(9H-Fluoren-9-yl)(phen­yl)phosphinic acid

Burrow, R.A.; Siqueira da Silva, R.M.

doi:10.1107/S160053681204891X

organic compounds

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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Page o1

https://doi.org/10.1107/S160053681204891X

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(9H-Fluoren-9-yl)(phenyl)phosphinic acid

Robert A. Burrow ^a ^* and Rubia M. Siqueira da Silva ^a

^aLaboratório de Materiais Inorgânicos, Universidade Federal de Santa Maria, 97105–900 Santa Maria–RS, Brazil
^*Correspondence e-mail: rburrow@ewald.base.ufsm.br

(Received 22 November 2012; accepted 28 November 2012; online 5 December 2012)

The crystal structure of the title compound, C₁₉H₁₅O₂P, features pairs of molecules joined by O—H⋯O hydrogen bonds across crystallographic inversion centers. In addition, π–π interactions, with a centroid–centroid distance of 3.6273 (9) Å between the fluorene ring systems, connect the dimers into chains along [01-1]. The three rings make dihedral angles of 1.34 (9), 1.52 (10) and 1.51 (7)° with each other.

Related literature

For related structues, see: Burrow et al. (2000 ); Vioux et al. (2004 ); Siqueira et al. (2006 ); Burrow & Siqueira da Silva (2011a ,b ); Burrow & Siqueira da Silva (2012 ). For a description of the Cambridge Structural Database and geometry checks using Mogul, see: Allen (2002 ); Bruno et al. (2004 ). For hydrogen-bond information, see: Jeffrey (1997 ). For the synthesis, see: Boyd & Regan (1994 ).

Experimental

Crystal data

C₁₉H₁₅O₂P
M_r = 306.28
Triclinic, $[P \overline 1]$
a = 8.5736 (7) Å
b = 9.5668 (8) Å
c = 9.6750 (7) Å
α = 73.348 (5)°
β = 87.388 (5)°
γ = 83.619 (6)°
V = 755.49 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 100 K
0.28 × 0.13 × 0.07 mm

Data collection

Bruker X8 Kappa APEXII diffractometer
Absorption correction: numerical (SADABS; Bruker, 2012 ) T_min = 0.941, T_max = 0.988
21221 measured reflections
4614 independent reflections
3560 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.112
S = 1.03
4614 reflections
202 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.90 (2)	1.61 (2)	2.5107 (15)	177.9 (19)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681204891X/lh5563sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681204891X/lh5563Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681204891X/lh5563Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S160053681204891X/lh5563Isup4.cml

checkCIF report

Comment top

Phosphinic acids usually form continuous chain structures via hydrogen bonding interactions between neighboring phosphinic acid groups in the solid state (Burrow et al., 2000; Burrow & Siqueira da Silva, 2011a,b; Burrow & Siqueira da Silva, 2012). This tendency, due to the strong P—O dipole moment, aids in the formation of chain like structures in coordination polymers (Vioux et al., 2004; Siqueira et al., 2006). Smaller organyl groups, such as the methyl group, bound to the P atom can direct the the structure to form lamellar structures (Burrow & Siqueira da Silva, 2011b). Larger groups such as fluorenyl in the title compound have the ability to do the opposite, reducing the structure to dimeric structures by making chain formation an unfavorable process due to steric interactions between the bulky groups. Here we report the synthesis and crystal structure of the title compound which demonstrates the steric effects of the organyl groups in the solid state.

The molecular structure of the title compound is shown in Fig. 1. The geometry of the molecule shows no usual features. An analysis by Mogul (Bruno et al., 2004) using the Cambridge Strucrtural Database (Version 5.32, May, 2012 update; Allen, 2002) reports no |z-score| greater than 1 for the bond lengths. The highest |z-scores| for bond angles are 1.743 and 1.661 for the C31—C32—C33 and C22—C23—C24 angles, respectively, which are significantly smaller than the 120 ° expected for a benzene ring. This deviation is due to the strained, planar 5-membered C21/C22/C27/C28/C33 ring. The three ring systems of the fluorenyl group is almost planar with an r.m.s. deviation of 0.026 Å of the thirteen atoms from a least squares fitted plane through the atoms. Considering each ring systems individually, central five-membered ring and the two benzene rings of the fluorenyl moiety are all each essentially planar with r.m.s. deviations of 0.0099 Å, 0.0022 Å and 0.0032 Å for the rings C21/C22/C27/C28/C33 (A), C22/C23/C24/C25/C26/C27 (B) and C28/C29/C30/C31/C32/C33 (C) rings, respectively. The dihedral angles between the planes (A) and (B), (A) and (C), and (B) and (C) are 1.34 (9) °, 1.52 (10) °, and 1.51 (7) °, respectively.

