.2324	0.034*
C27	0.21322 (13)	0.28556 (16)	0.26844 (14)	0.0230 (5)
H27	0.2193	0.2806	0.2248	0.028*
Br1	0.456153 (14)	0.381335 (18)	0.588418 (14)	0.02564 (7)
O3	0.5000	0.49982 (19)	0.7500	0.0300 (5)
H3O	0.485 (2)	0.455 (3)	0.702 (2)	0.090 (14)*

	U11	U22	U33	U12	U13	U23
P1	0.0136 (2)	0.0170 (3)	0.0155 (2)	−0.0005 (2)	0.0084 (2)	0.0006 (2)
C1	0.0142 (9)	0.0186 (10)	0.0169 (10)	−0.0006 (8)	0.0077 (8)	0.0010 (8)
C2	0.0129 (9)	0.0227 (11)	0.0153 (9)	0.0020 (8)	0.0064 (8)	0.0026 (8)
C3	0.0206 (11)	0.0213 (11)	0.0230 (11)	−0.0003 (9)	0.0146 (9)	0.0007 (9)
C4	0.0208 (11)	0.0208 (11)	0.0260 (11)	−0.0012 (9)	0.0144 (10)	−0.0006 (9)
C5	0.0146 (10)	0.0261 (12)	0.0147 (10)	0.0029 (8)	0.0053 (8)	−0.0020 (8)
C6	0.0200 (11)	0.0386 (14)	0.0201 (10)	0.0080 (10)	0.0140 (9)	0.0060 (10)
C7	0.0208 (11)	0.0294 (13)	0.0227 (11)	0.0054 (10)	0.0132 (9)	0.0101 (10)
C8	0.0173 (11)	0.0318 (13)	0.0184 (11)	0.0062 (10)	0.0047 (9)	−0.0048 (9)
O1	0.0263 (9)	0.0428 (11)	0.0333 (9)	0.0090 (8)	0.0176 (8)	−0.0058 (8)
O2	0.0256 (9)	0.0222 (9)	0.0494 (11)	0.0018 (7)	0.0189 (9)	−0.0084 (8)
C9	0.0380 (16)	0.0257 (14)	0.078 (2)	0.0020 (12)	0.0304 (16)	−0.0167 (15)
C10	0.0177 (10)	0.0144 (10)	0.0174 (10)	0.0010 (8)	0.0100 (9)	0.0024 (8)
C11	0.0197 (11)	0.0266 (12)	0.0195 (10)	0.0039 (9)	0.0121 (9)	0.0022 (9)
C12	0.0204 (11)	0.0298 (13)	0.0185 (10)	0.0031 (10)	0.0077 (9)	0.0019 (9)
C13	0.0305 (12)	0.0228 (12)	0.0183 (10)	0.0019 (10)	0.0143 (10)	0.0027 (9)
C14	0.0291 (12)	0.0274 (12)	0.0231 (11)	−0.0023 (10)	0.0190 (10)	0.0021 (9)
C15	0.0185 (10)	0.0236 (12)	0.0204 (10)	−0.0018 (9)	0.0109 (9)	0.0011 (9)
C16	0.0186 (10)	0.0171 (10)	0.0188 (10)	0.0007 (8)	0.0110 (9)	0.0012 (8)
C17	0.0184 (11)	0.0266 (13)	0.0435 (15)	−0.0029 (10)	0.0156 (11)	−0.0082 (11)
C18	0.0274 (13)	0.0282 (14)	0.0588 (18)	0.0024 (11)	0.0283 (13)	−0.0050 (12)
C19	0.0387 (14)	0.0191 (12)	0.0342 (13)	0.0025 (10)	0.0258 (12)	−0.0011 (10)
C20	0.0260 (12)	0.0220 (12)	0.0203 (11)	−0.0020 (9)	0.0094 (10)	−0.0039 (9)
C21	0.0181 (10)	0.0233 (11)	0.0205 (10)	0.0016 (9)	0.0088 (9)	−0.0008 (9)
C22	0.0144 (10)	0.0180 (11)	0.0182 (10)	−0.0003 (8)	0.0092 (8)	0.0013 (8)
C23	0.0215 (11)	0.0256 (12)	0.0212 (11)	−0.0001 (9)	0.0134 (9)	0.0005 (9)
C24	0.0284 (12)	0.0319 (13)	0.0268 (12)	0.0044 (10)	0.0205 (10)	0.0072 (10)
C25	0.0282 (12)	0.0236 (12)	0.0413 (14)	−0.0011 (10)	0.0255 (12)	0.0058 (10)
