Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102008508/na1572sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102008508/na1572Isup2.hkl |
CCDC reference: 192981
The title compound was obtained by the reaction of equimolar amounts of 4-oxo-4H-benzopyran-3-carboxyaldehyde (0.87 g, 0.005 mol) and N1-diphenyloxyphosphonate-N1-methylhydrazide (1.38 g) in anhydrous methanol solution (see reaction Scheme). After 24 h, the product was precipitated from the reaction solution (m.p. 393–395 K). Crystals of (I) suitable for X-ray analysis were obtained by recrystallization from methanol.
H atoms in benzenoid rings were constrained to their parent C atoms by a rigid body model, using the AFIX 43 instruction in SHELXL97 (Sheldrick, 1997). The remaining H atoms were freely refined.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1989); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1998); software used to prepare material for publication: SHELXL97 and PARST97 (Nardelli, 1996).
Fig. 1. A view of the molecule of (I) showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. |
C23H19N2O5P | F(000) = 904 |
Mr = 434.37 | Dx = 1.385 Mg m−3 Dm = 1.378 Mg m−3 Dm measured by flotation in a solution of KI and KBr in water |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 8.312 (2) Å | θ = 21.3–23.8° |
b = 10.611 (1) Å | µ = 0.17 mm−1 |
c = 23.595 (2) Å | T = 293 K |
β = 90.76 (1)° | Prism, colourless |
V = 2082.8 (5) Å3 | 0.6 × 0.5 × 0.4 mm |
Z = 4 |
Rigaku AFC-5S diffractometer | 2746 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 25.0°, θmin = 3.5° |
ω scans | h = −9→9 |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | k = 0→12 |
Tmin = 0.915, Tmax = 0.944 | l = 0→28 |
3738 measured reflections | 3 standard reflections every 150 reflections |
3648 independent reflections | intensity decay: <2% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0798P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max < 0.001 |
3648 reflections | Δρmax = 0.28 e Å−3 |
301 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.018 (2) |
C23H19N2O5P | V = 2082.8 (5) Å3 |
Mr = 434.37 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.312 (2) Å | µ = 0.17 mm−1 |
b = 10.611 (1) Å | T = 293 K |
c = 23.595 (2) Å | 0.6 × 0.5 × 0.4 mm |
β = 90.76 (1)° |
Rigaku AFC-5S diffractometer | 2746 reflections with I > 2σ(I) |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | Rint = 0.015 |
Tmin = 0.915, Tmax = 0.944 | 3 standard reflections every 150 reflections |
3738 measured reflections | intensity decay: <2% |
3648 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.28 e Å−3 |
3648 reflections | Δρmin = −0.24 e Å−3 |
301 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
P1 | 0.22022 (6) | 0.36544 (5) | 0.18452 (2) | 0.0514 (2) | |