In the crystal, molecules are joined into dimeric units by pairs of O—H···O═P hydrogen bonds across crystallographic inversion centers (Fig. 2). The O···O distance at 2.5107 (15) Å is reasonably short indicating moderately-strong hydrogen bonding (Jeffrey, 1997). The dimeric units are joined into continuous chains along the the crystallographic [011] direction by π–π interactions between the fluorenyl ring systems across crystallographic inversion centers. An analysis by PLATON (Spek, 2009) shows a ring-to-ring centroid distance of 3.6273 (9)Å for the 5-membered rings (C21/C22/C27/C28/C33) which are co-planar and have a ring slippage distance of 0.825 Å. The perpendicular distances between the benzene rings are 3.4831 (6) and 3.4608 (6) Å.

The packing diagram, Fig. 3, shows columns of phosphinate groups alternating with columns of fluorenyl groups along [100]. The phenyl groups pack parallel to the columns, pointing along [100].

Related literature top

For related structues, see: Burrow et al. (2000); Vioux et al. (2004); Siqueira et al. (2006); Burrow & Siqueira da Silva (2011a,b); Burrow & Siqueira da Silva (2012). For structural data, see: Allen, 2002; Bruno et al. (2004). For geometry calculations, see: Spek (2009). For hydrogen-bond information, see: Jeffrey (1997). For the synthesis, see: Boyd & Regan (1994).

Experimental top

The procedure of Boyd & Regan (1994) was followed. To a solution of phenylphosphinic acid (2.0 g, 14.1 mmol) in dichloromethane (30 ml), diisopropylethylamine (5.16 ml, 29.6 mmol) and trimethylsilyl chloride (3.74 ml, 29.6 mmol) were separately added at 273K under argon. The reaction mixture was stirred at room temperature for 2–3 h, cooled to 273K and 9H-9-bromofluorene (3.46 g, 14.1 mmol) was added. After further stirring at room temperature for 3 days, the solvent was removed under vacuum. The residue was suspended in hydrochloric acid (2 M, 20 ml) and filtered on a glass frit. The white solid was washed with water and dried giving a yield of 2.30 g (53%) of pure product. IR: 3064 (w), 1592 (m), 1476 (w), 1440 (m), 1174 (vs), 1131 (s), 982 (vs), 818 (s), 735 (s), 717 (s), 692 (s), 545 (vs), 494 (m), 423 (m) cm^-1. Crystals suitable for single-crystal X-ray analysis were grown from an acetone solution of the title compound in a desiccator with silical gel.

Structure description top

The packing diagram, Fig. 3, shows columns of phosphinate groups alternating with columns of fluorenyl groups along [100]. The phenyl groups pack parallel to the columns, pointing along [100].

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, with 50% probability ellipsoids.
	Fig. 2. The H bonding interactions, dashed red lines, and π-π interactions, dashed gray lines, which join the molecules of the title compound into continuous chains along the crystallographic [011] direction. Non-essential H atoms are omitted and C atoms are shown as sticks for clarity. Symmetry codes: (i) 1–x, 1–y, 1–z; (ii) 1–x, 2–y, 1–z; (iii) x, -1 + y, 1 + z.
	Fig. 3. The packing diagram of the title compound in the crystallographic bc direction with the crystallographic a axis pointing down. Non-essential H atoms are omitted and C atoms are shown as sticks for clarity.

