The title compound, C
18H
18NO
5P, adopts the keto–amine tautomeric form, forming an intramolecular N—H
O hydrogen bond. The oxaphosphinine ring has a screw-boat conformation. The molecules are linked by O—H
O and C—H
O hydrogen bonds and by a π–π stacking interaction.
Supporting information
CCDC reference: 605552
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.003 Å
- R factor = 0.038
- wR factor = 0.102
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
PLAT128_ALERT_4_C Non-standard setting of Space group C2/c .... I2/a
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: Win-Xpose in IPDS-II Software (Stoe & Cie, 2000); cell refinement: Win-Cell in IPDS-II Software; data reduction: Win-Integrate in IPDS-II Software; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PARST97 (Nardelli, 1996).
3-[
α-(2-Hydroxyethylamino)benzylidene]-2-methoxy-2,3-dihydro-
1,2
λ5-benzoxaphosphinine-2,4-dione
top
Crystal data top
C18H18NO5P | F(000) = 1504 |
Mr = 359.30 | Dx = 1.440 Mg m−3 |
Monoclinic, I2/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -I 2ya | Cell parameters from 4841 reflections |
a = 19.178 (3) Å | θ = 2.4–26.0° |
b = 9.8913 (6) Å | µ = 0.20 mm−1 |
c = 19.1983 (19) Å | T = 193 K |
β = 114.513 (11)° | Plate, colorless |
V = 3313.6 (7) Å3 | 0.42 × 0.24 × 0.12 mm |
Z = 8 | |
Data collection top
Stoe IPDS-II diffractometer | 3166 independent reflections |
Radiation source: fine-focus sealed tube | 2339 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 150 pixels mm-1 | θmax = 26.0°, θmin = 2.3° |
φ scans | h = −22→23 |
Absorption correction: multi-scan (XPREP; Sheldrick, 1996) | k = −12→12 |
Tmin = 0.946, Tmax = 0.973 | l = −22→22 |
16527 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0716P)2] where P = (Fo2 + 2Fc2)/3 |
3166 reflections | (Δ/σ)max = 0.001 |
227 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
Special details top
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 | Uiso*/Ueq | |
O1 | 0.11578 (7) | 0.82819 (13) | 0.17994 (8) | 0.0243 (3) | |
P2 | 0.16733 (3) | 0.93725 (5) | 0.24110 (3) | 0.02004 (15) | |
C3 | 0.24130 (10) | 0.97114 (17) | 0.21142 (11) | 0.0200 (4) | |
C4 | 0.22772 (11) | 0.94492 (17) | 0.13330 (12) | 0.0214 (4) | |
C5 | 0.12901 (11) | 0.91110 (19) | −0.00057 (12) | 0.0261 (4) | |
C6 | 0.05594 (12) | 0.8740 (2) | −0.05259 (13) | 0.0287 (5) | |
C7 | 0.00297 (11) | 0.82609 (19) | −0.02609 (12) | 0.0284 (5) | |
C8 | 0.02289 (11) | 0.81330 (18) | 0.05133 (12) | 0.0257 (4) | |
