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The title compound, C
16H
20NO
2P [O=P(C
6H
5)(C
6H
4OH)(Et
2N) or P(Ph)(PhOH)(Et
2N)], crystallizes as a 21:79 racemic mixture of the
R and
S isomers in the asymmetric unit and is stabilized by strong intramolecular hydrogen bonds with H
O = 1.97 (4) and 1.84 (5) Å. The Tolman cone angle is calculated to be 199°.
Supporting information
CCDC reference: 245329
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.005 Å
- R factor = 0.057
- wR factor = 0.145
- Data-to-parameter ratio = 19.4
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.77 Ratio
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... C15
PLAT301_ALERT_3_C Main Residue Disorder ......................... 5.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
PLAT415_ALERT_2_C Short Inter D-H..H-X H10 .. H2B .. 2.12 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H8A .. O1 .. 2.61 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
7 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 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
2 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus and XPREP (Bruker, 1999); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).
Crystal data top
C16H20NO2P | F(000) = 616 |
Mr = 289.3 | Dx = 1.232 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ybc | Cell parameters from 789 reflections |
a = 8.4348 (15) Å | θ = 2.9–22.9° |
b = 13.635 (2) Å | µ = 0.18 mm−1 |
c = 13.842 (2) Å | T = 294 K |
β = 101.606 (3)° | Plates, colorless |
V = 1559.4 (5) Å3 | 0.44 × 0.15 × 0.08 mm |
Z = 4 | |
Data collection top
Bruker SMART 1K CCD diffractometer | Rint = 0.060 |
ω scans | θmax = 28.3°, θmin = 2.1° |
10440 measured reflections | h = −9→11 |
3854 independent reflections | k = −18→16 |
2053 reflections with I > 2σ(I) | l = −18→17 |
Refinement top
Refinement on F2 | 4 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.057 | w = 1/[σ2(Fo2) + (0.0595P)2 + 0.1233P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.145 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.27 e Å−3 |
3854 reflections | Δρmin = −0.29 e Å−3 |
199 parameters | |
Special details top
Experimental. The intensity data was collected on a Siemens SMART CCD 1 K
diffractometer using an exposure time of 30 s/frame. A total of 1350 frames
were collected with a frame width of 0.3° covering up to θ = 28.33° with
98.9% completeness accomplished. The first 50 frames were recollected at the
end of each data collection to check for decay; none was found. |
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 (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
P | 0.33957 (8) | 0.47060 (5) | 0.23808 (5) | 0.0386 (2) | |
O1 | 0.2463 (2) | 0.44905 (13) | 0.31624 (12) | 0.0522 (5) | |
N | 0.3091 (2) | 0.57609 (14) | 0.17943 (13) | 0.0431 (5) | |