C26	0.0308 (13)	0.0243 (12)	0.0350 (13)	−0.0084 (10)	0.0217 (11)	−0.0059 (10)
C27	0.0258 (12)	0.0223 (12)	0.0238 (11)	−0.0034 (9)	0.0162 (10)	−0.0020 (9)
Br1	0.02436 (12)	0.03282 (14)	0.02411 (12)	−0.00150 (10)	0.01670 (10)	0.00167 (10)
O3	0.0276 (13)	0.0313 (14)	0.0331 (13)	0.000	0.0190 (11)	0.000

P1—C22	1.795 (2)	C12—H12	0.9500
P1—C16	1.799 (2)	C13—C14	1.383 (3)
P1—C10	1.800 (2)	C13—H13	0.9500
P1—C1	1.806 (2)	C14—C15	1.399 (3)
C1—C2	1.508 (3)	C14—H14	0.9500
C1—H1A	0.9900	C15—H15	0.9500
C1—H1B	0.9900	C16—C17	1.397 (3)
C2—C3	1.395 (3)	C16—C21	1.397 (3)
C2—C7	1.397 (3)	C17—C18	1.384 (4)
C3—C4	1.385 (3)	C17—H17	0.9500
C3—H3	0.9500	C18—C19	1.381 (4)
C4—C5	1.393 (3)	C18—H18	0.9500
C4—H4	0.9500	C19—C20	1.379 (4)
C5—C6	1.390 (3)	C19—H19	0.9500
C5—C8	1.495 (3)	C20—C21	1.388 (3)
C6—C7	1.388 (3)	C20—H20	0.9500
C6—H6	0.9500	C21—H21	0.9500
C7—H7	0.9500	C22—C27	1.391 (3)
C8—O1	1.207 (3)	C22—C23	1.399 (3)
C8—O2	1.343 (3)	C23—C24	1.384 (3)
O2—C9	1.454 (3)	C23—H23	0.9500
C9—H9A	0.9800	C24—C25	1.383 (4)
C9—H9B	0.9800	C24—H24	0.9500
C9—H9C	0.9800	C25—C26	1.387 (4)
C10—C15	1.388 (3)	C25—H25	0.9500
C10—C11	1.401 (3)	C26—C27	1.392 (3)
C11—C12	1.390 (3)	C26—H26	0.9500
C11—H11	0.9500	C27—H27	0.9500
C12—C13	1.389 (3)	O3—H3O	1.03 (4)
C22—P1—C16	107.00 (11)	C13—C12—H12	119.7
C22—P1—C10	108.96 (10)	C11—C12—H12	119.7
C16—P1—C10	109.85 (10)	C14—C13—C12	120.1 (2)
C22—P1—C1	112.43 (10)	C14—C13—H13	120.0
C16—P1—C1	107.06 (10)	C12—C13—H13	120.0
C10—P1—C1	111.41 (10)	C13—C14—C15	119.8 (2)
C2—C1—P1	116.34 (15)	C13—C14—H14	120.1
C2—C1—H1A	108.2	C15—C14—H14	120.1
P1—C1—H1A	108.2	C10—C15—C14	120.2 (2)
C2—C1—H1B	108.2	C10—C15—H15	119.9
P1—C1—H1B	108.2	C14—C15—H15	119.9
H1A—C1—H1B	107.4	C17—C16—C21	119.7 (2)
C3—C2—C7	118.9 (2)	C17—C16—P1	119.02 (17)
C3—C2—C1	120.7 (2)	C21—C16—P1	121.27 (17)
C7—C2—C1	120.3 (2)	C18—C17—C16	119.7 (2)
C4—C3—C2	120.7 (2)	C18—C17—H17	120.2
C4—C3—H3	119.7	C16—C17—H17	120.2
C2—C3—H3	119.7	C19—C18—C17	120.5 (2)
C3—C4—C5	120.4 (2)	C19—C18—H18	119.8
C3—C4—H4	119.8	C17—C18—H18	119.8
C5—C4—H4	119.8	C20—C19—C18	120.1 (2)
C6—C5—C4	119.1 (2)	C20—C19—H19	119.9
C6—C5—C8	118.7 (2)	C18—C19—H19	119.9
C4—C5—C8	122.2 (2)	C19—C20—C21	120.4 (2)
C7—C6—C5	120.7 (2)	C19—C20—H20	119.8
C7—C6—H6	119.7	C21—C20—H20	119.8
C5—C6—H6	119.7	C20—C21—C16	119.6 (2)
C6—C7—C2	120.2 (2)	C20—C21—H21	120.2
C6—C7—H7	119.9	C16—C21—H21	120.2
C2—C7—H7	119.9	C27—C22—C23	120.0 (2)