O2 | 0.25073 (18) | 0.42753 (14) | 0.23831 (6) | 0.0654 (4) | |
N3 | 0.33831 (19) | 0.24397 (15) | 0.17406 (7) | 0.0543 (4) | |
C31 | 0.4785 (3) | 0.2169 (3) | 0.20950 (11) | 0.0658 (6) | |
N4 | 0.29932 (18) | 0.16982 (15) | 0.12761 (7) | 0.0525 (4) | |
C5 | 0.3904 (2) | 0.07810 (18) | 0.11550 (8) | 0.0503 (5) | |
O61 | 0.17005 (17) | −0.06544 (14) | −0.00660 (6) | 0.0646 (4) | |
C62 | 0.2186 (2) | 0.0101 (2) | 0.03608 (9) | 0.0561 (5) | |
H62 | 0.145 (3) | 0.077 (2) | 0.0397 (9) | 0.072 (7)* | |
C63 | 0.3510 (2) | −0.00580 (17) | 0.06826 (8) | 0.0472 (4) | |
C64 | 0.4587 (2) | −0.11072 (18) | 0.05635 (9) | 0.0543 (5) | |
O641 | 0.58513 (19) | −0.12694 (15) | 0.08232 (8) | 0.0838 (5) | |
C65 | 0.4924 (3) | −0.2997 (2) | −0.00597 (12) | 0.0748 (7) | |
H65 | 0.5881 | −0.3194 | 0.0128 | 0.090* | |
C66 | 0.4379 (4) | −0.3747 (2) | −0.04955 (12) | 0.0866 (8) | |
H66 | 0.4982 | −0.4439 | −0.0607 | 0.104* | |
C67 | 0.2949 (4) | −0.3482 (3) | −0.07680 (12) | 0.0878 (8) | |
H67 | 0.2583 | −0.4004 | −0.1059 | 0.105* | |
C68 | 0.2065 (3) | −0.2459 (2) | −0.06157 (10) | 0.0785 (7) | |
H68 | 0.1093 | −0.2284 | −0.0798 | 0.094* | |
C69 | 0.2629 (3) | −0.16894 (19) | −0.01875 (9) | 0.0565 (5) | |
C70 | 0.4040 (2) | −0.19352 (18) | 0.01031 (9) | 0.0548 (5) | |
O11 | 0.04154 (15) | 0.31704 (12) | 0.17435 (5) | 0.0530 (4) | |
C12 | −0.0294 (2) | 0.2327 (2) | 0.21271 (8) | 0.0544 (5) | |
C13 | −0.0638 (3) | 0.1127 (2) | 0.19307 (11) | 0.0744 (7) | |
H13 | −0.0312 | 0.0883 | 0.1572 | 0.089* | |
C14 | −0.1455 (3) | 0.0301 (3) | 0.22641 (15) | 0.0970 (9) | |
H14 | −0.1707 | −0.0500 | 0.2129 | 0.116* | |
C15 | −0.1903 (3) | 0.0649 (3) | 0.27954 (14) | 0.0972 (9) | |
H15 | −0.2471 | 0.0088 | 0.3020 | 0.117* | |
C16 | −0.1528 (3) | 0.1795 (4) | 0.29954 (11) | 0.0979 (10) | |
H16 | −0.1808 | 0.2009 | 0.3363 | 0.118* | |
C17 | −0.0707 (3) | 0.2690 (3) | 0.26554 (10) | 0.0747 (7) | |
H17 | −0.0465 | 0.3492 | 0.2791 | 0.090* | |
O21 | 0.24129 (17) | 0.44753 (12) | 0.12929 (6) | 0.0603 (4) | |
C22 | 0.1556 (2) | 0.56025 (17) | 0.12009 (8) | 0.0513 (5) | |
C23 | 0.1895 (3) | 0.66578 (19) | 0.15090 (9) | 0.0625 (5) | |
H23 | 0.2681 | 0.6638 | 0.1793 | 0.075* | |
C24 | 0.1064 (3) | 0.7754 (2) | 0.13971 (10) | 0.0710 (6) | |
H24 | 0.1296 | 0.8479 | 0.1604 | 0.085* | |
C25 | −0.0089 (3) | 0.7778 (3) | 0.09874 (12) | 0.0806 (7) | |
H25 | −0.0669 | 0.8514 | 0.0920 | 0.097* | |
C26 | −0.0401 (3) | 0.6730 (3) | 0.06736 (12) | 0.0868 (8) | |
H26 | −0.1176 | 0.6759 | 0.0386 | 0.104* | |
C27 | 0.0425 (3) | 0.5617 (2) | 0.07787 (10) | 0.0716 (6) | |
H27 | 0.0211 | 0.4897 | 0.0566 | 0.086* | |
H51 | 0.488 (3) | 0.0604 (19) | 0.1351 (9) | 0.063 (6)* | |
H311 | 0.578 (3) | 0.227 (2) | 0.1883 (10) | 0.076 (7)* | |
H312 | 0.482 (3) | 0.277 (3) | 0.2376 (12) | 0.090 (8)* | |