C13 | 0.1536 (3) | 0.5914 (2) | 0.1095 (2) | 0.0591 (8) | |
H13A | 0.0839 | 0.6322 | 0.1406 | 0.071* | |
H13B | 0.1004 | 0.5286 | 0.0944 | 0.071* | |
C14 | 0.1756 (5) | 0.6394 (3) | 0.0147 (2) | 0.0920 (11) | |
H14A | 0.2314 | 0.7006 | 0.0294 | 0.138* | |
H14B | 0.0716 | 0.651 | −0.0267 | 0.138* | |
H14C | 0.2378 | 0.597 | −0.0188 | 0.138* | |
C15 | 0.3802 (3) | 0.66596 (19) | 0.2303 (2) | 0.0557 (7) | |
H15A | 0.3792 | 0.717 | 0.1813 | 0.067* | |
H15B | 0.4925 | 0.6527 | 0.2599 | 0.067* | |
C16 | 0.2977 (5) | 0.7045 (3) | 0.3088 (3) | 0.1025 (13) | |
H16A | 0.184 | 0.7119 | 0.2823 | 0.154* | |
H16B | 0.3431 | 0.767 | 0.3313 | 0.154* | |
H16C | 0.313 | 0.6593 | 0.3631 | 0.154* | |
C1 | 0.5534 (3) | 0.46614 (16) | 0.28914 (17) | 0.0370 (5) | |
C3 | 0.7691 (4) | 0.4318 (2) | 0.4279 (2) | 0.0720 (9) | |
H3 | 0.8027 | 0.4155 | 0.4941 | 0.086* | |
C4 | 0.8805 (4) | 0.4466 (2) | 0.3714 (3) | 0.0693 (9) | |
H4 | 0.9902 | 0.4402 | 0.3987 | 0.083* | |
C5 | 0.8321 (4) | 0.4709 (3) | 0.2742 (3) | 0.0725 (9) | |
H5 | 0.9088 | 0.4801 | 0.2354 | 0.087* | |
C6 | 0.6705 (3) | 0.4819 (2) | 0.2336 (2) | 0.0584 (8) | |
H6 | 0.6392 | 0.5001 | 0.1677 | 0.07* | |
C7 | 0.2973 (3) | 0.37750 (17) | 0.14421 (17) | 0.0403 (6) | |
C9 | 0.2049 (4) | 0.2134 (2) | 0.0949 (2) | 0.0708 (9) | |
H9 | 0.1571 | 0.1549 | 0.1084 | 0.085* | |
C10 | 0.2555 (4) | 0.2245 (3) | 0.0087 (3) | 0.0793 (10) | |
H10 | 0.2429 | 0.1731 | −0.0364 | 0.095* | |
C11 | 0.3251 (4) | 0.3106 (3) | −0.0130 (2) | 0.0768 (10) | |
H11 | 0.3576 | 0.318 | −0.0729 | 0.092* | |
C12 | 0.3463 (3) | 0.3856 (2) | 0.0545 (2) | 0.0603 (8) | |
H12 | 0.3949 | 0.4435 | 0.0398 | 0.072* | |
O2 | 0.5261 (11) | 0.4095 (10) | 0.4487 (6) | 0.091 (5) | 0.213 (6) |
C2 | 0.6049 (4) | 0.4408 (2) | 0.3877 (2) | 0.0553 (7) | |
H2A | 0.5292 | 0.4298 | 0.427 | 0.066* | 0.787 (6) |
C8 | 0.2242 (3) | 0.2899 (2) | 0.16384 (19) | 0.0522 (7) | |
H8A | 0.1883 | 0.2823 | 0.2227 | 0.063* | 0.213 (6) |
O8 | 0.1689 (4) | 0.2719 (2) | 0.2458 (2) | 0.0788 (11) | 0.787 (6) |
H2B | 0.427 (3) | 0.415 (13) | 0.424 (7) | 0.118* | 0.213 (6) |
H8B | 0.173 (6) | 0.326 (4) | 0.277 (4) | 0.118* | 0.787 (6) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P | 0.0364 (4) | 0.0379 (4) | 0.0414 (4) | −0.0006 (3) | 0.0074 (3) | −0.0001 (3) |
O1 | 0.0476 (11) | 0.0569 (12) | 0.0562 (10) | −0.0030 (8) | 0.0202 (9) | −0.0003 (9) |
N | 0.0423 (12) | 0.0357 (12) | 0.0467 (11) | −0.0005 (9) | −0.0018 (10) | 0.0011 (10) |
C13 | 0.0474 (17) | 0.0524 (18) | 0.0691 (18) | 0.0046 (13) | −0.0083 (14) | 0.0081 (15) |
C14 | 0.098 (3) | 0.097 (3) | 0.068 (2) | 0.010 (2) | −0.0127 (19) | 0.027 (2) |
C15 | 0.0586 (18) | 0.0367 (15) | 0.0660 (17) | −0.0032 (13) | −0.0016 (15) | −0.0033 (14) |
C16 | 0.151 (4) | 0.065 (2) | 0.103 (3) | −0.016 (2) | 0.053 (3) | −0.031 (2) |
C1 | 0.0375 (13) | 0.0306 (12) | 0.0415 (13) | −0.0003 (11) | 0.0043 (11) | −0.0027 (11) |
