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A combined experimental and theoretical study of one oxaphosphinane derivative was made on the basis of a topological analysis of its electron density distributions. The electron density was determined from a high-resolution X-ray diffraction data set measured with synchrotron radiation at 100 K, whereas theoretical calculations were performed using density functional theory (DFT) methods at the B3LYP\6-311++G(3df,3pd) level of approximation. The charge-density distribution and analysis of topological properties revealed that the P—O bond is of the transit closed-shell type. The crystal structure possesses one intra- and several intermolecular hydrogen bonds. They were characterized quantitatively by topological properties using Bader's Atoms in Molecules theory. All hydrogen bonds were classified as weak. Further analysis of the experimental electron density by the source function allowed the intramolecular hydrogen bond to be characterized as an isolated hydrogen bond, in contrast to the resonance-assisted hydrogen bond in related molecules, such as chromone derivatives.
Supporting information
CCDC reference: 964654
Crystal data, data collection and structure refinement details are summarized in Table 1.
S2. Results and discussion
top
Data collection: MarCCD (Paulmann & Morgenroth, 2006); cell refinement: EVAL 15 (Schreurs, 2010); data reduction: EVAL 15 (Schreurs, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: Volkov et al., (2006); molecular graphics: Volkov et al., (2006); software used to prepare material for publication: Volkov et al., (2006).
3-(1-amino-ethylidene)-2-methoxy-2-oxo-2,3-dihydro-2
λ5-benzo[
e][1,2] oxaphosphinin-4-one
top
Crystal data top
C11H12NO4P | Z = 4 |
Mr = 253.19 | F(000) = 528 |
Orthorhombic, P212121 | Dx = 1.413 Mg m−3 |
Hall symbol: P 2ac 2ab | Synchrotron radiation, λ = 0.60000 Å |
a = 9.2532 (10) Å | µ = 0.23 mm−1 |
b = 10.1555 (16) Å | T = 100 K |
c = 12.6610 (12) Å | Block, colourless |
V = 1189.8 (3) Å3 | 0.45 × 0.3 × 0.18 mm |
Data collection top
Huber diffractometer | Rint = 0.035 |
Radiation source: synchrotron | θmax = 48.6°, θmin = 2.2° |
ϕ scan | h = −23→21 |
98994 measured reflections | k = −17→25 |
17584 independent reflections | l = −29→29 |
16534 reflections with I > 2σ(I) | |
Refinement top
Refinement on F | 534 parameters |
Least-squares matrix: full | 0 restraints |
R[F2 > 2σ(F2)] = 0.015 | w1 = 1/[s2(Fo)] |
wR(F2) = 0.017 | (Δ/σ)max < 0.001 |
