5-Ethyl-6-oxo-4-thio­xo-1,3,2-ox­aza­phospho­lidino­[3,2-a][1,3,2]­benzodi­aza­phospho­rine

Deng, S.-L.; Chen, R.-Y.; Leng, X.-B.; Weng, L.-H.

doi:10.1107/S1600536803002290

5-Ethyl-6-oxo-4-thioxo-1,3,2-oxazaphospholidino[3,2-a][1,3,2]benzodiazaphosphorine

S.-L. Deng, R.-Y. Chen, X.-B. Leng and L.-H. Weng

The title fused tricyclic phosphoroheterocycle, C₁₁H₁₃N₂O₂PS, was unexpectedly synthesized by the reaction of a multifunctional compound, 2-[N-(2'-hydroxy)ethyl]amino-N'-ethylbenzamide, with tris(diethylamino)phosphine in the presence of iodine as catalyst. The crystallographic data analysis reveals that the title compound is triclinic with space group P $\overline 1$ and there are three rings in the molecule. The phenyl ring, the two N atoms and the carbonyl C atom are coplanar; the P atom and the carbonyl C atom deviate by -0.692 (2) and 0.1116 (13) Å, respectively, from the phenyl ring plane. The five-membered ring exists in an boat conformation.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803002290/ww6058sup1.cif Contains datablocks 2, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803002290/ww60582sup2.hkl Contains datablock 2

CCDC reference: 206763

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Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.004 Å
R factor = 0.041
wR factor = 0.118
Data-to-parameter ratio = 14.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



ABSTM_02  Alert B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
          Tmin and Tmax reported:      0.564     0.927
          Tmin' and Tmax expected:      0.891     0.927
          RR' =      0.633
          Please check that your absorption correction is appropriate.


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 0 Alert Level C = Please check

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS7 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

5-Ethyl-6-oxo-4-thioxo-1,3,2- oxazaphospholidino[3,2-a][1,3,2]benzodiazaphosphorine top

Crystal data top

C₁₁H₁₃N₂O₂PS	F(000) = 280
M_r = 268.26	D_x = 1.422 Mg m⁻³
Triclinic, P1	Melting point: 384 K
a = 6.9347 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9827 (10) Å	Cell parameters from 231 reflections
c = 10.4868 (11) Å	θ = 2.8–22.8°
α = 61.633 (2)°	µ = 0.38 mm⁻¹
β = 78.828 (2)°	T = 298 K
γ = 83.139 (2)°	Prism, colourless
V = 626.38 (11) Å³	0.30 × 0.25 × 0.20 mm
Z = 2

Data collection top

Bruker CCD area-detector diffractometer	2208 independent reflections
Radiation source: fine-focus sealed tube	1940 reflections with I > 2σ(1)
Graphite monochromator	R_int = 0.017
φ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→6
T_min = 0.564, T_max = 0.927	k = −11→11
2621 measured reflections	l = −12→12

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0718P)² + 0.2182P] where P = (F_o² + 2F_c²)/3
2208 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.29 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 4.5884 (0.0034) x + 5.1438 (0.0051) y + 5.6283 (0.0060) z = 8.9976 (0.0088)

* -0.0191 (0.0018) C1 * 0.0564 (0.0019) C2 * 0.0639 (0.0020) C3 * -0.0306 (0.0020) C4 * -0.0743 (0.0018) C5 * -0.0412 (0.0017) C6 * -0.0667 (0.0014) N1 * 0.1116 (0.0013) C7 - 0.0946 (0.0025) N2 - 0.6918 (0.0020) P1

Rms deviation of fitted atoms = 0.0639

- 0.2223 (0.0082) x + 6.0673 (0.0080) y + 10.0487 (0.0033) z = 12.9030 (0.0066)

Angle to previous plane (with approximate e.s.d.) = 41.81 (0.09)

* -0.0347 (0.0010) P1 * 0.0380 (0.0011) N1 * -0.0268 (0.0008) C8 * 0.0235 (0.0007) O1 0.4468 (0.0035) C9

Rms deviation of fitted atoms = 0.0313

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.