C3 | 0.073 (2) | 0.065 (2) | 0.0643 (19) | −0.0067 (17) | −0.0189 (18) | 0.0163 (16) |
C4 | 0.0444 (18) | 0.060 (2) | 0.094 (3) | 0.0096 (14) | −0.0091 (18) | −0.0106 (18) |
C5 | 0.0453 (18) | 0.091 (3) | 0.084 (2) | 0.0014 (17) | 0.0198 (18) | −0.022 (2) |
C6 | 0.0433 (17) | 0.082 (2) | 0.0503 (15) | −0.0015 (15) | 0.0114 (14) | −0.0036 (15) |
C7 | 0.0391 (14) | 0.0369 (14) | 0.0424 (13) | −0.0021 (11) | 0.0020 (11) | 0.0014 (11) |
C9 | 0.078 (2) | 0.0389 (18) | 0.085 (2) | −0.0062 (15) | −0.0093 (19) | −0.0044 (17) |
C10 | 0.090 (3) | 0.062 (2) | 0.078 (2) | 0.0061 (19) | −0.003 (2) | −0.0277 (19) |
C11 | 0.094 (3) | 0.077 (2) | 0.0624 (19) | −0.009 (2) | 0.0210 (18) | −0.0255 (18) |
C12 | 0.068 (2) | 0.0550 (18) | 0.0583 (17) | −0.0096 (15) | 0.0145 (15) | −0.0091 (15) |
O2 | 0.059 (7) | 0.166 (12) | 0.043 (6) | −0.045 (7) | −0.001 (5) | 0.027 (6) |
C2 | 0.0523 (18) | 0.0591 (18) | 0.0509 (16) | −0.0069 (14) | 0.0020 (15) | 0.0026 (14) |
C8 | 0.0545 (17) | 0.0470 (18) | 0.0507 (16) | −0.0026 (13) | −0.0001 (14) | 0.0058 (14) |
O8 | 0.106 (2) | 0.0608 (19) | 0.072 (2) | −0.0267 (17) | 0.0213 (17) | 0.0048 (14) |
Geometric parameters (Å, º) top
P—O1 | 1.4896 (17) | C3—C2 | 1.391 (4) |
P—N | 1.646 (2) | C3—H3 | 0.93 |
P—C7 | 1.800 (2) | C4—C5 | 1.365 (4) |
P—C1 | 1.801 (2) | C4—H4 | 0.93 |
N—C15 | 1.479 (3) | C5—C6 | 1.374 (4) |
N—C13 | 1.480 (3) | C5—H5 | 0.93 |
C13—C14 | 1.511 (4) | C6—H6 | 0.93 |
C13—H13A | 0.97 | C7—C12 | 1.390 (3) |
C13—H13B | 0.97 | C7—C8 | 1.396 (3) |
C14—H14A | 0.96 | C9—C10 | 1.355 (4) |
C14—H14B | 0.96 | C9—C8 | 1.400 (4) |
C14—H14C | 0.96 | C9—H9 | 0.93 |
C15—C16 | 1.499 (4) | C10—C11 | 1.372 (5) |
C15—H15A | 0.97 | C10—H10 | 0.93 |
C15—H15B | 0.97 | C11—C12 | 1.373 (4) |
C16—H16A | 0.96 | C11—H11 | 0.93 |
C16—H16B | 0.96 | C12—H12 | 0.93 |
C16—H16C | 0.96 | O2—H2B | 0.84 (2) |
C1—C6 | 1.385 (3) | C2—H2A | 0.93 |
C1—C2 | 1.390 (4) | C8—H8A | 0.93 |
C3—C4 | 1.353 (4) | O8—H8B | 0.85 (5) |
| | | |
O1—P—N | 118.53 (10) | C2—C1—P | 119.0 (2) |
O1—P—C7 | 109.16 (11) | C4—C3—C2 | 120.5 (3) |
N—P—C7 | 105.75 (10) | C4—C3—H3 | 119.7 |
O1—P—C1 | 110.00 (10) | C2—C3—H3 | 119.7 |
N—P—C1 | 105.53 (10) | C3—C4—C5 | 120.0 (3) |
C7—P—C1 | 107.27 (11) | C3—C4—H4 | 120 |
C15—N—C13 | 114.6 (2) | C5—C4—H4 | 120 |
C15—N—P | 118.76 (16) | C4—C5—C6 | 120.4 (3) |
C13—N—P | 118.38 (16) | C4—C5—H5 | 119.8 |
N—C13—C14 | 112.4 (2) | C6—C5—H5 | 119.8 |
N—C13—H13A | 109.1 | C5—C6—C1 | 121.0 (3) |
C14—C13—H13A | 109.1 | C5—C6—H6 | 119.5 |
N—C13—H13B | 109.1 | C1—C6—H6 | 119.5 |
C14—C13—H13B | 109.1 | C12—C7—C8 | 117.7 (2) |
H13A—C13—H13B | 107.9 | C12—C7—P | 122.49 (19) |
C13—C14—H14A | 109.5 | C8—C7—P | 119.61 (19) |
C13—C14—H14B | 109.5 | C10—C9—C8 | 120.2 (3) |
H14A—C14—H14B | 109.5 | C10—C9—H9 | 119.9 |
C13—C14—H14C | 109.5 | C8—C9—H9 | 119.9 |
H14A—C14—H14C | 109.5 | C9—C10—C11 | 120.9 (3) |