H313 | 0.467 (3) | 0.136 (2) | 0.2267 (10) | 0.078 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0536 (3) | 0.0488 (3) | 0.0518 (3) | 0.0030 (2) | −0.0007 (2) | −0.0055 (2) |
O2 | 0.0721 (9) | 0.0631 (9) | 0.0608 (9) | 0.0006 (7) | −0.0044 (7) | −0.0154 (7) |
N3 | 0.0539 (9) | 0.0540 (9) | 0.0548 (9) | 0.0062 (7) | −0.0092 (7) | −0.0089 (8) |
C31 | 0.0571 (13) | 0.0751 (16) | 0.0649 (14) | 0.0098 (12) | −0.0147 (11) | −0.0099 (13) |
N4 | 0.0536 (9) | 0.0488 (9) | 0.0549 (9) | 0.0051 (7) | −0.0055 (7) | −0.0049 (8) |
C5 | 0.0459 (10) | 0.0491 (11) | 0.0557 (11) | 0.0029 (9) | −0.0030 (9) | 0.0013 (9) |
O61 | 0.0632 (8) | 0.0660 (9) | 0.0641 (9) | 0.0094 (7) | −0.0145 (7) | −0.0117 (7) |
C62 | 0.0543 (11) | 0.0528 (11) | 0.0609 (12) | 0.0105 (9) | −0.0054 (9) | −0.0050 (10) |
C63 | 0.0460 (10) | 0.0436 (10) | 0.0522 (11) | 0.0039 (8) | 0.0023 (8) | 0.0025 (8) |
C64 | 0.0503 (11) | 0.0506 (11) | 0.0620 (12) | 0.0052 (9) | 0.0020 (9) | 0.0023 (9) |
O641 | 0.0642 (10) | 0.0849 (11) | 0.1015 (13) | 0.0287 (8) | −0.0251 (9) | −0.0147 (10) |
C65 | 0.0747 (14) | 0.0566 (13) | 0.0934 (17) | 0.0078 (11) | 0.0187 (13) | −0.0068 (13) |
C66 | 0.110 (2) | 0.0545 (14) | 0.096 (2) | −0.0043 (14) | 0.0463 (17) | −0.0201 (14) |
C67 | 0.114 (2) | 0.0811 (18) | 0.0693 (16) | −0.0205 (16) | 0.0199 (15) | −0.0220 (14) |
C68 | 0.0929 (17) | 0.0759 (16) | 0.0665 (15) | −0.0072 (14) | −0.0016 (13) | −0.0167 (13) |
C69 | 0.0612 (12) | 0.0538 (11) | 0.0546 (12) | −0.0031 (9) | 0.0050 (9) | −0.0012 (9) |
C70 | 0.0567 (11) | 0.0456 (11) | 0.0625 (12) | 0.0000 (9) | 0.0131 (9) | −0.0008 (9) |
O11 | 0.0514 (7) | 0.0550 (8) | 0.0524 (8) | 0.0046 (6) | −0.0027 (6) | 0.0034 (6) |
C12 | 0.0425 (10) | 0.0618 (12) | 0.0587 (12) | 0.0117 (9) | −0.0003 (8) | 0.0089 (10) |
C13 | 0.0775 (15) | 0.0535 (13) | 0.0929 (17) | 0.0108 (11) | 0.0190 (13) | 0.0082 (12) |
C14 | 0.092 (2) | 0.0692 (17) | 0.131 (3) | 0.0103 (14) | 0.0194 (18) | 0.0289 (18) |
C15 | 0.0747 (17) | 0.115 (2) | 0.101 (2) | 0.0013 (17) | −0.0004 (16) | 0.046 (2) |
C16 | 0.0648 (15) | 0.176 (3) | 0.0533 (14) | 0.0050 (19) | 0.0032 (11) | 0.0157 (18) |
C17 | 0.0550 (12) | 0.1051 (18) | 0.0640 (14) | −0.0002 (12) | 0.0025 (10) | −0.0077 (14) |
O21 | 0.0662 (9) | 0.0526 (8) | 0.0625 (9) | 0.0077 (7) | 0.0114 (7) | 0.0014 (7) |
C22 | 0.0497 (10) | 0.0489 (11) | 0.0553 (11) | −0.0026 (8) | 0.0091 (9) | 0.0040 (9) |
C23 | 0.0682 (13) | 0.0574 (12) | 0.0617 (13) | −0.0049 (10) | −0.0036 (10) | 0.0015 (10) |
C24 | 0.0941 (17) | 0.0520 (12) | 0.0671 (15) | 0.0053 (12) | 0.0093 (13) | 0.0029 (11) |
C25 | 0.0832 (17) | 0.0718 (16) | 0.0872 (18) | 0.0183 (13) | 0.0203 (14) | 0.0220 (15) |
C26 | 0.0695 (15) | 0.106 (2) | 0.0840 (18) | 0.0013 (15) | −0.0188 (13) | 0.0220 (17) |