(9H-Fluoren-9-yl)(phenyl)phosphinic acid top

Crystal data top

C₁₉H₁₅O₂P	Z = 2
M_r = 306.28	F(000) = 320
Triclinic, P1	D_x = 1.346 Mg m⁻³
a = 8.5736 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5668 (8) Å	Cell parameters from 3726 reflections
c = 9.6750 (7) Å	θ = 2.2–29.6°
α = 73.348 (5)°	µ = 0.19 mm⁻¹
β = 87.388 (5)°	T = 100 K
γ = 83.619 (6)°	Block, colourless
V = 755.49 (10) Å³	0.28 × 0.13 × 0.07 mm

Data collection top

Bruker X8 Kappa APEXII diffractometer	4614 independent reflections
Radiation source: sealed ceramic X ray tube, Siemens KFF	3560 reflections with I > 2σ(I)
Graphite crystal monochromator	R_int = 0.047
Detector resolution: 8.3333 pixels mm^-1	θ_max = 30.6°, θ_min = 3.1°
0.5 ° ω & φ scans	h = −12→12
Absorption correction: numerical (SADABS; Bruker, 2012)	k = −13→13
T_min = 0.941, T_max = 0.988	l = −13→13
21221 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0492P)² + 0.2304P] where P = (F_o² + 2F_c²)/3
4614 reflections	(Δ/σ)_max = 0.001
202 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₉H₁₅O₂P	γ = 83.619 (6)°
M_r = 306.28	V = 755.49 (10) Å³
Triclinic, P1	Z = 2
a = 8.5736 (7) Å	Mo Kα radiation
b = 9.5668 (8) Å	µ = 0.19 mm⁻¹
c = 9.6750 (7) Å	T = 100 K
α = 73.348 (5)°	0.28 × 0.13 × 0.07 mm
β = 87.388 (5)°

Data collection top

Bruker X8 Kappa APEXII diffractometer	4614 independent reflections
Absorption correction: numerical (SADABS; Bruker, 2012)	3560 reflections with I > 2σ(I)
T_min = 0.941, T_max = 0.988	R_int = 0.047
21221 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.33 e Å⁻³
4614 reflections	Δρ_min = −0.41 e Å⁻³
202 parameters

Special details top

Experimental. The crystal was cooled to 100 K under a cold nitrogen stream.