H14B—C14—H14C | 109.5 | C9—C10—H10 | 119.6 |
N—C15—C16 | 115.6 (2) | C11—C10—H10 | 119.6 |
N—C15—H15A | 108.4 | C10—C11—C12 | 119.4 (3) |
C16—C15—H15A | 108.4 | C10—C11—H11 | 120.3 |
N—C15—H15B | 108.4 | C12—C11—H11 | 120.3 |
C16—C15—H15B | 108.4 | C11—C12—C7 | 121.8 (3) |
H15A—C15—H15B | 107.4 | C11—C12—H12 | 119.1 |
C15—C16—H16A | 109.5 | C7—C12—H12 | 119.1 |
C15—C16—H16B | 109.5 | C1—C2—C3 | 120.2 (3) |
H16A—C16—H16B | 109.5 | C1—C2—H2A | 119.9 |
C15—C16—H16C | 109.5 | C3—C2—H2A | 119.9 |
H16A—C16—H16C | 109.5 | C7—C8—C9 | 120.0 (3) |
H16B—C16—H16C | 109.5 | C7—C8—H8A | 120 |
C6—C1—C2 | 117.8 (2) | C9—C8—H8A | 120 |
C6—C1—P | 123.12 (19) | | |
| | | |
O1—P—N—C15 | 75.8 (2) | P—C1—C6—C5 | −175.4 (2) |
C7—P—N—C15 | −161.42 (19) | O1—P—C7—C12 | 169.7 (2) |
C1—P—N—C15 | −47.9 (2) | N—P—C7—C12 | 41.2 (2) |
O1—P—N—C13 | −70.9 (2) | C1—P—C7—C12 | −71.1 (2) |
C7—P—N—C13 | 51.9 (2) | O1—P—C7—C8 | −15.6 (2) |
C1—P—N—C13 | 165.38 (18) | N—P—C7—C8 | −144.2 (2) |
C15—N—C13—C14 | 75.3 (3) | C1—P—C7—C8 | 103.6 (2) |
P—N—C13—C14 | −136.6 (2) | C8—C9—C10—C11 | −0.5 (5) |
C13—N—C15—C16 | 73.3 (3) | C9—C10—C11—C12 | 1.2 (5) |
P—N—C15—C16 | −74.6 (3) | C10—C11—C12—C7 | −0.8 (5) |
O1—P—C1—C6 | 179.1 (2) | C8—C7—C12—C11 | −0.3 (4) |
N—P—C1—C6 | −51.9 (2) | P—C7—C12—C11 | 174.5 (2) |
C7—P—C1—C6 | 60.5 (2) | C6—C1—C2—C3 | 0.0 (4) |
O1—P—C1—C2 | 2.6 (2) | P—C1—C2—C3 | 176.7 (2) |
N—P—C1—C2 | 131.5 (2) | C4—C3—C2—C1 | −0.7 (4) |
C7—P—C1—C2 | −116.0 (2) | C12—C7—C8—C9 | 1.0 (4) |
C2—C3—C4—C5 | 0.3 (5) | P—C7—C8—C9 | −173.9 (2) |
C3—C4—C5—C6 | 0.9 (5) | C10—C9—C8—C7 | −0.7 (4) |
C4—C5—C6—C1 | −1.7 (5) | C14—C13—C15—C16 | 128.2 (3) |
C2—C1—C6—C5 | 1.2 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2B···O1 | 0.84 (2) | 1.97 (4) | 2.735 (9) | 152 (7) |
O8—H8B···O1 | 0.85 (5) | 1.84 (5) | 2.637 (3) | 157 (5) |
C2—H2A···O1 | 0.93 | 2.58 | 2.989 (3) | 107 |
C8—H8A···O1 | 0.93 | 2.61 | 3.006 (3) | 106 |
Comparative geometrical data (Å, °) for O═P(Ph)(X)(N(Y)(Z)) compounds top(X)(Y)(Z) | O═P | N—P | O═P—N | C—N—C | ΘT | Ref. |
(PhOH)(Et)(Et) | 1.491 (4) | 1.646 (4) | 118.6 (2) | 114.4 (4) | 199 | a |
(Ph)(Me)(Me) | 1.481 | 1.681 | 117.5 | 115.1 | | b |
(Ph)(Etn) | 1.479 | 1.672 | 117.6 | 59.8 | 177 | c |
(Ph)(Me)(PhEt) | 1.489 (1) | 1.646 (2) | 117.9 (1) | 114.0 (1) | 179 | d |
(PhOMe)(Et)(Et) | 1.473 | 1.654 | 118.3 | 114.3 | 177 | e |
Notes: (a) This work;
(b) Ul-Haque & Caughlan (1976) (methyl H atoms
not included in structure from CSD);
(c) Davidowitz et al. (1985);
(d) Cameron & Duncanson (1981);
(e) Utenova et al. (1998).
CSD data extracted from Cambridge Structural Database for a, b, c and d,
no s.u. values available. ΘT = Tolman cone angle.
Me = methyl, Et = ethyl, Ph = phenyl, PhOH = 2-hydroxyphenyl, Etn = ethylene,
PhEt = phenylethyl. |
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