Most of the non-H atoms were located from an E map, the others were determined with successive differential Fourier syntheses. Then, the structure was refined by full-matrix least-squares method with anisotropic thermal parameters for all the non-hydrogen atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P1	0.06801 (8)	0.80308 (6)	0.79721 (6)	0.0400 (2)
S1	0.26105 (11)	0.69681 (8)	0.71926 (8)	0.0618 (2)
N1	0.0079 (2)	0.98408 (19)	0.6938 (2)	0.0389 (4)
N2	0.1231 (3)	0.80694 (19)	0.94467 (19)	0.0370 (4)
O1	−0.1457 (3)	0.73971 (18)	0.8365 (2)	0.0553 (5)
O2	0.2619 (2)	0.92484 (17)	1.04101 (17)	0.0478 (4)
C1	0.1140 (3)	1.1021 (2)	0.6810 (2)	0.0366 (5)
C2	0.1124 (4)	1.2465 (3)	0.5611 (3)	0.0487 (6)
H2A	0.0372	1.2669	0.4891	0.058*
C3	0.2226 (4)	1.3591 (3)	0.5493 (3)	0.0561 (6)
H3A	0.2189	1.4560	0.4701	0.067*
C4	0.3392 (4)	1.3299 (3)	0.6543 (3)	0.0530 (6)
H4A	0.4175	1.4052	0.6433	0.064*
C5	0.3374 (3)	1.1884 (3)	0.7744 (3)	0.0430 (5)
H5A	0.4141	1.1690	0.8453	0.052*
C6	0.2228 (3)	1.0737 (2)	0.7917 (2)	0.0347 (4)
C7	0.2058 (3)	0.9315 (2)	0.9349 (2)	0.0347 (4)
C8	−0.1996 (3)	1.0010 (3)	0.6726 (3)	0.0468 (6)
H8A	−0.2102	1.0033	0.5807	0.056*
H8B	−0.2600	1.0937	0.6728	0.056*
C9	−0.2951 (3)	0.8625 (3)	0.8012 (3)	0.0539 (6)
H9A	−0.3404	0.8821	0.8845	0.065*
H9B	−0.4068	0.8356	0.7759	0.065*
C10	0.1155 (3)	0.6633 (2)	1.0859 (3)	0.0458 (5)
H10A	0.0252	0.5955	1.0870	0.055*
H10B	0.0641	0.6869	1.1661	0.055*
C11	0.3120 (4)	0.5822 (3)	1.1112 (3)	0.0571 (6)
H11A	0.2974	0.4910	1.2034	0.086*
H11B	0.4015	0.6475	1.1128	0.086*
H11C	0.3626	0.5561	1.0336	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0423 (3)	0.0377 (3)	0.05 (6)	0.0003 (2)	−0.0154 (2)	−0.0236 (3)
S1	0.0722 (5)	0.0643 (4)	0.0704 (5)	0.0241 (3)	−0.0284 (4)	−0.0482 (4)
N1	0.0352 (9)	0.0402 (10)	0.0464 (10)	0.0015 (7)	−0.0149 (7)	−0.0217 (8)
N2	0.0393 (9)	0.0336 (9)	0.0401 (9)	−0.0027 (7)	−0.0090 (7)	−0.0173 (8)
O1	0.0529 (10)	0.0480 (9)	0.0706 (12)	−0.0096 (8)	−0.0199 (8)	−0.0266 (9)
O2	0.0617 (10)	0.0467 (9)	0.0433 (9)	−0.0040 (7)	−0.0186 (7)	−0.0232 (7)
C1	0.0341 (10)	0.0385 (11)	0.0391 (11)	0.0002 (8)	−0.0050 (8)	−0.0201 (9)
C2	0.0542 (14)	0.0473 (13)	0.0404 (12)	−0.0027 (11)	−0.0120 (10)	−0.0150 (10)
C3	0.0648 (16)	0.0425 (13)	0.0475 (13)	−0.0075 (12)	−0.0064 (11)	−0.0098 (11)
C4	0.0525 (14)	0.0456 (13)	0.0576 (15)	−0.0166 (11)	−0.0006 (11)	−0.0208 (11)
C5	0.0385 (11)	0.0441 (12)	0.0487 (13)	−0.0067 (9)	−0.0055 (9)	−0.0228 (10)
C6	0.0308 (10)	0.0369 (11)	0.0378 (11)	0.0000 (8)	−0.0039 (8)	−0.0193 (9)
C7	0.0292 (10)	0.0373 (10)	0.0401 (11)	0.0002 (8)	−0.0059 (8)	−0.0201 (9)
C8	0.0357 (11)	0.0575 (14)	0.0539 (13)	0.0035 (10)	−0.0168 (10)	−0.0287 (12)
C9	0.0410 (13)	0.0673 (16)	0.0661 (16)	−0.0062 (11)	−0.0113 (11)	−0.0391 (14)
C10	0.0522 (13)	0.0377 (11)	0.0439 (12)	−0.0063 (10)	−0.0063 (10)	−0.0154 (10)
C11	0.0637 (16)	0.0437 (13)	0.0572 (15)	0.0071 (11)	−0.0180 (12)	−0.0170 (11)