C27 | 0.0764 (15) | 0.0703 (14) | 0.0678 (14) | −0.0122 (12) | −0.0118 (12) | −0.0022 (12) |
P1—O2 | 1.450 (1) | C68—H68 | 0.9300 |
P1—O21 | 1.579 (1) | C69—C70 | 1.376 (3) |
P1—O11 | 1.588 (1) | O11—C12 | 1.408 (2) |
P1—N3 | 1.641 (2) | C12—C17 | 1.354 (3) |
N3—N4 | 1.384 (2) | C12—C13 | 1.384 (3) |
N3—C31 | 1.455 (3) | C13—C14 | 1.365 (3) |
C31—H311 | 0.98 (2) | C13—H13 | 0.9300 |
C31—H312 | 0.92 (3) | C14—C15 | 1.364 (4) |
C31—H313 | 0.95 (2) | C14—H14 | 0.9300 |
N4—C5 | 1.269 (2) | C15—C16 | 1.340 (4) |
C5—C63 | 1.460 (3) | C15—H15 | 0.9300 |
C5—H51 | 0.95 (2) | C16—C17 | 1.424 (4) |
O61—C62 | 1.345 (2) | C16—H16 | 0.9300 |
O61—C69 | 1.375 (2) | C17—H17 | 0.9300 |
C62—C63 | 1.340 (3) | O21—C22 | 1.408 (2) |
C62—H62 | 0.94 (2) | C22—C27 | 1.361 (3) |
C63—C64 | 1.459 (2) | C22—C23 | 1.363 (3) |
C64—O641 | 1.222 (2) | C23—C24 | 1.377 (3) |
C64—C70 | 1.465 (3) | C23—H23 | 0.9300 |
C65—C66 | 1.372 (4) | C24—C25 | 1.353 (4) |
C65—C70 | 1.402 (3) | C24—H24 | 0.9300 |
C65—H65 | 0.9300 | C25—C26 | 1.360 (4) |
C66—C67 | 1.374 (4) | C25—H25 | 0.9300 |
C66—H66 | 0.9300 | C26—C27 | 1.387 (4) |
C67—C68 | 1.361 (4) | C26—H26 | 0.9300 |
C67—H67 | 0.9300 | C27—H27 | 0.9300 |
C68—C69 | 1.377 (3) | ||
O2—P1—O21 | 116.86 (8) | C70—C69—C68 | 122.2 (2) |
O2—P1—O11 | 115.59 (8) | C69—C70—C65 | 117.6 (2) |
O21—P1—O11 | 99.66 (7) | C69—C70—C64 | 120.7 (2) |
O2—P1—N3 | 112.98 (9) | C65—C70—C64 | 121.8 (2) |
O21—P1—N3 | 103.64 (8) | C12—O11—P1 | 120.54 (11) |
O11—P1—N3 | 106.52 (8) | C17—C12—C13 | 121.1 (2) |
N4—N3—C31 | 121.4 (2) | C17—C12—O11 | 121.6 (2) |
N4—N3—P1 | 115.5 (1) | C13—C12—O11 | 117.15 (19) |
C31—N3—P1 | 123.1 (2) | C14—C13—C12 | 120.0 (3) |
N3—C31—H311 | 111.2 (15) | C14—C13—H13 | 120.0 |
N3—C31—H312 | 107.1 (17) | C12—C13—H13 | 120.0 |
H311—C31—H312 | 106 (2) | C15—C14—C13 | 120.0 (3) |
N3—C31—H313 | 110.0 (14) | C15—C14—H14 | 120.0 |
H311—C31—H313 | 114 (2) | C13—C14—H14 | 120.0 |
H312—C31—H313 | 108 (2) | C16—C15—C14 | 120.3 (3) |
C5—N4—N3 | 118.7 (2) | C16—C15—H15 | 119.9 |
N4—C5—C63 | 120.7 (2) | C14—C15—H15 | 119.9 |
N4—C5—H51 | 123.6 (13) | C15—C16—C17 | 121.2 (3) |
C63—C5—H51 | 115.7 (13) | C15—C16—H16 | 119.4 |
C62—O61—C69 | 117.9 (2) | C17—C16—H16 | 119.4 |
C63—C62—O61 | 125.9 (2) | C12—C17—C16 | 117.3 (3) |
C63—C62—H62 | 125.2 (12) | C12—C17—H17 | 121.4 |
O61—C62—H62 | 108.9 (13) | C16—C17—H17 | 121.4 |
C62—C63—C64 | 119.3 (2) | C22—O21—P1 | 122.30 (12) |
C62—C63—C5 | 122.0 (2) | C27—C22—C23 | 121.2 (2) |
C64—C63—C5 | 118.7 (2) | C27—C22—O21 | 117.78 (18) |
O641—C64—C63 | 122.5 (2) | C23—C22—O21 | 121.00 (18) |
O641—C64—C70 | 122.9 (2) | C22—C23—C24 | 119.5 (2) |
C63—C64—C70 | 114.5 (2) | C22—C23—H23 | 120.3 |
C66—C65—C70 | 120.1 (2) | C24—C23—H23 | 120.3 |
C66—C65—H65 | 119.9 | C25—C24—C23 | 120.2 (2) |
C70—C65—H65 | 119.9 | C25—C24—H24 | 119.9 |