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	0.38649 (4)	0.66642 (4)	0.34500 (4)	0.01663 (10)
O1	0.43045 (13)	0.51673 (11)	0.31276 (11)	0.0229 (2)
H1	0.468 (2)	0.446 (2)	0.390 (2)	0.034*
O2	0.46941 (12)	0.68440 (11)	0.47107 (10)	0.0194 (2)
C11	0.17814 (16)	0.68985 (15)	0.37075 (14)	0.0175 (3)
C12	0.11582 (17)	0.78050 (16)	0.45427 (15)	0.0211 (3)
H12	0.1836	0.8302	0.4944	0.025*
C13	−0.04498 (18)	0.79814 (18)	0.47880 (16)	0.0259 (3)
H13	−0.0872	0.8602	0.5353	0.031*
C14	−0.14413 (18)	0.72501 (18)	0.42077 (16)	0.0270 (3)
H14	−0.254	0.7363	0.4386	0.032*
C15	−0.08337 (18)	0.63552 (18)	0.33692 (16)	0.0263 (3)
H15	−0.1517	0.5862	0.297	0.032*
C16	0.07715 (18)	0.61796 (17)	0.31121 (16)	0.0228 (3)
H16	0.1185	0.5571	0.2532	0.027*
C21	0.43723 (16)	0.80119 (15)	0.18013 (14)	0.0169 (3)
H21	0.5521	0.786	0.1589	0.02*
C22	0.39388 (16)	0.95586 (15)	0.18998 (14)	0.0177 (3)
C23	0.44714 (18)	1.02482 (16)	0.28454 (15)	0.0224 (3)
H23	0.5212	0.9741	0.3566	0.027*
C24	0.3897 (2)	1.16927 (18)	0.27144 (17)	0.0272 (3)
H24	0.4249	1.218	0.3353	0.033*
C25	0.2816 (2)	1.24361 (17)	0.16620 (18)	0.0286 (4)
H25	0.2444	1.3428	0.1586	0.034*
C26	0.22646 (19)	1.17511 (17)	0.07137 (17)	0.0251 (3)
H26	0.1517	1.2262	0.0001	0.03*
C27	0.28382 (17)	1.02979 (15)	0.08387 (14)	0.0184 (3)
C28	0.25172 (17)	0.93164 (16)	−0.00072 (14)	0.0190 (3)
C29	0.15364 (18)	0.95394 (19)	−0.11764 (16)	0.0254 (3)
H29	0.0904	1.0443	−0.1533	0.031*
C30	0.15047 (19)	0.8417 (2)	−0.18061 (16)	0.0301 (4)
H30	0.0847	0.8558	−0.2609	0.036*
C31	0.2418 (2)	0.7084 (2)	−0.12883 (17)	0.0298 (4)
H31	0.2379	0.6331	−0.1743	0.036*
C32	0.33901 (19)	0.68459 (17)	−0.01075 (16)	0.0244 (3)
H32	0.4007	0.5934	0.0255	0.029*
C33	0.34340 (17)	0.79710 (16)	0.05227 (14)	0.0183 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.01661 (18)	0.01688 (17)	0.01648 (17)	−0.00126 (13)	−0.00200 (12)	−0.00478 (13)
O1	0.0300 (6)	0.0182 (5)	0.0207 (5)	0.0024 (4)	−0.0058 (4)	−0.0071 (4)
O2	0.0200 (5)	0.0194 (5)	0.0196 (5)	−0.0018 (4)	−0.0046 (4)	−0.0060 (4)
C11	0.0177 (7)	0.0192 (6)	0.0148 (6)	−0.0048 (5)	−0.0007 (5)	−0.0024 (5)
C12	0.0193 (7)	0.0264 (7)	0.0186 (6)	−0.0042 (6)	−0.0009 (5)	−0.0073 (5)
C13	0.0205 (7)	0.0342 (8)	0.0222 (7)	−0.0016 (6)	0.0021 (6)	−0.0076 (6)
C14	0.0163 (7)	0.0356 (9)	0.0247 (7)	−0.0047 (6)	0.0000 (6)	−0.0009 (6)
C15	0.0224 (8)	0.0301 (8)	0.0256 (7)	−0.0106 (6)	−0.0053 (6)	−0.0031 (6)
C16	0.0243 (8)	0.0234 (7)	0.0216 (7)	−0.0055 (6)	−0.0033 (6)	−0.0062 (6)
C21	0.0151 (6)	0.0191 (6)	0.0169 (6)	−0.0027 (5)	0.0010 (5)	−0.0054 (5)
C22	0.0175 (7)	0.0186 (6)	0.0174 (6)	−0.0052 (5)	0.0049 (5)	−0.0052 (5)
C23	0.0234 (8)	0.0253 (7)	0.0206 (7)	−0.0090 (6)	0.0033 (5)	−0.0078 (6)
C24	0.0330 (9)	0.0273 (8)	0.0269 (8)	−0.0133 (7)	0.0089 (6)	−0.0144 (6)
C25	0.0331 (9)	0.0199 (7)	0.0339 (8)	−0.0058 (6)	0.0124 (7)	−0.0102 (6)
C26	0.0227 (8)	0.0230 (7)	0.0265 (7)	−0.0005 (6)	0.0061 (6)	−0.0037 (6)
C27	0.0186 (7)	0.0199 (7)	0.0164 (6)	−0.0043 (5)	0.0048 (5)	−0.0048 (5)
C28	0.0179 (7)	0.0239 (7)	0.0149 (6)	−0.0043 (5)	0.0032 (5)	−0.0048 (5)
C29	0.0191 (7)	0.0367 (9)	0.0191 (7)	−0.0033 (6)	0.0010 (5)	−0.0057 (6)
C30	0.0247 (8)	0.0501 (10)	0.0190 (7)	−0.0090 (7)	−0.0006 (6)	−0.0135 (7)
C31	0.0322 (9)	0.0407 (9)	0.0244 (7)	−0.0133 (7)	0.0052 (6)	−0.0188 (7)
C32	0.0266 (8)	0.0264 (8)	0.0232 (7)	−0.0066 (6)	0.0061 (6)	−0.0112 (6)
C33	0.0186 (7)	0.0219 (7)	0.0157 (6)	−0.0052 (5)	0.0031 (5)	−0.0066 (5)