S = 1.37 | Δρmax = 0.13 e Å−3 |
14864 reflections | Δρmin = −0.30 e Å−3 |
Crystal data top
C11H12NO4P | V = 1189.8 (3) Å3 |
Mr = 253.19 | Z = 4 |
Orthorhombic, P212121 | Synchrotron radiation, λ = 0.60000 Å |
a = 9.2532 (10) Å | µ = 0.23 mm−1 |
b = 10.1555 (16) Å | T = 100 K |
c = 12.6610 (12) Å | 0.45 × 0.3 × 0.18 mm |
Data collection top
Huber diffractometer | 16534 reflections with I > 2σ(I) |
98994 measured reflections | Rint = 0.035 |
17584 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.015 | 534 parameters |
wR(F2) = 0.017 | 0 restraints |
S = 1.37 | Δρmax = 0.13 e Å−3 |
14864 reflections | Δρmin = −0.30 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P(2) | 0.661925 (5) | 0.482849 (4) | 0.074523 (4) | 0.014 | |
O(1) | 0.79064 (2) | 0.589242 (19) | 0.07178 (2) | 0.018 | |
O(4) | 0.94685 (3) | 0.24666 (3) | 0.20485 (2) | 0.021 | |
O(21) | 0.53019 (3) | 0.55035 (3) | 0.11139 (2) | 0.021 | |
O(22) | 0.65057 (3) | 0.43039 (2) | −0.042492 (16) | 0.019 | |
N(1) | 0.68818 (3) | 0.17020 (2) | 0.264657 (19) | 0.020 | |
C(3) | 0.73085 (2) | 0.350744 (18) | 0.147879 (15) | 0.015 | |
C(4) | 0.88637 (2) | 0.334200 (19) | 0.151694 (15) | 0.015 | |
C(5) | 1.12308 (2) | 0.38966 (2) | 0.066650 (18) | 0.018 | |
C(6) | 1.21239 (3) | 0.47156 (3) | 0.00743 (2) | 0.022 | |
C(7) | 1.16036 (3) | 0.59292 (3) | −0.02899 (2) | 0.023 | |
C(8) | 1.01866 (3) | 0.63147 (2) | −0.00725 (2) | 0.021 | |
C(9) | 0.93004 (2) | 0.546727 (18) | 0.050172 (16) | 0.016 | |
C(10) | 0.97952 (2) | 0.425563 (18) | 0.088410 (14) | 0.015 | |
C(23) | 0.60537 (4) | 0.51966 (3) | −0.12529 (2) | 0.025 | |
C(31) | 0.63736 (2) | 0.26343 (2) | 0.201981 (16) | 0.017 | |
C(311) | 0.47572 (3) | 0.26942 (3) | 0.19046 (2) | 0.025 | |
H(1) | 0.796474 | 0.16279 | 0.271845 | 0.035 | |
H(2) | 0.614406 | 0.117774 | 0.305578 | 0.040 | |
H(5) | 1.161608 | 0.295929 | 0.096151 | 0.036 | |
H(6) | 1.322238 | 0.441658 | −0.009789 | 0.043 | |
H(7) | 1.22733 | 0.659594 | −0.074373 | 0.044 | |
H(8) | 0.973804 | 0.723838 | −0.034655 | 0.038 | |
H(23A) | 0.586691 | 0.460366 | −0.192751 | 0.046 | |
H(23B) | 0.691586 | 0.586417 | −0.137821 | 0.043 | |
H(23C) | 0.509378 | 0.567889 | −0.10134 | 0.045 | |
H(31A) | 0.422351 | 0.191569 | 0.23015 | 0.046 | |
H(31B) | 0.451524 | 0.260552 | 0.10902 | 0.041 | |
H(31C) | 0.432393 | 0.362726 | 0.210244 | 0.042 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P(2) | 0.017529 (15) | 0.011967 (15) | 0.012494 (15) | 0.001408 (12) | 0.000818 (12) | −0.000247 (11) |
