Phase change in tetra­phenyl­phospho­nium perchlorate

The title compound, C₂₄H₂₀P⁺·ClO₄^-, undergoes a sudden reversible phase change in the region of 173-180 K which involves ordering of three quarters of the perchlorate anions.

Computing details

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-III (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.

Tetraphenylphosphonium perchlorate

Crystal data

C24H20P^+·ClO4^−	Dx = 1.458 Mg m^−3
Mr = 438.82	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 11973 reflections
Hall symbol: I -4	θ = 1.7–30.5°
a = 17.0481 (4) Å	µ = 0.30 mm^−1
c = 13.7568 (3) Å	T = 123 K
V = 3998.24 (16) Å^3	Block, colourless
Z = 8	0.40 × 0.28 × 0.15 mm
F(000) = 1824

Data collection

Nonius KappaCCD diffractometer	5981 independent reflections
Radiation source: fine-focus sealed tube	5030 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 9 pixels mm^-1	θmax = 30.5°, θmin = 1.7°
φ and ω scans	h = −24→17
Absorption correction: integration (XPREP; Siemens, 1994)	k = −20→24
Tmin = 0.913, Tmax = 0.954	l = −18→13
11969 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0486P)^2 + 1.5872P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
5981 reflections	Δρmax = 0.27 e Å^−3
279 parameters	Δρmin = −0.36 e Å^−3
0 restraints	Absolute structure: Flack (1983), 2804 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (5)

