Tri­phenyl­(benzoyl­methyl)­phospho­nium nitrate: a three-dimensional hydrogen-bonded network

The title phospho­nium salt, C₂₆H₂₂OP⁺·NO₃⁻, is formed by the hydro­lytic cleavage of the acetyl group with concomitant protonation of the yl­idic carbon of α-acetyl-α-benzoyl­methyl­enetri­phenyl­phospho­rane. The structure is stabilized by significant intermolecular C—H...O interactions, involving both the methyl­ene H atoms. The O atoms of the nitrate ion and the benzoyl group, acting as acceptors, contribute to the network of hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.039
• wR factor = 0.114
• Data-to-parameter ratio = 17.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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Computing details

Data collection: SMART-NT (Bruker, 1998); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON97 (Spek, 1997); software used to prepare material for publication: PARST (Nardelli, 1983).

Triphenyl(benzoylmethyl)phosphonium nitrate

Crystal data

C26H22OP^+·NO3^−	Dx = 1.329 Mg m^−3
Mr = 443.42	Melting point: 465.5 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 10.7617 (5) Å	Cell parameters from 940 reflections
b = 19.1957 (7) Å	θ = 10.2–22.5°
c = 21.4568 (9) Å	µ = 0.16 mm^−1
V = 4432.5 (3) Å^3	T = 120 K
Z = 8	Block, colourless
F(000) = 1856	0.36 × 0.30 × 0.26 mm

Data collection

Bruker SMART-6000 CCD diffractometer	5801 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 30.5°, θmin = 1.9°
ω scans	h = −15→15
63180 measured reflections	k = −27→27
6766 independent reflections	l = −30→30

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: difference Fourier map
wR(F^2) = 0.114	All H-atom parameters refined
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0594P)^2 + 1.9368P] where P = (Fo^2 + 2Fc^2)/3
6766 reflections	(Δ/σ)max = 0.001
377 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. Five sets of ω scans (each scan 0.3° in ω, exposure time 20 s), each set at different φ and/or 2θ angles, nominally covered a full sphere of reciprocal space. Crystal to detector distance 5.85 cm.

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 (Ų)