O(1) | 0.02055 (6) | 0.01086 (5) | 0.02307 (7) | 0.00051 (5) | −0.00017 (6) | −0.00030 (5) |
O(4) | 0.02124 (7) | 0.01938 (7) | 0.02338 (9) | 0.00517 (6) | 0.00429 (7) | 0.00844 (7) |
O(21) | 0.02100 (7) | 0.02011 (7) | 0.02270 (8) | 0.00577 (6) | 0.00369 (7) | −0.00002 (7) |
O(22) | 0.02992 (9) | 0.01515 (6) | 0.01176 (5) | −0.00107 (6) | −0.00087 (6) | 0.00053 (4) |
N(1) | 0.02209 (7) | 0.01893 (7) | 0.01913 (7) | 0.00005 (6) | 0.00286 (6) | 0.00668 (6) |
C(3) | 0.01831 (6) | 0.01347 (5) | 0.01276 (5) | 0.00047 (5) | 0.00122 (5) | 0.00145 (4) |
C(4) | 0.01857 (6) | 0.01286 (5) | 0.01443 (6) | 0.00179 (5) | 0.00243 (5) | 0.00152 (4) |
C(5) | 0.01772 (6) | 0.01542 (6) | 0.02166 (7) | −0.00023 (5) | 0.00226 (5) | 0.00093 (5) |
C(6) | 0.01860 (7) | 0.01981 (8) | 0.02660 (9) | −0.00359 (6) | 0.00263 (6) | 0.00174 (7) |
C(7) | 0.02188 (7) | 0.01935 (7) | 0.02827 (10) | −0.00631 (7) | 0.00154 (7) | 0.00454 (7) |
C(8) | 0.02301 (8) | 0.01417 (6) | 0.02590 (9) | −0.00413 (6) | −0.00030 (6) | 0.00427 (6) |
C(9) | 0.01930 (6) | 0.01118 (5) | 0.01810 (6) | −0.00129 (5) | −0.00008 (5) | 0.00044 (4) |
C(10) | 0.01797 (6) | 0.01196 (5) | 0.01555 (6) | −0.00007 (4) | 0.00149 (4) | 0.00017 (4) |
C(23) | 0.03553 (11) | 0.02295 (9) | 0.01653 (7) | −0.00569 (9) | −0.00431 (8) | 0.00664 (7) |
C(31) | 0.01919 (6) | 0.01649 (6) | 0.01408 (6) | −0.00068 (5) | 0.00135 (5) | 0.00236 (5) |
C(311) | 0.01989 (7) | 0.02841 (11) | 0.02535 (10) | −0.00272 (8) | −0.00058 (7) | 0.00854 (8) |
H(1) | 0.028540 | 0.038772 | 0.038718 | 0.002235 | 0.001399 | 0.013738 |
H(2) | 0.035769 | 0.043627 | 0.039504 | −0.004827 | 0.007242 | 0.019888 |
H(5) | 0.033045 | 0.028072 | 0.048354 | 0.007933 | 0.005758 | 0.010379 |
H(6) | 0.026194 | 0.045977 | 0.057409 | 0.002887 | 0.012001 | 0.008524 |
H(7) | 0.037782 | 0.038773 | 0.054565 | −0.011459 | 0.009585 | 0.015414 |
H(8) | 0.041533 | 0.022123 | 0.050895 | −0.000455 | 0.000643 | 0.011577 |
H(23A) | 0.064812 | 0.048447 | 0.025551 | −0.006588 | −0.010956 | −0.000789 |
H(23B) | 0.040322 | 0.042842 | 0.044646 | −0.013230 | −0.005697 | 0.017506 |
H(23C) | 0.039060 | 0.052588 | 0.042363 | 0.011650 | 0.002289 | 0.013691 |
H(31A) | 0.037072 | 0.047705 | 0.051792 | −0.009061 | 0.006355 | 0.022578 |
H(31B) | 0.037087 | 0.058937 | 0.025816 | −0.003626 | −0.001535 | 0.001158 |
H(31C) | 0.035110 | 0.038214 | 0.052426 | 0.006607 | 0.003491 | −0.004192 |
Geometric parameters (Å, º) top
P(2)—O(1) | 1.6085 (2) | C(6)—C(7) | 1.4012 (4) |