C65—C66—C67 | 120.5 (2) | C23—C24—H24 | 119.9 |
C65—C66—H66 | 119.8 | C24—C25—C26 | 120.1 (2) |
C67—C66—H66 | 119.8 | C24—C25—H25 | 119.9 |
C68—C67—C66 | 120.5 (2) | C26—C25—H25 | 119.9 |
C68—C67—H67 | 119.8 | C25—C26—C27 | 120.6 (2) |
C66—C67—H67 | 119.8 | C25—C26—H26 | 119.7 |
C67—C68—C69 | 119.1 (3) | C27—C26—H26 | 119.7 |
C67—C68—H68 | 120.5 | C22—C27—C26 | 118.4 (2) |
C69—C68—H68 | 120.5 | C22—C27—H27 | 120.8 |
O61—C69—C70 | 121.7 (2) | C26—C27—H27 | 120.8 |
O61—C69—C68 | 116.1 (2) | ||
O2—P1—N3—N4 | 170.7 (1) | O641—C64—C70—C69 | −178.0 (2) |
O21—P1—N3—N4 | −61.82 (15) | C63—C64—C70—C69 | 1.1 (3) |
O11—P1—N3—N4 | 42.77 (16) | O641—C64—C70—C65 | 1.8 (3) |
O2—P1—N3—C31 | −11.4 (2) | C63—C64—C70—C65 | −179.08 (19) |
O21—P1—N3—C31 | 116.05 (19) | O2—P1—O11—C12 | −56.98 (16) |
O11—P1—N3—C31 | −139.35 (19) | O21—P1—O11—C12 | 176.89 (13) |
C31—N3—N4—C5 | −1.4 (3) | N3—P1—O11—C12 | 69.43 (15) |
P1—N3—N4—C5 | 176.5 (1) | P1—O11—C12—C17 | 70.1 (2) |
N3—N4—C5—C63 | 177.5 (2) | P1—O11—C12—C13 | −113.46 (18) |
C69—O61—C62—C63 | 0.2 (3) | C17—C12—C13—C14 | 2.3 (3) |
O61—C62—C63—C64 | 2.2 (3) | O11—C12—C13—C14 | −174.1 (2) |
O61—C62—C63—C5 | −177.17 (18) | C12—C13—C14—C15 | −1.4 (4) |
N4—C5—C63—C62 | 0.0 (3) | C13—C14—C15—C16 | −0.8 (4) |
N4—C5—C63—C64 | −179.4 (2) | C14—C15—C16—C17 | 2.2 (4) |
C62—C63—C64—O641 | 176.4 (2) | C13—C12—C17—C16 | −0.9 (3) |
C5—C63—C64—O641 | −4.2 (3) | O11—C12—C17—C16 | 175.35 (19) |
C62—C63—C64—C70 | −2.7 (3) | C15—C16—C17—C12 | −1.3 (4) |
C5—C63—C64—C70 | 176.66 (16) | O2—P1—O21—C22 | −57.06 (17) |
C70—C65—C66—C67 | −1.4 (4) | O11—P1—O21—C22 | 68.20 (15) |
C65—C66—C67—C68 | 1.1 (4) | N3—P1—O21—C22 | 177.96 (14) |
C66—C67—C68—C69 | 0.5 (4) | P1—O21—C22—C27 | −111.79 (19) |
C62—O61—C69—C70 | −2.0 (3) | P1—O21—C22—C23 | 70.8 (2) |
C62—O61—C69—C68 | 178.1 (2) | C27—C22—C23—C24 | 0.9 (3) |
C67—C68—C69—O61 | 178.2 (2) | O21—C22—C23—C24 | 178.18 (18) |
C67—C68—C69—C70 | −1.7 (4) | C22—C23—C24—C25 | 0.5 (4) |
O61—C69—C70—C65 | −178.57 (18) | C23—C24—C25—C26 | −1.8 (4) |
C68—C69—C70—C65 | 1.3 (3) | C24—C25—C26—C27 | 1.7 (4) |
O61—C69—C70—C64 | 1.2 (3) | C23—C22—C27—C26 | −1.1 (3) |
C68—C69—C70—C64 | −178.8 (2) | O21—C22—C27—C26 | −178.4 (2) |
C66—C65—C70—C69 | 0.2 (3) | C25—C26—C27—C22 | −0.2 (4) |
C66—C65—C70—C64 | −179.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C31—H312···O2 | 0.92 (3) | 2.50 (3) | 3.013 (3) | 116 (2) |
C5—H51···O641 | 0.95 (2) | 2.49 (2) | 2.828 (2) | 101 (2) |
C65—H65···O641 | 0.94 | 2.62 | 2.873 (3) | 96 |
C62—H62···N4 | 0.94 (2) | 2.62 (2) | 2.819 (3) | 92 (1) |
Experimental details
Crystal data | |
Chemical formula | C23H19N2O5P |
Mr | 434.37 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.312 (2), 10.611 (1), 23.595 (2) |
β (°) | 90.76 (1) |
