The arsenic(V) compound PhAs(O)(OH)(OSiPh₃)

The structure of the arsenosilicate compound, hydro­xooxo­(phenyl)(tri­phenyl­siloxy)­arsenic(V), PhAs(O)(OH)(OSiPh₃) or [As(C₆H₅)(C₁₈H₁₅OSi)O(OH)], is dimeric with the monomers joined by two As—O—H...O=As hydrogen-bonding sequences about an inversion centre, with O...O = 2.528 (3) Å. The monomer unit has a tetrahedral AsO₃C_Ph entity. The As—O—Si angle [140.79 (12)°] is larger than any previously reported As^V—O—Si angle in a molecular species. The three independent As—O bond lengths are 1.6551 (18), 1.6740 (18) and 1.7086 (17) Å, respectively, for the As=O, As—OH and As—OSiPh₃ bonds.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.035
• wR factor = 0.079
• Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT074_ALERT_1_C Occupancy Parameter = 0.0 for ..................        CG1
PLAT074_ALERT_1_C Occupancy Parameter = 0.0 for ..................        CG2
PLAT074_ALERT_1_C Occupancy Parameter = 0.0 for ..................        CG3
PLAT074_ALERT_1_C Occupancy Parameter = 0.0 for ..................        CG4
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.67 Ratio
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....        C13
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....        C43
PLAT480_ALERT_4_C Long H...A H-Bond Reported H15    ..  CG2      =       2.85 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H24    ..  CG4      =       3.04 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H33    ..  CG4      =       2.96 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H35    ..  CG2      =       3.01 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H42    ..  CG1      =       3.14 Ang.
PLAT481_ALERT_4_C Long D...A H-Bond Reported C24    ..  CG4      =       3.93 Ang.
PLAT481_ALERT_4_C Long D...A H-Bond Reported C42    ..  CG1      =       3.95 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  14 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CAD-4-PC Software (Enraf–Nonius, 1992); cell refinement: SET4 and CELDIM (Enraf–Nonius, 1992); data reduction: DATRD2 in NRCVAX94 (Gabe et al., 1989); program(s) used to solve structure: NRCVAX94 via Patterson heavy-atom method; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and WinGX (Farrugia 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

(V)

Crystal data

[As(C6H5)(C18H15OSi)O(OH)]	Z = 2
Mr = 460.42	F(000) = 472
Triclinic, P1	? #Insert any comments here.
Hall symbol: -P 1	Dx = 1.413 Mg m^−3
a = 8.3350 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8193 (8) Å	Cell parameters from 25 reflections
c = 14.8736 (14) Å	θ = 14.6–21.6°
α = 89.948 (6)°	µ = 1.65 mm^−1
β = 74.391 (9)°	T = 294 K
γ = 68.276 (5)°	Lath, colorless
V = 1082.51 (18) Å^3	0.42 × 0.38 × 0.22 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	3281 reflections with I > 2σ(I)
Radiation source: X-ray tube	Rint = 0.000
Graphite monochromator	θmax = 27.0°, θmin = 2.2°
θ/2θ scans	h = −10→9
Absorption correction: ψ scan North et al., 1968)	k = 0→12
Tmin = 0.549, Tmax = 0.702	l = −18→19
4751 measured reflections	3 standard reflections every 120 min
4751 independent reflections	intensity decay: none

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)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0386P)^2 + 0.0624P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.002
4751 reflections	Δρmax = 0.30 e Å^−3
264 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0044 (9)

Special details

Experimental. ? #Insert any special details here.