P(2)—O(21) | 1.4743 (2) | C(6)—H(6) | 1.0830 |
P(2)—O(22) | 1.5779 (2) | C(7)—C(8) | 1.3959 (4) |
P(2)—C(3) | 1.7519 (2) | C(7)—H(7) | 1.0829 |
O(1)—C(9) | 1.3874 (3) | C(8)—C(9) | 1.3934 (3) |
O(4)—C(4) | 1.2476 (3) | C(8)—H(8) | 1.0828 |
N(1)—C(31) | 1.3218 (3) | C(9)—C(10) | 1.3993 (3) |
N(1)—H(1) | 1.0090 | C(23)—H(23A) | 1.0593 |
N(1)—H(2) | 1.0089 | C(23)—H(23B) | 1.0589 |
C(3)—C(4) | 1.4497 (3) | C(23)—H(23C) | 1.0586 |
C(3)—C(31) | 1.4155 (3) | C(31)—C(311) | 1.5040 (3) |
C(4)—C(10) | 1.4986 (3) | C(311)—H(31A) | 1.0589 |
C(5)—C(6) | 1.3918 (3) | C(311)—H(31B) | 1.0590 |
C(5)—C(10) | 1.4048 (3) | C(311)—H(31C) | 1.0590 |
C(5)—H(5) | 1.0829 | | |
| | | |
O(1)—P(2)—O(21) | 107.861 (14) | C(6)—C(7)—H(7) | 121.87 |
O(1)—P(2)—O(22) | 104.823 (13) | C(8)—C(7)—H(7) | 117.83 |
O(1)—P(2)—C(3) | 104.851 (11) | C(7)—C(8)—C(9) | 118.85 (2) |
O(21)—P(2)—O(22) | 113.525 (16) | C(7)—C(8)—H(8) | 122.67 |
O(21)—P(2)—C(3) | 119.290 (13) | C(9)—C(8)—H(8) | 118.47 |
O(22)—P(2)—C(3) | 105.276 (10) | O(1)—C(9)—C(8) | 117.24 (2) |
P(2)—O(1)—C(9) | 118.922 (15) | O(1)—C(9)—C(10) | 120.639 (19) |
C(31)—N(1)—H(1) | 117.44 | C(8)—C(9)—C(10) | 122.08 (2) |
C(31)—N(1)—H(2) | 116.46 | C(4)—C(10)—C(5) | 119.209 (18) |
H(1)—N(1)—H(2) | 125.89 | C(4)—C(10)—C(9) | 122.768 (18) |
P(2)—C(3)—C(4) | 117.891 (14) | C(5)—C(10)—C(9) | 118.022 (19) |
P(2)—C(3)—C(31) | 120.916 (16) | H(23A)—C(23)—H(23B) | 111.47 |
C(4)—C(3)—C(31) | 121.193 (17) | H(23A)—C(23)—H(23C) | 110.92 |
O(4)—C(4)—C(3) | 123.08 (2) | H(23B)—C(23)—H(23C) | 112.27 |
O(4)—C(4)—C(10) | 118.14 (2) | N(1)—C(31)—C(3) | 121.45 (2) |
C(3)—C(4)—C(10) | 118.775 (17) | N(1)—C(31)—C(311) | 116.16 (2) |
C(6)—C(5)—C(10) | 120.80 (2) | C(3)—C(31)—C(311) | 122.38 (2) |
C(6)—C(5)—H(5) | 121.04 | C(31)—C(311)—H(31A) | 112.81 |
C(10)—C(5)—H(5) | 118.15 | C(31)—C(311)—H(31B) | 107.53 |
C(5)—C(6)—C(7) | 119.93 (2) | C(31)—C(311)—H(31C) | 112.94 |
C(5)—C(6)—H(6) | 119.88 | H(31A)—C(311)—H(31B) | 107.45 |
C(7)—C(6)—H(6) | 120.19 | H(31A)—C(311)—H(31C) | 112.29 |
C(6)—C(7)—C(8) | 120.30 (2) | H(31B)—C(311)—H(31C) | 103.08 |
Experimental details
Crystal data |
Chemical formula | C11H12NO4P |
Mr | 253.19 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 9.2532 (10), 10.1555 (16), 12.6610 (12) |
V (Å3) | 1189.8 (3) |
Z | 4 |
Radiation type | Synchrotron, λ = 0.60000 Å |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.45 × 0.3 × 0.18 |
|
Data collection |