	x	y	z	Uiso*/Ueq
P1	0.38531 (2)	0.121424 (14)	0.331702 (12)	0.01791 (8)
O1	0.21672 (8)	0.18309 (4)	0.24087 (4)	0.02713 (18)
C1	0.40900 (10)	0.20290 (5)	0.29175 (5)	0.02005 (19)
H1	0.4942 (15)	0.2036 (8)	0.2772 (7)	0.031 (4)*
H2	0.4027 (16)	0.2377 (9)	0.3211 (8)	0.037 (4)*
C2	0.31488 (10)	0.21526 (5)	0.24053 (5)	0.02083 (19)
C3	0.34443 (10)	0.26673 (6)	0.19095 (5)	0.0218 (2)
C4	0.26177 (12)	0.27205 (7)	0.14083 (6)	0.0294 (2)
H4	0.1903 (15)	0.2423 (9)	0.1405 (7)	0.032 (4)*
C5	0.28494 (14)	0.31903 (8)	0.09318 (6)	0.0358 (3)
H5	0.2284 (19)	0.3227 (10)	0.0601 (9)	0.052 (5)*
C6	0.38956 (14)	0.36121 (7)	0.09552 (6)	0.0343 (3)
H6	0.4063 (17)	0.3932 (10)	0.0626 (9)	0.045 (5)*
C7	0.47223 (13)	0.35638 (7)	0.14484 (6)	0.0320 (3)
H7	0.5453 (18)	0.3854 (9)	0.1463 (8)	0.042 (5)*
C8	0.44980 (11)	0.30895 (6)	0.19276 (6)	0.0259 (2)
H8	0.5099 (16)	0.3070 (8)	0.2272 (8)	0.035 (4)*
C11	0.51618 (10)	0.11068 (6)	0.38258 (5)	0.02004 (19)
C12	0.60549 (12)	0.05961 (8)	0.37170 (6)	0.0333 (3)
H12	0.6000 (17)	0.0296 (10)	0.3344 (9)	0.045 (5)*
C13	0.70482 (14)	0.05308 (10)	0.41277 (7)	0.0449 (4)
H13	0.765 (2)	0.0155 (11)	0.4055 (10)	0.062 (6)*
C14	0.71501 (12)	0.09698 (9)	0.46363 (6)	0.0369 (3)
H14	0.7833 (18)	0.0924 (10)	0.4910 (9)	0.051 (5)*
C15	0.62633 (12)	0.14813 (7)	0.47423 (6)	0.0310 (3)
H15	0.6320 (17)	0.1796 (9)	0.5096 (9)	0.042 (5)*
C16	0.52603 (11)	0.15504 (6)	0.43402 (5)	0.0265 (2)
H16	0.4631 (17)	0.1886 (9)	0.4413 (8)	0.040 (4)*
C21	0.25170 (10)	0.12243 (5)	0.38161 (5)	0.01963 (19)
C22	0.16844 (11)	0.17834 (6)	0.38242 (5)	0.0249 (2)
H22	0.1809 (14)	0.2165 (8)	0.3541 (7)	0.028 (4)*
C23	0.07192 (11)	0.17887 (7)	0.42578 (6)	0.0291 (2)
H23	0.0148 (16)	0.2189 (9)	0.4249 (8)	0.038 (4)*
C24	0.05856 (11)	0.12458 (7)	0.46799 (6)	0.0291 (2)
H24	−0.0046 (16)	0.1260 (8)	0.4979 (8)	0.031 (4)*
C25	0.14083 (12)	0.06897 (7)	0.46696 (5)	0.0277 (2)
H25	0.1296 (15)	0.0324 (9)	0.4958 (8)	0.033 (4)*
C26	0.23824 (11)	0.06772 (6)	0.42437 (5)	0.0238 (2)
H26	0.2954 (15)	0.0290 (9)	0.4246 (8)	0.033 (4)*
C31	0.38548 (10)	0.05312 (5)	0.27485 (5)	0.02001 (19)
C32	0.31005 (10)	−0.00558 (6)	0.27995 (5)	0.0239 (2)
H32	0.2535 (15)	−0.0102 (8)	0.3143 (7)	0.027 (4)*
C33	0.31837 (12)	−0.05798 (6)	0.23508 (6)	0.0279 (2)
H33	0.2691 (16)	−0.0991 (9)	0.2403 (8)	0.036 (4)*
C34	0.40235 (12)	−0.05229 (6)	0.18638 (6)	0.0273 (2)
H34	0.4088 (16)	−0.0876 (9)	0.1563 (8)	0.039 (4)*
C35	0.47783 (12)	0.00612 (7)	0.18133 (6)	0.0287 (2)
H35	0.5343 (15)	0.0099 (8)	0.1474 (8)	0.033 (4)*
C36	0.46983 (11)	0.05906 (6)	0.22523 (5)	0.0266 (2)
H36	0.5229 (15)	0.0997 (8)	0.2217 (7)	0.030 (4)*