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
As1	0.39390 (4)	0.67046 (3)	0.418064 (19)	0.04001 (11)
Si1	0.61356 (10)	0.74695 (8)	0.22909 (5)	0.03830 (18)
O1	0.4832 (2)	0.7677 (2)	0.33838 (12)	0.0500 (5)
O2	0.4793 (3)	0.49333 (19)	0.37839 (14)	0.0611 (6)
O3	0.4450 (3)	0.7061 (2)	0.51450 (14)	0.0606 (6)
H3	0.4583	0.6354	0.5452	0.091*
C11	0.1419 (4)	0.7557 (3)	0.43679 (18)	0.0467 (7)
C12	0.0386 (5)	0.6913 (4)	0.4950 (2)	0.0766 (10)
H12	0.0930	0.6096	0.5236	0.092*
C13	−0.1459 (6)	0.7484 (6)	0.5107 (3)	0.0995 (14)
H13	−0.2162	0.7048	0.5496	0.119*
C14	−0.2235 (5)	0.8662 (6)	0.4699 (3)	0.0910 (14)
H14	−0.3480	0.9038	0.4809	0.109*
C15	−0.1243 (5)	0.9330 (4)	0.4123 (3)	0.0802 (11)
H15	−0.1814	1.0155	0.3850	0.096*
C16	0.0619 (4)	0.8775 (4)	0.3945 (2)	0.0631 (8)
H16	0.1311	0.9215	0.3551	0.076*
C21	0.6663 (3)	0.9156 (3)	0.22219 (17)	0.0387 (6)
C22	0.5343 (4)	1.0514 (3)	0.26476 (19)	0.0476 (7)
H22	0.4182	1.0576	0.2952	0.057*
C23	0.5720 (4)	1.1777 (3)	0.2629 (2)	0.0551 (7)
H23	0.4819	1.2674	0.2923	0.066*
C24	0.7429 (5)	1.1701 (4)	0.2176 (2)	0.0623 (8)
H24	0.7690	1.2544	0.2170	0.075*
C25	0.8739 (5)	1.0385 (4)	0.1737 (2)	0.0675 (9)
H25	0.9889	1.0336	0.1423	0.081*
C26	0.8365 (4)	0.9115 (3)	0.1756 (2)	0.0570 (8)
H26	0.9269	0.8226	0.1452	0.068*
C31	0.4854 (3)	0.7400 (3)	0.14577 (18)	0.0405 (6)
C32	0.4058 (4)	0.6368 (3)	0.1486 (2)	0.0541 (7)
H32	0.4146	0.5719	0.1943	0.065*
C33	0.3148 (4)	0.6287 (4)	0.0854 (2)	0.0618 (8)
H33	0.2638	0.5585	0.0885	0.074*
C34	0.2993 (4)	0.7237 (4)	0.0183 (2)	0.0613 (8)
H34	0.2378	0.7180	−0.0243	0.074*
C35	0.3739 (4)	0.8274 (4)	0.0135 (2)	0.0645 (9)
H35	0.3633	0.8923	−0.0321	0.077*
C36	0.4653 (4)	0.8348 (3)	0.0773 (2)	0.0554 (8)
H36	0.5149	0.9060	0.0739	0.067*
C41	0.8222 (4)	0.5768 (3)	0.20707 (18)	0.0435 (6)
C42	0.9197 (5)	0.5417 (4)	0.2714 (2)	0.0820 (12)
H42	0.8781	0.6026	0.3275	0.098*
C43	1.0782 (5)	0.4178 (5)	0.2542 (3)	0.1036 (16)
H43	1.1418	0.3965	0.2985	0.124*
C44	1.1412 (5)	0.3266 (4)	0.1722 (3)	0.0781 (11)
H44	1.2466	0.2426	0.1610	0.094*
C45	1.0495 (4)	0.3596 (3)	0.1077 (3)	0.0653 (9)
H45	1.0925	0.2986	0.0515	0.078*
C46	0.8912 (4)	0.4840 (3)	0.1249 (2)	0.0501 (7)
H46	0.8300	0.5052	0.0795	0.060*
Cg1	−0.0419	0.81202	0.45320	0.01*	0.0
Cg2	0.70432	1.04413	0.21946	0.01*	0.0
Cg3	0.39075	0.73190	0.08148	0.01*	0.0
Cg4	0.98367	0.45108	0.18958	0.01*	0.0