C9 | 0.09615 (11) | 0.84997 (18) | 0.10254 (11) | 0.0217 (4) | |
C10 | 0.14994 (11) | 0.90083 (17) | 0.07794 (11) | 0.0215 (4) | |
O4 | 0.27768 (8) | 0.96271 (14) | 0.10824 (8) | 0.0284 (3) | |
O21 | 0.12065 (8) | 1.05158 (13) | 0.24599 (9) | 0.0281 (3) | |
O22 | 0.20179 (8) | 0.84842 (13) | 0.31517 (8) | 0.0273 (3) | |
C23 | 0.18791 (13) | 0.8748 (2) | 0.38236 (13) | 0.0334 (5) | |
C31 | 0.31167 (11) | 1.02721 (18) | 0.26348 (11) | 0.0206 (4) | |
N32 | 0.36838 (9) | 1.04725 (17) | 0.24269 (10) | 0.0261 (4) | |
C33 | 0.44017 (11) | 1.1189 (2) | 0.28604 (12) | 0.0305 (5) | |
C34 | 0.47227 (11) | 1.1743 (2) | 0.23199 (12) | 0.0268 (4) | |
O35 | 0.42068 (9) | 1.26017 (15) | 0.17514 (9) | 0.0337 (4) | |
C311 | 0.32403 (10) | 1.06717 (18) | 0.34267 (11) | 0.0200 (4) | |
C312 | 0.37835 (11) | 0.99853 (19) | 0.40515 (12) | 0.0250 (4) | |
C313 | 0.38963 (12) | 1.0329 (2) | 0.47910 (13) | 0.0309 (5) | |
C314 | 0.34822 (12) | 1.1380 (2) | 0.49136 (12) | 0.0304 (5) | |
C315 | 0.29501 (12) | 1.2079 (2) | 0.42954 (12) | 0.0273 (4) | |
C316 | 0.28240 (11) | 1.17185 (18) | 0.35549 (12) | 0.0227 (4) | |
H5 | 0.1642 | 0.9431 | −0.0184 | 0.031* | |
H6 | 0.0424 | 0.8811 | −0.1049 | 0.034* | |
H7 | −0.0461 | 0.8026 | −0.0609 | 0.034* | |
H8 | −0.0123 | 0.7805 | 0.0690 | 0.031* | |
H23B | 0.2142 | 0.8086 | 0.4209 | 0.050* | |
H23A | 0.1339 | 0.8699 | 0.3692 | 0.050* | |
H23C | 0.2064 | 0.9634 | 0.4016 | 0.050* | |
H32 | 0.3625 | 1.0147 | 0.1991 | 0.031* | |
H33A | 0.4310 | 1.1925 | 0.3146 | 0.037* | |
H33B | 0.4769 | 1.0576 | 0.3222 | 0.037* | |
H34A | 0.5189 | 1.2242 | 0.2614 | 0.032* | |
H34B | 0.4857 | 1.0994 | 0.2073 | 0.032* | |
H35 | 0.4058 | 1.3196 | 0.1955 | 0.051* | |
H312 | 0.4071 | 0.9294 | 0.3972 | 0.030* | |
H313 | 0.4250 | 0.9854 | 0.5205 | 0.037* | |
H314 | 0.3561 | 1.1616 | 0.5410 | 0.036* | |
H315 | 0.2677 | 1.2791 | 0.4378 | 0.033* | |
H316 | 0.2459 | 1.2179 | 0.3142 | 0.027* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0269 (7) | 0.0271 (7) | 0.0231 (8) | −0.0076 (5) | 0.0145 (6) | −0.0044 (6) |
P2 | 0.0207 (2) | 0.0218 (2) | 0.0212 (3) | −0.00224 (18) | 0.0123 (2) | −0.00311 (18) |
C3 | 0.0204 (9) | 0.0212 (9) | 0.0203 (11) | 0.0006 (7) | 0.0105 (8) | −0.0016 (7) |
C4 | 0.0218 (9) | 0.0221 (9) | 0.0224 (11) | −0.0003 (7) | 0.0113 (8) | −0.0019 (7) |
C5 | 0.0269 (10) | 0.0290 (10) | 0.0246 (12) | −0.0041 (8) | 0.0129 (9) | −0.0031 (8) |
C6 | 0.0298 (10) | 0.0324 (10) | 0.0207 (12) | −0.0017 (8) | 0.0073 (9) | −0.0032 (8) |