N1	0.84451 (11)	0.14572 (5)	0.61723 (5)	0.0298 (2)
O2	0.91347 (17)	0.19044 (6)	0.59453 (7)	0.0732 (5)
O3	0.84495 (12)	0.08553 (5)	0.59537 (5)	0.0424 (3)
O4	0.77706 (11)	0.16155 (6)	0.66242 (5)	0.0434 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.01691 (13)	0.01813 (13)	0.01869 (13)	0.00044 (9)	−0.00048 (8)	0.00010 (9)
O1	0.0215 (4)	0.0310 (4)	0.0289 (4)	−0.0041 (3)	−0.0039 (3)	0.0035 (3)
C1	0.0197 (4)	0.0192 (4)	0.0212 (4)	−0.0003 (4)	−0.0025 (4)	0.0013 (4)
C2	0.0196 (4)	0.0213 (4)	0.0217 (5)	0.0019 (4)	−0.0015 (4)	−0.0004 (4)
C3	0.0219 (5)	0.0219 (5)	0.0217 (5)	0.0029 (4)	−0.0007 (4)	0.0006 (4)
C4	0.0276 (5)	0.0345 (6)	0.0261 (5)	0.0013 (5)	−0.0055 (4)	0.0036 (4)
C5	0.0399 (7)	0.0413 (7)	0.0263 (6)	0.0063 (6)	−0.0058 (5)	0.0076 (5)
C6	0.0421 (7)	0.0318 (6)	0.0290 (6)	0.0073 (5)	0.0055 (5)	0.0096 (5)
C7	0.0334 (6)	0.0277 (6)	0.0348 (6)	−0.0018 (5)	0.0038 (5)	0.0064 (5)
C8	0.0259 (5)	0.0244 (5)	0.0273 (5)	−0.0006 (4)	−0.0012 (4)	0.0029 (4)
C11	0.0182 (4)	0.0230 (5)	0.0189 (4)	0.0006 (4)	−0.0004 (3)	0.0020 (3)
C12	0.0303 (6)	0.0447 (7)	0.0250 (5)	0.0165 (5)	−0.0044 (4)	−0.0068 (5)
C13	0.0327 (7)	0.0686 (10)	0.0334 (7)	0.0271 (7)	−0.0078 (5)	−0.0088 (7)
C14	0.0237 (6)	0.0602 (9)	0.0268 (6)	0.0065 (6)	−0.0061 (4)	0.0012 (6)
C15	0.0299 (6)	0.0378 (6)	0.0254 (5)	−0.0009 (5)	−0.0063 (4)	−0.0025 (5)
C16	0.0271 (5)	0.0260 (5)	0.0263 (5)	0.0030 (4)	−0.0044 (4)	−0.0027 (4)
C21	0.0169 (4)	0.0217 (4)	0.0203 (4)	−0.0007 (3)	−0.0001 (3)	−0.0020 (3)
C22	0.0222 (5)	0.0257 (5)	0.0267 (5)	0.0028 (4)	0.0003 (4)	−0.0019 (4)
C23	0.0224 (5)	0.0343 (6)	0.0306 (5)	0.0041 (4)	0.0018 (4)	−0.0065 (5)
C24	0.0221 (5)	0.0408 (7)	0.0243 (5)	−0.0050 (5)	0.0039 (4)	−0.0080 (4)
C25	0.0282 (5)	0.0322 (6)	0.0228 (5)	−0.0069 (4)	0.0023 (4)	−0.0005 (4)
C26	0.0248 (5)	0.0239 (5)	0.0228 (5)	−0.0014 (4)	0.0003 (4)	−0.0007 (4)
C31	0.0200 (4)	0.0200 (4)	0.0200 (4)	0.0007 (3)	−0.0009 (3)	−0.0005 (3)
C32	0.0249 (5)	0.0232 (5)	0.0237 (5)	−0.0028 (4)	0.0016 (4)	0.0002 (4)
C33	0.0316 (6)	0.0233 (5)	0.0287 (5)	−0.0047 (4)	−0.0009 (4)	−0.0029 (4)
C34	0.0301 (6)	0.0264 (5)	0.0252 (5)	0.0020 (4)	−0.0030 (4)	−0.0060 (4)
C35	0.0280 (6)	0.0335 (6)	0.0245 (5)	−0.0014 (5)	0.0041 (4)	−0.0048 (4)
C36	0.0271 (5)	0.0273 (5)	0.0255 (5)	−0.0051 (4)	0.0040 (4)	−0.0029 (4)
N1	0.0412 (6)	0.0209 (4)	0.0272 (5)	−0.0038 (4)	−0.0043 (4)	0.0013 (4)
O2	0.1173 (12)	0.0338 (6)	0.0686 (8)	−0.0297 (7)	0.0626 (9)	−0.0180 (5)
O3	0.0752 (8)	0.0203 (4)	0.0316 (5)	−0.0033 (4)	−0.0154 (5)	−0.0018 (3)
O4	0.0463 (6)	0.0355 (5)	0.0483 (6)	−0.0099 (4)	0.0144 (5)	−0.0015 (4)