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
As1	0.04947 (18)	0.03256 (15)	0.03596 (16)	−0.01297 (12)	−0.01315 (11)	0.00818 (10)
Si1	0.0401 (4)	0.0340 (4)	0.0385 (4)	−0.0130 (3)	−0.0094 (3)	0.0063 (3)
O1	0.0541 (12)	0.0406 (10)	0.0449 (11)	−0.0159 (9)	−0.0012 (9)	0.0097 (8)
O2	0.0915 (16)	0.0311 (10)	0.0551 (12)	−0.0127 (10)	−0.0279 (11)	0.0005 (9)
O3	0.0908 (16)	0.0523 (12)	0.0535 (12)	−0.0320 (12)	−0.0377 (12)	0.0119 (10)
C11	0.0451 (16)	0.0540 (17)	0.0395 (15)	−0.0186 (14)	−0.0106 (12)	0.0018 (13)
C12	0.070 (2)	0.089 (3)	0.069 (2)	−0.036 (2)	−0.0086 (18)	0.0189 (19)
C13	0.063 (3)	0.140 (4)	0.090 (3)	−0.045 (3)	−0.004 (2)	0.012 (3)
C14	0.047 (2)	0.133 (4)	0.078 (3)	−0.022 (2)	−0.012 (2)	−0.028 (3)
C15	0.069 (2)	0.084 (3)	0.076 (3)	−0.004 (2)	−0.038 (2)	−0.009 (2)
C16	0.059 (2)	0.069 (2)	0.062 (2)	−0.0187 (17)	−0.0280 (16)	0.0103 (17)
C21	0.0434 (15)	0.0387 (14)	0.0383 (14)	−0.0184 (12)	−0.0149 (12)	0.0082 (11)
C22	0.0457 (16)	0.0434 (16)	0.0533 (17)	−0.0177 (13)	−0.0132 (13)	0.0038 (13)
C23	0.064 (2)	0.0389 (16)	0.0612 (19)	−0.0172 (14)	−0.0204 (16)	0.0018 (13)
C24	0.082 (2)	0.055 (2)	0.068 (2)	−0.0436 (19)	−0.0260 (18)	0.0160 (16)
C25	0.061 (2)	0.070 (2)	0.076 (2)	−0.0389 (19)	−0.0066 (17)	0.0144 (18)
C26	0.0478 (18)	0.0532 (18)	0.0619 (19)	−0.0204 (15)	−0.0017 (15)	0.0006 (15)
C31	0.0398 (15)	0.0369 (14)	0.0425 (14)	−0.0138 (12)	−0.0098 (12)	0.0030 (11)
C32	0.0605 (19)	0.0512 (17)	0.0589 (19)	−0.0292 (15)	−0.0195 (15)	0.0159 (14)
C33	0.067 (2)	0.064 (2)	0.072 (2)	−0.0403 (18)	−0.0247 (17)	0.0086 (17)
C34	0.057 (2)	0.074 (2)	0.062 (2)	−0.0303 (17)	−0.0242 (16)	0.0016 (17)
C35	0.079 (2)	0.074 (2)	0.061 (2)	−0.0408 (19)	−0.0358 (18)	0.0256 (17)
C36	0.065 (2)	0.0569 (18)	0.0625 (19)	−0.0372 (16)	−0.0282 (16)	0.0201 (15)
C41	0.0442 (15)	0.0388 (14)	0.0436 (15)	−0.0144 (12)	−0.0088 (12)	0.0093 (12)
C42	0.069 (2)	0.092 (3)	0.0486 (19)	0.010 (2)	−0.0186 (17)	−0.0004 (18)
C43	0.069 (3)	0.126 (4)	0.069 (3)	0.017 (2)	−0.024 (2)	0.031 (3)
C44	0.054 (2)	0.063 (2)	0.083 (3)	0.0033 (17)	−0.0016 (19)	0.023 (2)
C45	0.054 (2)	0.0478 (18)	0.077 (2)	−0.0153 (15)	0.0020 (17)	−0.0083 (16)
C46	0.0472 (17)	0.0447 (16)	0.0581 (18)	−0.0188 (14)	−0.0132 (14)	0.0014 (14)

Geometric parameters (Å, º)