Geometric parameters (Å, º) top

P1—O2	1.4997 (10)	C22—C27	1.403 (2)
P1—O1	1.5541 (11)	C23—C24	1.386 (2)
P1—C11	1.7905 (15)	C23—H23	0.95
P1—C21	1.8108 (14)	C24—C25	1.388 (2)
O1—H1	0.90 (2)	C24—H24	0.95
C11—C12	1.396 (2)	C25—C26	1.396 (2)
C11—C16	1.400 (2)	C25—H25	0.95
C12—C13	1.388 (2)	C26—C27	1.395 (2)
C12—H12	0.95	C26—H26	0.95
C13—C14	1.389 (2)	C27—C28	1.4648 (19)
C13—H13	0.95	C28—C29	1.393 (2)
C14—C15	1.387 (2)	C28—C33	1.404 (2)
C14—H14	0.95	C29—C30	1.381 (2)
C15—C16	1.388 (2)	C29—H29	0.95
C15—H15	0.95	C30—C31	1.392 (3)
C16—H16	0.95	C30—H30	0.95
C21—C22	1.5140 (19)	C31—C32	1.395 (2)
C21—C33	1.5181 (19)	C31—H31	0.95
C21—H21	1.0	C32—C33	1.385 (2)
C22—C23	1.3898 (19)	C32—H32	0.95

O2—P1—O1	114.59 (6)	C24—C23—C22	118.52 (15)
O2—P1—C11	110.59 (6)	C24—C23—H23	120.7
O1—P1—C11	108.24 (6)	C22—C23—H23	120.7
O2—P1—C21	110.70 (6)	C23—C24—C25	120.83 (15)
O1—P1—C21	104.29 (6)	C23—C24—H24	119.6
C11—P1—C21	108.08 (6)	C25—C24—H24	119.6
P1—O1—H1	113.2 (12)	C24—C25—C26	121.12 (15)
C12—C11—C16	119.49 (13)	C24—C25—H25	119.4
C12—C11—P1	118.86 (11)	C26—C25—H25	119.4
C16—C11—P1	121.64 (11)	C27—C26—C25	118.36 (15)
C13—C12—C11	120.14 (14)	C27—C26—H26	120.8
C13—C12—H12	119.9	C25—C26—H26	120.8
C11—C12—H12	119.9	C26—C27—C22	120.10 (14)
C12—C13—C14	119.98 (15)	C26—C27—C28	130.83 (14)
C12—C13—H13	120.0	C22—C27—C28	109.06 (12)
C14—C13—H13	120.0	C29—C28—C33	120.35 (14)
C15—C14—C13	120.26 (14)	C29—C28—C27	130.97 (14)
C15—C14—H14	119.9	C33—C28—C27	108.67 (12)
C13—C14—H14	119.9	C30—C29—C28	118.50 (15)
C14—C15—C16	120.11 (14)	C30—C29—H29	120.7
C14—C15—H15	119.9	C28—C29—H29	120.7
C16—C15—H15	119.9	C29—C30—C31	121.31 (15)
C15—C16—C11	120.00 (14)	C29—C30—H30	119.3
C15—C16—H16	120.0	C31—C30—H30	119.3
C11—C16—H16	120.0	C30—C31—C32	120.56 (15)
C22—C21—C33	102.97 (11)	C30—C31—H31	119.7
C22—C21—P1	111.40 (9)	C32—C31—H31	119.7
C33—C21—P1	112.47 (9)	C33—C32—C31	118.38 (15)
C22—C21—H21	109.9	C33—C32—H32	120.8
C33—C21—H21	109.9	C31—C32—H32	120.8
P1—C21—H21	109.9	C32—C33—C28	120.90 (14)
C23—C22—C27	121.07 (14)	C32—C33—C21	129.44 (14)
C23—C22—C21	129.34 (13)	C28—C33—C21	109.66 (12)
C27—C22—C21	109.59 (12)