Geometric parameters (Å, º)

P1—C31	1.7909 (11)	C15—C16	1.3883 (16)
P1—C21	1.7929 (11)	C15—H15	0.971 (19)
P1—C11	1.7939 (11)	C16—H16	0.947 (18)
P1—C1	1.8016 (11)	C21—C22	1.3982 (15)
O1—C2	1.2237 (13)	C21—C26	1.4022 (15)
C1—C2	1.5132 (14)	C22—C23	1.3945 (16)
C1—H1	0.969 (17)	C22—H22	0.960 (16)
C1—H2	0.921 (18)	C23—C24	1.3881 (19)
C2—C3	1.4863 (15)	C23—H23	0.984 (17)
C3—C8	1.3943 (16)	C24—C25	1.3870 (19)
C3—C4	1.3994 (15)	C24—H24	0.935 (17)
C4—C5	1.3858 (18)	C25—C26	1.3908 (16)
C4—H4	0.958 (17)	C25—H25	0.943 (17)
C5—C6	1.388 (2)	C26—H26	0.966 (17)
C5—H5	0.94 (2)	C31—C32	1.3930 (15)
C6—C7	1.386 (2)	C31—C36	1.4038 (15)
C6—H6	0.95 (2)	C32—C33	1.3952 (16)
C7—C8	1.3943 (17)	C32—H32	0.960 (16)
C7—H7	0.964 (19)	C33—C34	1.3858 (17)
C8—H8	0.982 (17)	C33—H33	0.957 (17)
C11—C12	1.3926 (16)	C34—C35	1.3886 (17)
C11—C16	1.3979 (15)	C34—H34	0.938 (18)
C12—C13	1.3910 (18)	C35—C36	1.3884 (16)
C12—H12	0.988 (19)	C35—H35	0.951 (17)
C13—C14	1.383 (2)	C36—H36	0.969 (16)
C13—H13	0.98 (2)	N1—O2	1.2348 (15)
C14—C15	1.388 (2)	N1—O3	1.2469 (14)
C14—H14	0.94 (2)	N1—O4	1.2487 (15)
C31—P1—C21	114.55 (5)	C14—C15—C16	120.01 (12)
C31—P1—C11	109.24 (5)	C14—C15—H15	121.6 (11)
C21—P1—C11	105.51 (5)	C16—C15—H15	118.4 (11)
C31—P1—C1	108.14 (5)	C15—C16—C11	119.44 (11)
C21—P1—C1	112.85 (5)	C15—C16—H16	121.2 (11)
C11—P1—C1	106.16 (5)	C11—C16—H16	119.4 (11)
C2—C1—P1	112.77 (7)	C22—C21—C26	120.03 (10)
C2—C1—H1	113.4 (10)	C22—C21—P1	121.99 (8)
P1—C1—H1	107.4 (9)	C26—C21—P1	117.75 (8)
C2—C1—H2	109.5 (11)	C23—C22—C21	119.43 (11)
P1—C1—H2	107.1 (11)	C23—C22—H22	121.4 (9)
H1—C1—H2	106.3 (14)	C21—C22—H22	119.2 (9)
O1—C2—C3	121.63 (10)	C24—C23—C22	120.46 (11)
O1—C2—C1	119.63 (10)	C24—C23—H23	122.3 (10)
C3—C2—C1	118.74 (9)	C22—C23—H23	117.3 (10)
C8—C3—C4	119.73 (10)	C25—C24—C23	120.08 (11)
C8—C3—C2	122.71 (10)	C25—C24—H24	119.8 (10)
C4—C3—C2	117.56 (10)	C23—C24—H24	120.0 (10)
C5—C4—C3	120.01 (12)	C24—C25—C26	120.33 (11)
C5—C4—H4	121.8 (10)	C24—C25—H25	118.7 (10)
C3—C4—H4	118.2 (10)	C26—C25—H25	120.9 (10)
C4—C5—C6	119.93 (12)	C25—C26—C21	119.66 (11)
C4—C5—H5	119.4 (12)	C25—C26—H26	119.4 (10)
C6—C5—H5	120.7 (12)	C21—C26—H26	120.9 (10)
C7—C6—C5	120.63 (12)	C32—C31—C36	120.15 (10)
C7—C6—H6	119.2 (12)	C32—C31—P1	122.55 (8)
C5—C6—H6	120.2 (12)	C36—C31—P1	117.24 (8)
C6—C7—C8	119.72 (12)	C31—C32—C33	119.44 (10)
C6—C7—H7	120.7 (11)	C31—C32—H32	120.3 (9)
C8—C7—H7	119.6 (11)	C33—C32—H32	120.3 (9)
C7—C8—C3	119.98 (11)	C34—C33—C32	120.35 (11)
C7—C8—H8	117.7 (10)	C34—C33—H33	120.9 (10)
C3—C8—H8	122.3 (10)	C32—C33—H33	118.6 (10)
C12—C11—C16	120.58 (10)	C33—C34—C35	120.26 (11)
C12—C11—P1	121.38 (9)	C33—C34—H34	120.6 (11)
C16—C11—P1	118.03 (8)	C35—C34—H34	119.1 (11)
C13—C12—C11	119.18 (12)	C36—C35—C34	120.12 (11)