As1—O1	1.7086 (17)	C24—H24	0.93
As1—O2	1.6551 (18)	C25—C26	1.392 (4)
As1—O3	1.6740 (18)	C25—H25	0.93
As1—C11	1.891 (3)	C26—H26	0.93
Si1—O1	1.6585 (18)	C31—C36	1.380 (4)
Si1—C21	1.860 (3)	C31—C32	1.397 (4)
Si1—C31	1.857 (3)	C32—C33	1.375 (4)
Si1—C41	1.862 (3)	C32—H32	0.93
O3—H3	0.82	C33—C34	1.365 (4)
C11—C12	1.374 (4)	C33—H33	0.93
C11—C16	1.380 (4)	C34—C35	1.369 (4)
C12—C13	1.379 (5)	C34—H34	0.93
C12—H12	0.93	C35—C36	1.384 (4)
C13—C14	1.335 (6)	C35—H35	0.93
C13—H13	0.93	C36—H36	0.93
C14—C15	1.366 (6)	C41—C46	1.375 (4)
C14—H14	0.93	C41—C42	1.380 (4)
C15—C16	1.389 (5)	C42—C43	1.385 (5)
C15—H15	0.93	C42—H42	0.93
C16—H16	0.93	C43—C44	1.369 (5)
C21—C26	1.387 (4)	C43—H43	0.93
C21—C22	1.389 (4)	C44—C45	1.349 (5)
C22—C23	1.386 (4)	C44—H44	0.93
C22—H22	0.93	C45—C46	1.387 (4)
C23—C24	1.376 (4)	C45—H45	0.93
C23—H23	0.93	C46—H46	0.93
C24—C25	1.365 (4)
O2—As1—O3	114.05 (10)	C23—C24—H24	120.1
O2—As1—O1	110.76 (10)	C24—C25—C26	120.4 (3)
O3—As1—O1	103.12 (10)	C24—C25—H25	119.8
O2—As1—C11	111.69 (12)	C26—C25—H25	119.8
O3—As1—C11	110.74 (12)	C21—C26—C25	121.0 (3)
O1—As1—C11	105.85 (11)	C21—C26—H26	119.5
O1—Si1—C31	109.47 (11)	C25—C26—H26	119.5
O1—Si1—C21	103.41 (11)	C36—C31—C32	116.4 (3)
C31—Si1—C21	111.04 (11)	C36—C31—Si1	122.1 (2)
O1—Si1—C41	110.96 (11)	C32—C31—Si1	121.5 (2)
C31—Si1—C41	110.40 (12)	C33—C32—C31	121.7 (3)
C21—Si1—C41	111.37 (12)	C33—C32—H32	119.2
Si1—O1—As1	140.79 (12)	C31—C32—H32	119.2
As1—O3—H3	109.5	C34—C33—C32	120.0 (3)
C12—C11—C16	120.4 (3)	C34—C33—H33	120.0
C12—C11—As1	117.3 (2)	C32—C33—H33	120.0
C16—C11—As1	122.3 (2)	C33—C34—C35	120.2 (3)
C11—C12—C13	119.7 (4)	C33—C34—H34	119.9
C11—C12—H12	120.1	C35—C34—H34	119.9
C13—C12—H12	120.1	C34—C35—C36	119.3 (3)
C14—C13—C12	120.0 (4)	C34—C35—H35	120.3
C14—C13—H13	120.0	C36—C35—H35	120.3
C12—C13—H13	120.0	C31—C36—C35	122.3 (3)
C13—C14—C15	121.5 (4)	C31—C36—H36	118.9
C13—C14—H14	119.2	C35—C36—H36	118.9
C15—C14—H14	119.2	C46—C41—C42	116.8 (3)
C14—C15—C16	119.9 (4)	C46—C41—Si1	122.1 (2)
C14—C15—H15	120.1	C42—C41—Si1	121.1 (2)
C16—C15—H15	120.1	C41—C42—C43	121.4 (3)
C11—C16—C15	118.5 (3)	C41—C42—H42	119.3
C11—C16—H16	120.8	C43—C42—H42	119.3
C15—C16—H16	120.8	C44—C43—C42	120.2 (3)
C26—C21—C22	117.5 (2)	C44—C43—H43	119.9
C26—C21—Si1	122.0 (2)	C42—C43—H43	119.9