V (Å3) | 2082.8 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.6 × 0.5 × 0.4 |
Data collection | |
Diffractometer | Rigaku AFC-5S diffractometer |
Absorption correction | Analytical (de Meulenaer & Tompa, 1965) |
Tmin, Tmax | 0.915, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3738, 3648, 2746 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.130, 1.14 |
No. of reflections | 3648 |
No. of parameters | 301 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.24 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1989), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1989), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1998), SHELXL97 and PARST97 (Nardelli, 1996).
P1—O2 | 1.450 (1) | O61—C62 | 1.345 (2) |
P1—O21 | 1.579 (1) | O61—C69 | 1.375 (2) |
P1—O11 | 1.588 (1) | C62—C63 | 1.340 (3) |
P1—N3 | 1.641 (2) | C63—C64 | 1.459 (2) |
N3—N4 | 1.384 (2) | C64—O641 | 1.222 (2) |
N3—C31 | 1.455 (3) | C64—C70 | 1.465 (3) |
N4—C5 | 1.269 (2) | C69—C70 | 1.376 (3) |
C5—C63 | 1.460 (3) | ||
O2—P1—O21 | 116.86 (8) | C62—O61—C69 | 117.9 (2) |
O2—P1—O11 | 115.59 (8) | C63—C62—O61 | 125.9 (2) |
O21—P1—O11 | 99.66 (7) | C62—C63—C64 | 119.3 (2) |
O2—P1—N3 | 112.98 (9) | C62—C63—C5 | 122.0 (2) |
O21—P1—N3 | 103.64 (8) | C64—C63—C5 | 118.7 (2) |
O11—P1—N3 | 106.52 (8) | O641—C64—C63 | 122.5 (2) |
N4—N3—C31 | 121.4 (2) | O641—C64—C70 | 122.9 (2) |
N4—N3—P1 | 115.5 (1) | C63—C64—C70 | 114.5 (2) |
C31—N3—P1 | 123.1 (2) | O61—C69—C70 | 121.7 (2) |
C5—N4—N3 | 118.7 (2) | C69—C70—C64 | 120.7 (2) |
N4—C5—C63 | 120.7 (2) | ||
O2—P1—N3—N4 | 170.7 (1) | N3—N4—C5—C63 | 177.5 (2) |
O2—P1—N3—C31 | −11.4 (2) | N4—C5—C63—C62 | 0.0 (3) |
C31—N3—N4—C5 | −1.4 (3) | N4—C5—C63—C64 | −179.4 (2) |
P1—N3—N4—C5 | 176.5 (1) | C5—C63—C64—O641 | −4.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C31—H312···O2 | 0.92 (3) | 2.50 (3) | 3.013 (3) | 116 (2) |
C5—H51···O641 | 0.95 (2) | 2.49 (2) | 2.828 (2) | 101 (2) |
C65—H65···O641 | 0.94 | 2.62 | 2.873 (3) | 96 |
C62—H62···N4 | 0.94 (2) | 2.62 (2) | 2.819 (3) | 92 (1) |
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This paper is a part of our X-ray studies of a group of benzopyran derivatives substituted with phosphorohydrazide at position 3 (Rybarczyk et al., 1999; Rybarczyk-Pirek et al., 2002). These compounds, which are derivatives of biologically active chromones, are of interest because of their expected anticancer activity, by analogy with other chromones (Gabor, 1988; Valenti et al., 1996). The present X-ray investigation of the title benzopyran derivative, (I), was undertaken to obtain structural information regarding the details of the molecular conformation. We were also interested in the weak interactions in the crystal structure. \sch