O2—P1—C11—C12	28.54 (13)	C23—C24—C25—C26	0.5 (2)
O1—P1—C11—C12	154.83 (11)	C24—C25—C26—C27	−0.6 (2)
C21—P1—C11—C12	−92.78 (12)	C25—C26—C27—C22	0.1 (2)
O2—P1—C11—C16	−150.46 (11)	C25—C26—C27—C28	−178.32 (13)
O1—P1—C11—C16	−24.18 (13)	C23—C22—C27—C26	0.3 (2)
C21—P1—C11—C16	88.21 (13)	C21—C22—C27—C26	−179.72 (12)
C16—C11—C12—C13	0.5 (2)	C23—C22—C27—C28	179.08 (12)
P1—C11—C12—C13	−178.55 (11)	C21—C22—C27—C28	−0.95 (15)
C11—C12—C13—C14	0.3 (2)	C26—C27—C28—C29	−0.6 (3)
C12—C13—C14—C15	−0.7 (2)	C22—C27—C28—C29	−179.21 (14)
C13—C14—C15—C16	0.4 (2)	C26—C27—C28—C33	178.00 (14)
C14—C15—C16—C11	0.4 (2)	C22—C27—C28—C33	−0.60 (15)
C12—C11—C16—C15	−0.8 (2)	C33—C28—C29—C30	−0.8 (2)
P1—C11—C16—C15	178.15 (11)	C27—C28—C29—C30	177.70 (14)
O2—P1—C21—C22	−59.17 (11)	C28—C29—C30—C31	0.4 (2)
O1—P1—C21—C22	177.10 (9)	C29—C30—C31—C32	0.3 (2)
C11—P1—C21—C22	62.09 (11)	C30—C31—C32—C33	−0.7 (2)
O2—P1—C21—C33	−174.18 (9)	C31—C32—C33—C28	0.3 (2)
O1—P1—C21—C33	62.09 (11)	C31—C32—C33—C21	179.97 (13)
C11—P1—C21—C33	−52.93 (11)	C29—C28—C33—C32	0.4 (2)
C33—C21—C22—C23	−178.06 (13)	C27—C28—C33—C32	−178.41 (12)
P1—C21—C22—C23	61.18 (17)	C29—C28—C33—C21	−179.31 (12)
C33—C21—C22—C27	1.98 (14)	C27—C28—C33—C21	1.90 (15)
P1—C21—C22—C27	−118.78 (11)	C22—C21—C33—C32	177.99 (14)
C27—C22—C23—C24	−0.4 (2)	P1—C21—C33—C32	−61.99 (17)
C21—C22—C23—C24	179.68 (13)	C22—C21—C33—C28	−2.36 (14)
C22—C23—C24—C25	−0.1 (2)	P1—C21—C33—C28	117.67 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.90 (2)	1.61 (2)	2.5107 (15)	177.9 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₅O₂P
M_r	306.28
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.5736 (7), 9.5668 (8), 9.6750 (7)
α, β, γ (°)	73.348 (5), 87.388 (5), 83.619 (6)
V (Å³)	755.49 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.28 × 0.13 × 0.07

Data collection
Diffractometer	Bruker X8 Kappa APEXII
Absorption correction	Numerical (SADABS; Bruker, 2012)
T_min, T_max	0.941, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	21221, 4614, 3560
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.112, 1.03
No. of reflections	4614
No. of parameters	202
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.41

Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2012), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.90 (2)	1.61 (2)	2.5107 (15)	177.9 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

Financial support from the Conselho Nacional de Desenvolvimento Científico (CNPq, Brazil; grant No. 479747/2009–1), the Fundação de Amparo à Pesquisa (FAPERGS, Rio Grande do Sul; grant No. 10/1645–9) is gratefully acknowledged, as are fellowships from CNPq (RAB; grant No. 308731/2009–3) and the Coordenação de Aperfeiçoamento de Pessoas de Nível Superior (CAPES, Brazil; RMSS). The diffractometer was funded by a CT–INFRA grant from the Financiadora de Estrutos e Projetos (FINEP, Brazil).

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