Special details

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. The perchlorate centred on Cl4 was disordered, and modelled over two equal positions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.5000	0.5000	0.0000	0.02392 (17)
O1	0.43107 (12)	0.49866 (10)	−0.05823 (14)	0.0683 (6)
Cl2	0.5000	0.0000	0.2500	0.02114 (16)
O2	0.45890 (9)	0.05492 (9)	0.18958 (13)	0.0472 (4)
Cl3	0.5000	0.5000	0.5000	0.01817 (15)
O3	0.55610 (12)	0.53822 (12)	0.55890 (17)	0.0776 (8)
Cl4	1.0000	0.5000	0.2500	0.02563 (17)
O41	1.0371 (4)	0.4925 (6)	0.1677 (4)	0.163 (4)	0.50
O42	1.0847 (3)	0.4969 (4)	0.2330 (4)	0.0969 (17)	0.50
P1	1.25774 (2)	0.74761 (4)	0.87594 (2)	0.01245 (9)
C1	1.27460 (8)	0.83300 (8)	0.94939 (11)	0.0144 (3)
C2	1.34319 (9)	0.87823 (9)	0.94194 (12)	0.0186 (3)
H2A	1.3819	0.8659	0.8947	0.022*
C3	1.35378 (10)	0.94126 (9)	1.00454 (14)	0.0233 (3)
H3A	1.4006	0.9713	1.0011	0.028*
C4	1.29655 (11)	0.96079 (9)	1.07217 (13)	0.0237 (3)
H4A	1.3045	1.0038	1.1150	0.028*
C5	1.22744 (11)	0.91719 (9)	1.07712 (13)	0.0231 (3)
H5A	1.1875	0.9318	1.1217	0.028*
C6	1.21680 (10)	0.85277 (9)	1.01740 (11)	0.0188 (3)
H6A	1.1705	0.8221	1.0225	0.023*
C7	1.24378 (8)	0.66584 (8)	0.95617 (10)	0.0140 (3)
C8	1.30483 (9)	0.64715 (9)	1.02079 (11)	0.0196 (3)
H8A	1.3519	0.6770	1.0207	0.024*
C9	1.29602 (10)	0.58498 (9)	1.08456 (13)	0.0232 (3)
H9A	1.3376	0.5711	1.1272	0.028*
C10	1.22610 (10)	0.54285 (9)	1.08615 (13)	0.0217 (3)
H10A	1.2195	0.5013	1.1314	0.026*
C11	1.16589 (9)	0.56112 (9)	1.02194 (13)	0.0206 (3)
H11A	1.1186	0.5317	1.0230	0.025*
C12	1.17474 (8)	0.62224 (9)	0.95625 (12)	0.0168 (3)
H12A	1.1340	0.6343	0.9116	0.020*
C13	1.33910 (8)	0.72979 (10)	0.79592 (11)	0.0161 (3)
C14	1.35693 (9)	0.78723 (11)	0.72696 (11)	0.0234 (3)
H14A	1.3275	0.8345	0.7248	0.028*
C15	1.41761 (10)	0.77507 (14)	0.66181 (13)	0.0320 (4)
H15A	1.4310	0.8148	0.6163	0.038*
C16	1.45880 (10)	0.70495 (13)	0.66306 (13)	0.0293 (4)
H16A	1.4992	0.6962	0.6168	0.035*
C17	1.44170 (9)	0.64768 (11)	0.73101 (13)	0.0259 (4)
H17A	1.4705	0.6000	0.7314	0.031*
C18	1.38207 (9)	0.65989 (10)	0.79912 (12)	0.0193 (3)
H18A	1.3709	0.6213	0.8469	0.023*
C19	1.17206 (8)	0.76092 (9)	0.80204 (10)	0.0132 (3)
C20	1.12613 (8)	0.82850 (9)	0.80668 (12)	0.0164 (3)
H20A	1.1392	0.8692	0.8509	0.020*
C21	1.06126 (9)	0.83598 (10)	0.74637 (13)	0.0194 (3)
H21A	1.0302	0.8822	0.7490	0.023*
C22	1.04162 (9)	0.77626 (10)	0.68230 (12)	0.0199 (3)
H22A	0.9975	0.7820	0.6406	0.024*
C23	1.08635 (9)	0.70787 (10)	0.67890 (12)	0.0201 (3)
H23A	1.0718	0.6664	0.6364	0.024*