O1—C8—O2	123.9 (2)	C27—C22—P1	121.14 (17)
O1—C8—C5	124.3 (2)	C23—C22—P1	118.82 (16)
O2—C8—C5	111.8 (2)	C24—C23—C22	119.4 (2)
C8—O2—C9	116.1 (2)	C24—C23—H23	120.3
O2—C9—H9A	109.5	C22—C23—H23	120.3
O2—C9—H9B	109.5	C25—C24—C23	120.5 (2)
H9A—C9—H9B	109.5	C25—C24—H24	119.7
O2—C9—H9C	109.5	C23—C24—H24	119.7
H9A—C9—H9C	109.5	C24—C25—C26	120.2 (2)
H9B—C9—H9C	109.5	C24—C25—H25	119.9
C15—C10—C11	119.9 (2)	C26—C25—H25	119.9
C15—C10—P1	120.68 (16)	C25—C26—C27	119.8 (2)
C11—C10—P1	119.38 (17)	C25—C26—H26	120.1
C12—C11—C10	119.5 (2)	C27—C26—H26	120.1
C12—C11—H11	120.3	C22—C27—C26	119.9 (2)
C10—C11—H11	120.3	C22—C27—H27	120.1
C13—C12—C11	120.5 (2)	C26—C27—H27	120.1
C22—P1—C1—C2	54.37 (19)	C11—C10—C15—C14	−0.1 (3)
C16—P1—C1—C2	171.59 (16)	P1—C10—C15—C14	−176.59 (18)
C10—P1—C1—C2	−68.29 (19)	C13—C14—C15—C10	0.0 (4)
P1—C1—C2—C3	−71.4 (2)	C22—P1—C16—C17	−43.1 (2)
P1—C1—C2—C7	113.4 (2)	C10—P1—C16—C17	75.1 (2)
C7—C2—C3—C4	−1.9 (3)	C1—P1—C16—C17	−163.83 (19)
C1—C2—C3—C4	−177.2 (2)	C22—P1—C16—C21	136.78 (19)
C2—C3—C4—C5	1.1 (3)	C10—P1—C16—C21	−105.09 (19)
C3—C4—C5—C6	1.5 (3)	C1—P1—C16—C21	16.0 (2)
C3—C4—C5—C8	179.7 (2)	C21—C16—C17—C18	−0.8 (4)
C4—C5—C6—C7	−3.1 (3)	P1—C16—C17—C18	179.1 (2)
C8—C5—C6—C7	178.7 (2)	C16—C17—C18—C19	−0.3 (4)
C5—C6—C7—C2	2.2 (3)	C17—C18—C19—C20	1.2 (4)
C3—C2—C7—C6	0.3 (3)	C18—C19—C20—C21	−1.0 (4)
C1—C2—C7—C6	175.6 (2)	C19—C20—C21—C16	−0.1 (4)
C6—C5—C8—O1	11.6 (3)	C17—C16—C21—C20	1.0 (3)
C4—C5—C8—O1	−166.6 (2)	P1—C16—C21—C20	−178.90 (17)
C6—C5—C8—O2	−169.47 (19)	C16—P1—C22—C27	144.04 (18)
C4—C5—C8—O2	12.3 (3)	C10—P1—C22—C27	25.3 (2)
O1—C8—O2—C9	0.5 (3)	C1—P1—C22—C27	−98.69 (19)
C5—C8—O2—C9	−178.4 (2)	C16—P1—C22—C23	−36.1 (2)
C22—P1—C10—C15	−140.05 (18)	C10—P1—C22—C23	−154.78 (17)
C16—P1—C10—C15	103.04 (19)	C1—P1—C22—C23	81.2 (2)
C1—P1—C10—C15	−15.4 (2)	C27—C22—C23—C24	−2.5 (3)
C22—P1—C10—C11	43.5 (2)	P1—C22—C23—C24	177.58 (17)
C16—P1—C10—C11	−73.5 (2)	C22—C23—C24—C25	0.6 (4)
C1—P1—C10—C11	168.08 (17)	C23—C24—C25—C26	1.2 (4)
C15—C10—C11—C12	−0.1 (3)	C24—C25—C26—C27	−1.1 (4)
P1—C10—C11—C12	176.46 (18)	C23—C22—C27—C26	2.6 (3)
C10—C11—C12—C13	0.3 (4)	P1—C22—C27—C26	−177.47 (18)
C11—C12—C13—C14	−0.4 (4)	C25—C26—C27—C22	−0.8 (4)
C12—C13—C14—C15	0.2 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···Br1	1.03 (4)	2.22 (4)	3.2308 (17)	169 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯Br1	1.03 (4)	2.22 (4)	3.2308 (17)	169 (3)