C13—C12—H12	120.4 (11)	C36—C35—H35	120.2 (10)
C11—C12—H12	120.3 (11)	C34—C35—H35	119.7 (10)
C14—C13—C12	120.39 (13)	C35—C36—C31	119.68 (11)
C14—C13—H13	121.5 (13)	C35—C36—H36	120.0 (9)
C12—C13—H13	118.1 (13)	C31—C36—H36	120.3 (9)
C13—C14—C15	120.39 (12)	O2—N1—O3	119.57 (12)
C13—C14—H14	119.7 (12)	O2—N1—O4	119.10 (11)
C15—C14—H14	119.9 (12)	O3—N1—O4	121.32 (11)
C31—P1—C1—C2	55.23 (9)	P1—C11—C16—C15	−179.90 (10)
C21—P1—C1—C2	−72.54 (9)	C31—P1—C21—C22	−117.07 (9)
C11—P1—C1—C2	172.36 (7)	C11—P1—C21—C22	122.75 (9)
P1—C1—C2—O1	19.75 (13)	C1—P1—C21—C22	7.25 (11)
P1—C1—C2—C3	−160.44 (8)	C31—P1—C21—C26	68.43 (10)
O1—C2—C3—C8	173.52 (11)	C11—P1—C21—C26	−51.76 (9)
C1—C2—C3—C8	−6.28 (15)	C1—P1—C21—C26	−167.25 (8)
O1—C2—C3—C4	−6.54 (16)	C26—C21—C22—C23	−0.38 (17)
C1—C2—C3—C4	173.66 (10)	P1—C21—C22—C23	−174.76 (9)
C8—C3—C4—C5	0.15 (18)	C21—C22—C23—C24	0.23 (18)
C2—C3—C4—C5	−179.79 (11)	C22—C23—C24—C25	−0.53 (18)
C3—C4—C5—C6	−0.6 (2)	C23—C24—C25—C26	1.00 (18)
C4—C5—C6—C7	0.7 (2)	C24—C25—C26—C21	−1.15 (17)
C5—C6—C7—C8	−0.3 (2)	C22—C21—C26—C25	0.84 (16)
C6—C7—C8—C3	−0.10 (19)	P1—C21—C26—C25	175.45 (9)
C4—C3—C8—C7	0.20 (18)	C21—P1—C31—C32	−18.01 (11)
C2—C3—C8—C7	−179.87 (11)	C11—P1—C31—C32	100.08 (10)
C31—P1—C11—C12	5.77 (12)	C1—P1—C31—C32	−144.79 (9)
C21—P1—C11—C12	129.38 (11)	C21—P1—C31—C36	164.83 (8)
C1—P1—C11—C12	−110.62 (11)	C11—P1—C31—C36	−77.08 (10)
C31—P1—C11—C16	−173.95 (9)	C1—P1—C31—C36	38.04 (10)
C21—P1—C11—C16	−50.33 (10)	C36—C31—C32—C33	−0.55 (17)
C1—P1—C11—C16	69.66 (10)	P1—C31—C32—C33	−177.64 (9)
C16—C11—C12—C13	0.1 (2)	C31—C32—C33—C34	1.04 (18)
P1—C11—C12—C13	−179.58 (12)	C32—C33—C34—C35	−0.88 (19)
C11—C12—C13—C14	−0.3 (3)	C33—C34—C35—C36	0.22 (19)
C12—C13—C14—C15	−0.1 (3)	C34—C35—C36—C31	0.27 (19)
C13—C14—C15—C16	0.6 (2)	C32—C31—C36—C35	−0.10 (17)
C14—C15—C16—C11	−0.8 (2)	P1—C31—C36—C35	177.14 (9)
C12—C11—C16—C15	0.38 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1^i	0.969 (17)	2.457 (17)	3.4061 (14)	166.1 (13)
C1—H2···O2^ii	0.921 (18)	2.279 (18)	3.1856 (16)	168.2 (15)
C1—H2···O4^ii	0.921 (18)	2.386 (18)	3.1230 (15)	137.0 (14)
C16—H16···O2^ii	0.947 (18)	2.504 (18)	3.2621 (16)	137.0 (14)
C24—H24···O2^iii	0.935 (17)	2.571 (16)	3.3777 (16)	144.7 (13)
C24—H24···O3^iii	0.935 (17)	2.757 (17)	3.6491 (17)	159.9 (13)
C14—H14···O3	0.94 (2)	2.34 (2)	3.1614 (16)	145.1 (16)
C26—H26···O3^iv	0.966 (17)	2.701 (16)	3.1040 (15)	105.6 (11)
C32—H32···O3^iv	0.960 (16)	2.640 (16)	3.5064 (16)	150.3 (12)
C35—H35···O3^v	0.951 (17)	2.509 (17)	3.1834 (16)	128.0 (13)
C7—H7···O4^vi	0.964 (19)	2.674 (19)	3.3200 (18)	124.8 (13)
C22—H22···O4^ii	0.960 (16)	2.585 (16)	3.4260 (17)	146.5 (12)
C33—H33···O4^iv	0.957 (17)	2.459 (17)	3.1377 (16)	127.8 (13)

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