Diffractometer | Huber diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 98994, 17584, 16534 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 1.250 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.015, 0.017, 1.37 |
No. of reflections | 14864 |
No. of parameters | 534 |
Δρmax, Δρmin (e Å−3) | 0.13, −0.30 |
Selected geometric parameters (Å, º) topP(2)—O(1) | 1.6085 (2) | C(6)—C(7) | 1.4012 (4) |
P(2)—O(21) | 1.4743 (2) | C(6)—H(6) | 1.0830 |
P(2)—O(22) | 1.5779 (2) | C(7)—C(8) | 1.3959 (4) |
P(2)—C(3) | 1.7519 (2) | C(7)—H(7) | 1.0829 |
O(1)—C(9) | 1.3874 (3) | C(8)—C(9) | 1.3934 (3) |
O(4)—C(4) | 1.2476 (3) | C(8)—H(8) | 1.0828 |
N(1)—C(31) | 1.3218 (3) | C(9)—C(10) | 1.3993 (3) |
N(1)—H(1) | 1.0090 | C(23)—H(23A) | 1.0593 |
N(1)—H(2) | 1.0089 | C(23)—H(23B) | 1.0589 |
C(3)—C(4) | 1.4497 (3) | C(23)—H(23C) | 1.0586 |
C(3)—C(31) | 1.4155 (3) | C(31)—C(311) | 1.5040 (3) |
C(4)—C(10) | 1.4986 (3) | C(311)—H(31A) | 1.0589 |
C(5)—C(6) | 1.3918 (3) | C(311)—H(31B) | 1.0590 |
C(5)—C(10) | 1.4048 (3) | C(311)—H(31C) | 1.0590 |
C(5)—H(5) | 1.0829 | | |
| | | |
O(1)—P(2)—O(21) | 107.861 (14) | C(6)—C(7)—H(7) | 121.87 |
O(1)—P(2)—O(22) | 104.823 (13) | C(8)—C(7)—H(7) | 117.83 |
O(1)—P(2)—C(3) | 104.851 (11) | C(7)—C(8)—C(9) | 118.85 (2) |
O(21)—P(2)—O(22) | 113.525 (16) | C(7)—C(8)—H(8) | 122.67 |
O(21)—P(2)—C(3) | 119.290 (13) | C(9)—C(8)—H(8) | 118.47 |
O(22)—P(2)—C(3) | 105.276 (10) | O(1)—C(9)—C(8) | 117.24 (2) |
P(2)—O(1)—C(9) | 118.922 (15) | O(1)—C(9)—C(10) | 120.639 (19) |
C(31)—N(1)—H(1) | 117.44 | C(8)—C(9)—C(10) | 122.08 (2) |
C(31)—N(1)—H(2) | 116.46 | C(4)—C(10)—C(5) | 119.209 (18) |
H(1)—N(1)—H(2) | 125.89 | C(4)—C(10)—C(9) | 122.768 (18) |
P(2)—C(3)—C(4) | 117.891 (14) | C(5)—C(10)—C(9) | 118.022 (19) |
P(2)—C(3)—C(31) | 120.916 (16) | H(23A)—C(23)—H(23B) | 111.47 |
C(4)—C(3)—C(31) | 121.193 (17) | H(23A)—C(23)—H(23C) | 110.92 |
O(4)—C(4)—C(3) | 123.08 (2) | H(23B)—C(23)—H(23C) | 112.27 |
O(4)—C(4)—C(10) | 118.14 (2) | N(1)—C(31)—C(3) | 121.45 (2) |
C(3)—C(4)—C(10) | 118.775 (17) | N(1)—C(31)—C(311) | 116.16 (2) |
C(6)—C(5)—C(10) | 120.80 (2) | C(3)—C(31)—C(311) | 122.38 (2) |
C(6)—C(5)—H(5) | 121.04 | C(31)—C(311)—H(31A) | 112.81 |
C(10)—C(5)—H(5) | 118.15 | C(31)—C(311)—H(31B) | 107.53 |
C(5)—C(6)—C(7) | 119.93 (2) | C(31)—C(311)—H(31C) | 112.94 |
C(5)—C(6)—H(6) | 119.88 | H(31A)—C(311)—H(31B) | 107.45 |
C(7)—C(6)—H(6) | 120.19 | H(31A)—C(311)—H(31C) | 112.29 |
C(6)—C(7)—C(8) | 120.30 (2) | H(31B)—C(311)—H(31C) | 103.08 |
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