C22—C21—Si1	120.4 (2)	C45—C44—C43	119.5 (3)
C23—C22—C21	121.4 (3)	C45—C44—H44	120.2
C23—C22—H22	119.3	C43—C44—H44	120.2
C21—C22—H22	119.3	C44—C45—C46	120.2 (3)
C24—C23—C22	119.9 (3)	C44—C45—H45	119.9
C24—C23—H23	120.1	C46—C45—H45	119.9
C22—C23—H23	120.1	C41—C46—C45	121.9 (3)
C25—C24—C23	119.8 (3)	C41—C46—H46	119.1
C25—C24—H24	120.1	C45—C46—H46	119.1
C31—Si1—O1—As1	74.2 (2)	C22—C21—C26—C25	1.4 (4)
C21—Si1—O1—As1	−167.43 (18)	Si1—C21—C26—C25	−178.2 (2)
C41—Si1—O1—As1	−47.9 (2)	C24—C25—C26—C21	−0.2 (5)
O2—As1—O1—Si1	8.1 (2)	O1—Si1—C31—C36	124.7 (2)
O3—As1—O1—Si1	130.5 (2)	C21—Si1—C31—C36	11.1 (3)
C11—As1—O1—Si1	−113.1 (2)	C41—Si1—C31—C36	−112.9 (2)
O2—As1—C11—C12	56.0 (3)	O1—Si1—C31—C32	−56.1 (2)
O3—As1—C11—C12	−72.3 (3)	C21—Si1—C31—C32	−169.7 (2)
O1—As1—C11—C12	176.6 (2)	C41—Si1—C31—C32	66.3 (3)
O2—As1—C11—C16	−124.0 (2)	C36—C31—C32—C33	1.0 (4)
O3—As1—C11—C16	107.7 (2)	Si1—C31—C32—C33	−178.3 (2)
O1—As1—C11—C16	−3.4 (3)	C31—C32—C33—C34	−0.5 (5)
C16—C11—C12—C13	0.4 (5)	C32—C33—C34—C35	−0.1 (5)
As1—C11—C12—C13	−179.6 (3)	C33—C34—C35—C36	0.1 (5)
C11—C12—C13—C14	−0.4 (6)	C32—C31—C36—C35	−1.0 (5)
C12—C13—C14—C15	0.0 (7)	Si1—C31—C36—C35	178.3 (3)
C13—C14—C15—C16	0.5 (6)	C34—C35—C36—C31	0.5 (5)
C12—C11—C16—C15	0.0 (5)	O1—Si1—C41—C46	138.3 (2)
As1—C11—C16—C15	−179.9 (2)	C31—Si1—C41—C46	16.7 (3)
C14—C15—C16—C11	−0.5 (5)	C21—Si1—C41—C46	−107.1 (2)
O1—Si1—C21—C26	139.7 (2)	O1—Si1—C41—C42	−44.8 (3)
C31—Si1—C21—C26	−103.0 (2)	C31—Si1—C41—C42	−166.3 (3)
C41—Si1—C21—C26	20.5 (3)	C21—Si1—C41—C42	69.8 (3)
O1—Si1—C21—C22	−39.9 (2)	C46—C41—C42—C43	−0.8 (5)
C31—Si1—C21—C22	77.4 (2)	Si1—C41—C42—C43	−177.9 (3)
C41—Si1—C21—C22	−159.1 (2)	C41—C42—C43—C44	−0.2 (7)
C26—C21—C22—C23	−1.6 (4)	C42—C43—C44—C45	1.0 (6)
Si1—C21—C22—C23	178.0 (2)	C43—C44—C45—C46	−0.8 (5)
C21—C22—C23—C24	0.5 (4)	C42—C41—C46—C45	1.1 (4)
C22—C23—C24—C25	0.8 (5)	Si1—C41—C46—C45	178.1 (2)
C23—C24—C25—C26	−0.9 (5)	C44—C45—C46—C41	−0.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2^i	0.82	1.73	2.528 (3)	164
C15—H15···Cg2^ii	0.93	2.85	3.536	132
C24—H24···Cg4^iii	0.93	3.04	3.932	160
C33—H33···Cg4^ii	0.93	2.96	3.784	149
C35—H35···Cg2^iv	0.93	3.01	3.824	147
C42—H42···Cg1^v	0.93	3.14	3.946	146

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