The planarity of the pyranoid ring in (I) reveals its aromatic character; the maximum deviation from the least-squares plane (Nardelli, 1996) is 0.016 (2) Å for atom C69. On the other hand, the presence of heteroatom O61 in this cyclic system, as well as the oxo substituent at position 4, significantly modifies the geometric parameters within the ring. The C—C bond distances vary from 1.340 (3) to 1.465 (3) Å, in comparison with the typical aromatic bond length of 1.384 (13) Å (Allen et al., 1987). Moreover, the values of the bond angles within the heterocyclic ring vary from 114.5 (2) to 125.9 (2)° (Table 1).
Fused benzene and pyranoid rings form the benzopyran system, which can be described as planar, with a dihedral angle between the best planes of the rings of 1.21 (6)°.
The hydrazone group (atoms C5, N4 and N3) lies in almost the same plane as the benzopyran moiety. The dihedral angle between the hydrazone and benzopyran least-squares planes is 5.0 (1)°. This coplanar arrangement of the main part of the molecule provides π-conjugation along the C63—C5—N4—N3 bonds and induces planar geometry around atom N3. In addition, the P1—N3 bond length is much closer to the standard P—Nplanar distance of 1.65 (2) Å than to the P—Npyramidal distance of 1.683 (5) Å (Allen et al., 1987).
The Cmethyl and P atoms do not deviate much from the hydrazone best plane [0.030 (3) Å for atom C31 and 0.090 (1) Å for atom P1], and they are positioned on opposite sides of the plane. The normal to the hydrazone plane forms an angle of 81.4 (1)° with the P1—O2 bond. As a result, the central P1/N3(C31)/N4/C5/C63 chain of atoms can be regarded as planar.
The geometric parameters around the four-coordinate P atom indicate a slight deformation of the ideal tetrahedron towards a trigonal pyramid, caused by the different substituents and bond types. In particular, the P1═O2 double bond is the shortest and this has an influence on the bond angles in the P environment, which are significantly different from the ideal value of 109.5°.
Even though the majority of the atoms of the molecule lie in nearly the same plane, the tetrahedral geometry of the central phosphonate system results in the overall non-planar molecular conformation. The two phenoxy groups attached to atom P1 are inclined towards the benzopyran-hydrazone moiety; he angles between these rings and the main plane are 21.29 (6)° for the C12—C17 ring and 89.33 (5)° for the C22—C27 ring.
The coplanar arrangement of the main part of the molecule of (I) is additionally stabilized by the availability of acceptors in weak intramolecular contacts, of the non-conventional hydrogen-bonding type, with C—H donors. Some H···O and H···N distances shorter than the sum of the van der Waals radii are observed. The geometry of these weak hydrogen bonds is given in Table 2.