C24	1.15208 (9)	0.70031 (10)	0.73751 (11)	0.0176 (3)
H24A	1.1834	0.6543	0.7340	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0263 (2)	0.0263 (2)	0.0192 (4)	0.000	0.000	0.000
O1	0.0846 (13)	0.0463 (10)	0.0739 (12)	0.0161 (10)	−0.0578 (11)	−0.0097 (9)
Cl2	0.0167 (2)	0.0167 (2)	0.0300 (4)	0.000	0.000	0.000
O2	0.0343 (8)	0.0466 (9)	0.0608 (10)	0.0028 (7)	−0.0134 (7)	0.0233 (8)
Cl3	0.0179 (2)	0.0179 (2)	0.0188 (3)	0.000	0.000	0.000
O3	0.0713 (14)	0.0720 (13)	0.0893 (16)	0.0022 (10)	−0.0469 (12)	−0.0368 (12)
Cl4	0.0285 (3)	0.0285 (3)	0.0199 (4)	0.000	0.000	0.000
O41	0.191 (10)	0.196 (7)	0.103 (4)	0.038 (9)	0.123 (5)	−0.003 (7)
O42	0.044 (2)	0.152 (5)	0.094 (4)	0.024 (3)	0.023 (2)	−0.015 (4)
P1	0.01132 (16)	0.01236 (18)	0.0137 (2)	−0.00024 (14)	0.00027 (13)	0.00016 (12)
C1	0.0157 (6)	0.0112 (6)	0.0164 (7)	−0.0011 (5)	−0.0020 (5)	0.0007 (5)
C2	0.0148 (7)	0.0151 (7)	0.0260 (8)	−0.0009 (5)	−0.0007 (6)	0.0007 (6)
C3	0.0221 (8)	0.0151 (7)	0.0328 (9)	−0.0036 (5)	−0.0059 (7)	0.0003 (6)
C4	0.0344 (9)	0.0139 (7)	0.0228 (8)	−0.0019 (6)	−0.0062 (7)	−0.0023 (6)
C5	0.0331 (9)	0.0183 (7)	0.0178 (8)	−0.0011 (6)	0.0025 (7)	−0.0012 (6)
C6	0.0226 (8)	0.0162 (7)	0.0176 (7)	−0.0037 (6)	0.0043 (6)	−0.0012 (6)
C7	0.0154 (6)	0.0116 (6)	0.0151 (6)	−0.0006 (5)	−0.0011 (5)	0.0012 (5)
C8	0.0202 (7)	0.0177 (7)	0.0210 (8)	−0.0048 (5)	−0.0066 (6)	0.0030 (6)
C9	0.0283 (9)	0.0208 (7)	0.0205 (8)	−0.0021 (6)	−0.0097 (6)	0.0042 (6)
C10	0.0274 (8)	0.0162 (7)	0.0214 (8)	−0.0015 (6)	0.0011 (6)	0.0058 (6)
C11	0.0169 (7)	0.0163 (7)	0.0286 (9)	−0.0014 (5)	0.0007 (6)	0.0046 (6)
C12	0.0134 (6)	0.0156 (7)	0.0213 (7)	−0.0006 (5)	0.0002 (5)	0.0004 (6)
C13	0.0117 (6)	0.0209 (7)	0.0158 (7)	0.0003 (5)	0.0004 (5)	−0.0007 (6)
C14	0.0170 (7)	0.0335 (9)	0.0198 (8)	0.0047 (6)	0.0035 (6)	0.0094 (7)
C15	0.0191 (8)	0.0560 (13)	0.0209 (8)	0.0038 (8)	0.0021 (6)	0.0120 (8)
C16	0.0161 (7)	0.0529 (12)	0.0190 (8)	0.0024 (7)	0.0032 (6)	−0.0056 (8)
C17	0.0155 (7)	0.0302 (9)	0.0321 (10)	0.0018 (6)	0.0011 (6)	−0.0113 (7)
C18	0.0156 (6)	0.0181 (7)	0.0244 (8)	−0.0002 (5)	0.0014 (6)	−0.0054 (6)
C19	0.0105 (6)	0.0153 (7)	0.0136 (6)	−0.0006 (5)	0.0009 (5)	0.0006 (5)
C20	0.0156 (6)	0.0149 (7)	0.0187 (7)	0.0007 (5)	−0.0008 (6)	0.0000 (5)
C21	0.0153 (7)	0.0191 (7)	0.0239 (8)	0.0018 (5)	−0.0022 (6)	0.0015 (6)
C22	0.0156 (7)	0.0268 (8)	0.0174 (7)	−0.0017 (6)	−0.0015 (6)	0.0039 (6)
C23	0.0197 (7)	0.0244 (8)	0.0161 (7)	−0.0028 (6)	−0.0028 (6)	−0.0031 (6)
C24	0.0180 (7)	0.0177 (7)	0.0172 (7)	0.0021 (5)	0.0002 (6)	−0.0035 (6)

