[4-(Methoxy­carbon­yl)benz­yl]triphenyl­phospho­nium bromide hemihydrate

Nazir, S.; Khawar Rauf, M.; Ebihara, M.; Hameed, S.

doi:10.1107/S1600536808000184

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o423

doi:10.1107/S1600536808000184

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[4-(Methoxycarbonyl)benzyl]triphenylphosphonium bromide hemihydrate

Saba Nazir,^a M. Khawar Rauf,^b Masahiro Ebihara ^b and Shahid Hameed ^a ^*

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bDepartment of Chemistry, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan
^*Correspondence e-mail: shameed@qau.edu.pk

(Received 30 November 2007; accepted 3 January 2008; online 11 January 2008)

In the crystal structure of the title compound, C₂₇H₂₄O₂P⁺·Br⁻·0.5H₂O, there are intermolecular O—H⋯Br hydrogen bonds between the H atoms of the water of crystallization and the bromide anions. The three phenyl rings of the triphenylphosphonium 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_r = 500.35
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.043
wR(F²) = 0.079
S = 1.15
5425 reflections
290 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.53 e Å⁻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)

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.

Supporting information

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

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

checkCIF report

Comment top

One of the most useful methods for the synthesis of alkenes with control over the stereoselectivity is the well known Wittig reaction (Wittig & Schöllkopf, 1954). It is mainly due to the stereoselectivity of the Wittig reagent that not only its use in the synthesis (Kojima et al., 2002; Phillips et al., 2002; Harcken & Martin, 2001) has not seen a decline but new and improved methods for its synthesis are being constantly developed (Nassar et al., 2004; Tanaka et al., 2003; Kojima et al., 2002). The title compound, (I), is an intermediate in the synthesis of (E)-hydroxyalkyl 4-(4-substituted styryl)benzoate as a part of the project to synthesize ligands for polymeric liquid crystals. Here, we are going to present the crystal structure of the title compound (I). All the geometric parameters are in agreement with the the similar type of studies made by (Ahmed et al., 1996) There are standard electrostatic interactions between the triphenyl-(4-methylcarboxy)benzylphosphonium cations and the bromide anions. It is confirmed that the compound (I) is an ion pair (Fig. 1), with a distance of 4.382 (2)Å between the P⁺ and Br^- centres.

Related literature top

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 top

The triphenyl-(4-methylcarboxy)benzylphosphonium bromide (I) was synthesized following a method reported in the literature (Mcdonald & Campbell, 1959).A mixture of methyl 4-(bromomethyl)benzoate 2.5 g, 0.01 mol) and triphenylphosphine (2.43 g, 0.01 mol) in 40 ml of toluene was heated under reflux for 3 hr. After cooling to room temperature the salt was filtered, washed with ether and dried under reduced pressure.Yield: 81%, m.p: 245–248°C, R_f = 0.11 (n-Hexane: ethylacetate 7:3). IR (KBr, ν_max, cm^-1): 3010, 2926, 2830, 1719, 1605, 786. ¹H-NMR (CDCl₃): δ 3.87 (3H, s), 5.65 (2H, d, J = 15 Hz), 7.70 (17H, m), 8.04 (2H, d, J = 8.1 Hz). ¹³C-NMR (75 MHz, CDCl₃):δ 52.23, 30.58 (d, J = 186 Hz), 117.56 (d, J = 342 Hz),129.70 (d, J = 12 Hz), 129.87 (d, J = 18 Hz), 130.165 (d, J = 51 Hz), 131.73 (d, J = 21 Hz), 132.80 (d, J = 33 Hz), 134.45 (d, J = 36 Hz), 166.54.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); 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 (Sheldrick, 2008) and TEXSAN (Molecular Structure Corporation & Rigaku, 2004).

Figures top

Fig. 1. Molecular structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 30% probability level.

[4-(Methoxycarbonyl)benzyl]triphenylphosphonium bromide hemihydrate top

Crystal data top

C₂₇H₂₄O₂P⁺·Br⁻·0.5H₂O	F(000) = 2056
M_r = 500.35	D_x = 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 = 3.1–27.5°
b = 14.045 (5) Å	µ = 1.83 mm⁻¹
c = 19.868 (7) Å	T = 123 K
β = 126.107 (4)°	Block, colorless
V = 4738 (3) Å³	0.40 × 0.31 × 0.22 mm
Z = 8

Data collection top

Rigaku/MSC Mercury CCD diffractometer	5022 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: integration (ABSCOR; Higashi, 1999)	h = −27→25
T_min = 0.404, T_max = 0.520	k = −18→17
18847 measured reflections	l = −18→25
5425 independent 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ²(F_o²) + (0.0133P)² + 10.1118P] where P = (F_o² + 2F_c²)/3
5425 reflections	(Δ/σ)_max = 0.001
290 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

C₂₇H₂₄O₂P⁺·Br⁻·0.5H₂O	V = 4738 (3) Å³
M_r = 500.35	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 21.017 (8) Å	µ = 1.83 mm⁻¹
b = 14.045 (5) Å	T = 123 K
c = 19.868 (7) Å	0.40 × 0.31 × 0.22 mm
β = 126.107 (4)°

Data collection top

Rigaku/MSC Mercury CCD diffractometer	5425 independent reflections
Absorption correction: integration (ABSCOR; Higashi, 1999)	5022 reflections with I > 2σ(I)
T_min = 0.404, T_max = 0.520	R_int = 0.038
18847 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ²(F_o²) + (0.0133P)² + 10.1118P] where P = (F_o² + 2F_c²)/3
5425 reflections	Δρ_max = 0.51 e Å⁻³
290 parameters	Δρ_min = −0.53 e Å⁻³

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
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)*

Atomic displacement parameters (Å²) top

	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

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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)

Experimental details

Crystal data
Chemical formula	C₂₇H₂₄O₂P⁺·Br⁻·0.5H₂O
M_r	500.35
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	123
a, b, c (Å)	21.017 (8), 14.045 (5), 19.868 (7)
β (°)	126.107 (4)
V (Å³)	4738 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.83
Crystal size (mm)	0.40 × 0.31 × 0.22

Data collection
Diffractometer	Rigaku/MSC Mercury CCD diffractometer
Absorption correction	Integration (ABSCOR; Higashi, 1999)
T_min, T_max	0.404, 0.520
No. of measured, independent and observed [I > 2σ(I)] reflections	18847, 5425, 5022
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.079, 1.15
No. of reflections	5425
No. of parameters	290
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0133P)² + 10.1118P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.53

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2001), SIR97 (Altomare et al., 1999), ORTEPII (Johnson, 1976), SHELXL97 (Sheldrick, 2008) and TEXSAN (Molecular Structure Corporation & Rigaku, 2004).

Hydrogen-bond geometry (Å, º) top

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)

Acknowledgements

MKR is grateful to the Higher Education Commission of Pakistan for financial support under the International support initiative program for a Doctoral Fellowship at Gifu University, Japan.

References

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