C7 | 0.0233 (10) | 0.0293 (10) | 0.0276 (13) | −0.0030 (8) | 0.0055 (8) | −0.0073 (8) |
C8 | 0.0230 (10) | 0.0244 (9) | 0.0314 (13) | −0.0053 (8) | 0.0129 (9) | −0.0073 (8) |
C9 | 0.0256 (10) | 0.0202 (8) | 0.0215 (12) | −0.0004 (7) | 0.0118 (8) | −0.0047 (7) |
C10 | 0.0222 (9) | 0.0214 (8) | 0.0227 (11) | −0.0009 (7) | 0.0110 (8) | −0.0036 (7) |
O4 | 0.0242 (7) | 0.0422 (8) | 0.0245 (8) | −0.0060 (6) | 0.0157 (6) | −0.0057 (6) |
O21 | 0.0252 (7) | 0.0290 (7) | 0.0347 (9) | 0.0008 (6) | 0.0171 (6) | −0.0056 (6) |
O22 | 0.0350 (8) | 0.0286 (7) | 0.0240 (8) | −0.0010 (6) | 0.0180 (6) | −0.0002 (6) |
C23 | 0.0425 (13) | 0.0399 (11) | 0.0242 (13) | −0.0077 (10) | 0.0202 (10) | −0.0030 (9) |
C31 | 0.0215 (9) | 0.0214 (8) | 0.0196 (11) | 0.0018 (7) | 0.0093 (8) | 0.0011 (7) |
N32 | 0.0210 (8) | 0.0387 (9) | 0.0207 (10) | −0.0046 (7) | 0.0108 (7) | −0.0059 (7) |
C33 | 0.0183 (9) | 0.0448 (12) | 0.0240 (12) | −0.0054 (8) | 0.0044 (8) | 0.0028 (9) |
C34 | 0.0205 (9) | 0.0334 (10) | 0.0289 (12) | 0.0012 (8) | 0.0126 (8) | 0.0014 (8) |
O35 | 0.0420 (9) | 0.0363 (8) | 0.0256 (9) | 0.0115 (6) | 0.0169 (7) | 0.0030 (6) |
C311 | 0.0184 (9) | 0.0222 (8) | 0.0199 (11) | −0.0049 (7) | 0.0084 (8) | −0.0007 (7) |
C312 | 0.0215 (10) | 0.0278 (9) | 0.0235 (12) | −0.0012 (7) | 0.0072 (8) | 0.0021 (8) |
C313 | 0.0257 (11) | 0.0397 (11) | 0.0221 (12) | −0.0068 (9) | 0.0046 (9) | 0.0061 (9) |
C314 | 0.0317 (11) | 0.0439 (12) | 0.0186 (12) | −0.0157 (9) | 0.0135 (9) | −0.0074 (9) |
C315 | 0.0308 (10) | 0.0282 (10) | 0.0290 (13) | −0.0083 (8) | 0.0184 (9) | −0.0064 (8) |
C316 | 0.0228 (9) | 0.0240 (9) | 0.0226 (11) | −0.0020 (7) | 0.0107 (8) | 0.0009 (7) |
Geometric parameters (Å, º) top
P2—O21 | 1.4694 (14) | C312—C313 | 1.387 (3) |
P2—O22 | 1.5656 (15) | C312—H312 | 0.9300 |
P2—O1 | 1.5989 (14) | C8—C7 | 1.378 (3) |
P2—C3 | 1.7663 (19) | C8—H8 | 0.9300 |
O4—C4 | 1.250 (2) | C34—C33 | 1.512 (3) |
O35—C34 | 1.412 (2) | C34—H34A | 0.9700 |
O35—H35 | 0.8200 | C34—H34B | 0.9700 |
O22—C23 | 1.445 (3) | C33—H33B | 0.9700 |
O1—C9 | 1.390 (2) | C33—H33A | 0.9700 |
N32—C31 | 1.320 (3) | C315—C314 | 1.387 (3) |
N32—C33 | 1.463 (3) | C315—H315 | 0.9300 |
N32—H32 | 0.8600 | C313—C314 | 1.386 (3) |
C4—C3 | 1.435 (3) | C313—H313 | 0.9300 |
C4—C10 | 1.493 (3) | C7—C6 | 1.394 (3) |
C31—C3 | 1.417 (3) | C7—H7 | 0.9300 |
C31—C311 | 1.492 (3) | C5—C6 | 1.391 (3) |
C311—C316 | 1.390 (3) | C5—H5 | 0.9300 |
C311—C312 | 1.396 (3) | C314—H314 | 0.9300 |