Geometric parameters (Å, º)

Cl1—O1^i	1.4224 (15)	C1—C6	1.400 (2)
Cl1—O1^ii	1.4224 (15)	C1—C2	1.405 (2)
Cl1—O1^iii	1.4224 (15)	C2—C3	1.389 (2)
Cl1—O1	1.4224 (15)	C3—C4	1.389 (2)
Cl2—O2^iv	1.4346 (14)	C4—C5	1.395 (2)
Cl2—O2^v	1.4347 (14)	C5—C6	1.383 (2)
Cl2—O2^vi	1.4347 (14)	C7—C12	1.3920 (19)
Cl2—O2	1.4347 (14)	C7—C8	1.405 (2)
Cl3—O3^vii	1.4127 (16)	C8—C9	1.384 (2)
Cl3—O3^i	1.4128 (16)	C9—C10	1.392 (2)
Cl3—O3	1.4128 (17)	C10—C11	1.389 (2)
Cl3—O3^viii	1.4128 (16)	C11—C12	1.388 (2)
Cl4—O41^ix	1.303 (4)	C13—C14	1.397 (2)
Cl4—O41^x	1.303 (4)	C13—C18	1.399 (2)
Cl4—O41	1.303 (4)	C14—C15	1.384 (2)
Cl4—O41^xi	1.303 (4)	C15—C16	1.386 (3)
Cl4—O42^ix	1.463 (4)	C16—C17	1.383 (3)
Cl4—O42^x	1.463 (4)	C17—C18	1.398 (2)
Cl4—O42^xi	1.463 (4)	C19—C20	1.3944 (19)
Cl4—O42	1.463 (4)	C19—C24	1.4041 (19)
P1—C7	1.7940 (14)	C20—C21	1.389 (2)
P1—C19	1.7940 (14)	C21—C22	1.388 (2)
P1—C1	1.7952 (15)	C22—C23	1.394 (2)
P1—C13	1.7966 (15)	C23—C24	1.387 (2)
O1^i—Cl1—O1^ii	108.49 (9)	O42^x—Cl4—O42	91.47 (7)
O1^i—Cl1—O1^iii	108.49 (9)	O42^xi—Cl4—O42	161.6 (4)
O1^ii—Cl1—O1^iii	111.45 (19)	O42—O41—O41^xi	130.1 (4)
O1^i—Cl1—O1	111.45 (19)	O42—O41—Cl4	71.0 (4)
O1^ii—Cl1—O1	108.49 (9)	O41^xi—O41—Cl4	60.3 (4)
O1^iii—Cl1—O1	108.49 (9)	O41—O42—Cl4	57.4 (3)
O2^iv—Cl2—O2^v	109.61 (8)	C7—P1—C19	109.81 (6)
O2^iv—Cl2—O2^vi	109.19 (15)	C7—P1—C1	107.76 (7)
O2^v—Cl2—O2^vi	109.61 (8)	C19—P1—C1	110.29 (6)
O2^iv—Cl2—O2	109.61 (8)	C7—P1—C13	110.36 (7)
O2^v—Cl2—O2	109.19 (15)	C19—P1—C13	107.63 (7)
O2^vi—Cl2—O2	109.61 (8)	C1—P1—C13	111.00 (7)
O3^vii—Cl3—O3^i	109.20 (11)	C6—C1—C2	120.17 (14)
O3^vii—Cl3—O3	109.21 (11)	C6—C1—P1	117.31 (11)
O3^i—Cl3—O3	110.0 (2)	C2—C1—P1	122.51 (11)
O3^vii—Cl3—O3^viii	110.0 (2)	C3—C2—C1	119.20 (14)
O3^i—Cl3—O3^viii	109.20 (11)	C4—C3—C2	120.63 (14)
O3—Cl3—O3^viii	109.21 (11)	C3—C4—C5	119.90 (14)
O41^ix—Cl4—O41^x	59.3 (7)	C6—C5—C4	120.32 (16)
O41^ix—Cl4—O41	139.0 (5)	C5—C6—C1	119.72 (14)
O41^x—Cl4—O41	139.0 (5)	C12—C7—C8	120.31 (13)
O41^ix—Cl4—O41^xi	139.0 (5)	C12—C7—P1	121.84 (11)
O41^x—Cl4—O41^xi	139.0 (5)	C8—C7—P1	117.85 (11)
O41—Cl4—O41^xi	59.3 (7)	C9—C8—C7	119.61 (14)
O41^ix—Cl4—O42^ix	51.6 (3)	C8—C9—C10	119.88 (15)
O41^x—Cl4—O42^ix	110.1 (5)	C11—C10—C9	120.46 (14)
O41—Cl4—O42^ix	102.6 (5)	C12—C11—C10	120.14 (14)
O41^xi—Cl4—O42^ix	93.4 (5)	C11—C12—C7	119.56 (14)
O41^ix—Cl4—O42^x	110.1 (5)	C14—C13—C18	120.29 (14)
O41^x—Cl4—O42^x	51.6 (3)	C14—C13—P1	117.75 (11)
O41—Cl4—O42^x	93.4 (5)	C18—C13—P1	121.93 (12)
O41^xi—Cl4—O42^x	102.6 (5)	C15—C14—C13	119.82 (16)
O42^ix—Cl4—O42^x	161.6 (4)	C14—C15—C16	119.97 (17)
O41^ix—Cl4—O42^xi	102.6 (5)	C17—C16—C15	120.69 (16)
O41^x—Cl4—O42^xi	93.4 (5)	C16—C17—C18	120.08 (16)
O41—Cl4—O42^xi	110.1 (5)	C17—C18—C13	119.10 (15)
O41^xi—Cl4—O42^xi	51.6 (4)	C20—C19—C24	120.05 (13)
O42^ix—Cl4—O42^xi	91.47 (7)	C20—C19—P1	122.39 (11)
O42^x—Cl4—O42^xi	91.47 (7)	C24—C19—P1	117.56 (10)
O41^ix—Cl4—O42	93.4 (5)	C21—C20—C19	119.72 (14)
O41^x—Cl4—O42	102.6 (5)	C22—C21—C20	120.28 (14)
O41—Cl4—O42	51.6 (3)	C21—C22—C23	120.20 (14)
O41^xi—Cl4—O42	110.1 (5)	C24—C23—C22	120.02 (15)
O42^ix—Cl4—O42	91.47 (7)	C23—C24—C19	119.70 (14)

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