C10—C9 | 1.395 (3) | C6—H6 | 0.9300 |
C10—C5 | 1.393 (3) | C23—H23B | 0.9600 |
C9—C8 | 1.388 (3) | C23—H23A | 0.9600 |
C316—C315 | 1.386 (3) | C23—H23C | 0.9600 |
C316—H316 | 0.9300 | | |
| | | |
O21—P2—O22 | 114.37 (8) | C4—C3—P2 | 118.74 (14) |
O21—P2—O1 | 111.02 (8) | O35—C34—C33 | 113.20 (16) |
O22—P2—O1 | 100.82 (8) | O35—C34—H34A | 108.9 |
O21—P2—C3 | 117.82 (8) | C33—C34—H34A | 108.9 |
O22—P2—C3 | 107.86 (8) | O35—C34—H34B | 108.9 |
O1—P2—C3 | 103.05 (8) | C33—C34—H34B | 108.9 |
C34—O35—H35 | 109.5 | H34A—C34—H34B | 107.8 |
C23—O22—P2 | 123.02 (13) | N32—C33—C34 | 109.90 (17) |
C9—O1—P2 | 119.41 (11) | N32—C33—H33B | 109.7 |
C31—N32—C33 | 126.87 (18) | C34—C33—H33B | 109.7 |
C31—N32—H32 | 116.6 | N32—C33—H33A | 109.7 |
C33—N32—H32 | 116.6 | C34—C33—H33A | 109.7 |
O4—C4—C3 | 122.74 (17) | H33B—C33—H33A | 108.2 |
O4—C4—C10 | 117.78 (18) | C316—C315—C314 | 120.19 (19) |
C3—C4—C10 | 119.42 (16) | C316—C315—H315 | 119.9 |
N32—C31—C3 | 120.58 (18) | C314—C315—H315 | 119.9 |
N32—C31—C311 | 117.77 (17) | C312—C313—C314 | 120.04 (19) |
C3—C31—C311 | 121.65 (16) | C312—C313—H313 | 120.0 |
C316—C311—C312 | 119.25 (18) | C314—C313—H313 | 120.0 |
C316—C311—C31 | 121.18 (17) | C8—C7—C6 | 120.45 (18) |
C312—C311—C31 | 119.57 (17) | C8—C7—H7 | 119.8 |
C9—C10—C5 | 118.10 (17) | C6—C7—H7 | 119.8 |
C9—C10—C4 | 121.69 (18) | C6—C5—C10 | 120.65 (18) |
C5—C10—C4 | 120.21 (17) | C6—C5—H5 | 119.7 |
C8—C9—O1 | 117.54 (17) | C10—C5—H5 | 119.7 |
C8—C9—C10 | 121.88 (19) | C315—C314—C313 | 119.9 (2) |
O1—C9—C10 | 120.51 (17) | C315—C314—H314 | 120.0 |
C315—C316—C311 | 120.30 (19) | C313—C314—H314 | 120.0 |
C315—C316—H316 | 119.9 | C5—C6—C7 | 119.8 (2) |
C311—C316—H316 | 119.9 | C5—C6—H6 | 120.1 |
C313—C312—C311 | 120.29 (19) | C7—C6—H6 | 120.1 |
C313—C312—H312 | 119.9 | O22—C23—H23B | 109.5 |
C311—C312—H312 | 119.9 | O22—C23—H23A | 109.5 |
C7—C8—C9 | 119.09 (18) | H23B—C23—H23A | 109.5 |
C7—C8—H8 | 120.5 | O22—C23—H23C | 109.5 |
C9—C8—H8 | 120.5 | H23B—C23—H23C | 109.5 |
C31—C3—C4 | 120.96 (17) | H23A—C23—H23C | 109.5 |
C31—C3—P2 | 120.27 (15) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N32—H32···O35 | 0.86 | 2.86 | 2.788 (2) | 86 |
N32—H32···O4 | 0.86 | 1.90 | 2.581 (2) | 135 |
O35—H35···O21i | 0.82 | 1.90 | 2.717 (2) | 173 |
C5—H5···O4ii | 0.93 | 2.42 | 3.287 (3) | 155 |
C314—H314···O35iii | 0.93 | 2.47 | 3.365 (3) | 160 |
Symmetry codes: (i) −x+1/2, −y+5/2, −z+1/2; (ii) −x+1/2, y, −z; (iii) x, −y+5/2, z+1/2. |