Geometric parameters (Å, º) top

P1—O1	1.5827 (17)	C4—C5	1.374 (3)
P1—N1	1.6577 (18)	C4—H4A	0.9300
P1—N2	1.6815 (18)	C5—C6	1.393 (3)
P1—S1	1.9095 (9)	C5—H5A	0.9300
N1—C1	1.402 (3)	C6—C7	1.493 (3)
N1—C8	1.476 (3)	C8—C9	1.506 (4)
N2—C7	1.383 (3)	C8—H8A	0.9700
N2—C10	1.491 (3)	C8—H8B	0.9700
O1—C9	1.459 (3)	C9—H9A	0.9700
O2—C7	1.218 (3)	C9—H9B	0.9700
C1—C2	1.393 (3)	C10—C11	1.502 (3)
C1—C6	1.404 (3)	C10—H10A	0.9700
C2—C3	1.378 (4)	C10—H10B	0.9700
C2—H2A	0.9300	C11—H11A	0.9600
C3—C4	1.390 (4)	C11—H11B	0.9600
C3—H3A	0.9300	C11—H11C	0.9600

O1—P1—N1	96.62 (9)	C5—C6—C7	117.71 (18)
O1—P1—N2	108.83 (10)	C1—C6—C7	122.95 (18)
N1—P1—N2	102.08 (9)	O2—C7—N2	120.52 (19)
O1—P1—S1	113.05 (7)	O2—C7—C6	121.29 (18)
N1—P1—S1	120.73 (8)	N2—C7—C6	118.18 (18)
N2—P1—S1	113.68 (7)	N1—C8—C9	104.33 (18)
C1—N1—C8	123.70 (17)	N1—C8—H8A	110.9
C1—N1—P1	121.12 (14)	C9—C8—H8A	110.9
C8—N1—P1	110.81 (14)	N1—C8—H8B	110.9
C7—N2—C10	117.76 (17)	C9—C8—H8B	110.9
C7—N2—P1	122.34 (14)	H8A—C8—H8B	108.9
C10—N2—P1	119.04 (14)	O1—C9—C8	106.62 (19)
C9—O1—P1	111.43 (14)	O1—C9—H9A	110.4
C2—C1—N1	121.13 (19)	C8—C9—H9A	110.4
C2—C1—C6	119.7 (2)	O1—C9—H9B	110.4
N1—C1—C6	119.21 (18)	C8—C9—H9B	110.4
C3—C2—C1	119.9 (2)	H9A—C9—H9B	108.6
C3—C2—H2A	120.1	N2—C10—C11	113.49 (19)
C1—C2—H2A	120.1	N2—C10—H10A	108.9
C2—C3—C4	120.9 (2)	C11—C10—H10A	108.9
C2—C3—H3A	119.6	N2—C10—H10B	108.9
C4—C3—H3A	119.6	C11—C10—H10B	108.9
C5—C4—C3	119.3 (2)	H10A—C10—H10B	107.7
C5—C4—H4A	120.4	C10—C11—H11A	109.5
C3—C4—H4A	120.4	C10—C11—H11B	109.5
C4—C5—C6	121.1 (2)	H11A—C11—H11B	109.5
C4—C5—H5A	119.4	C10—C11—H11C	109.5
C6—C5—H5A	119.4	H11A—C11—H11C	109.5
C5—C6—C1	119.04 (19)	H11B—C11—H11C	109.5

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5-Ethyl-6-oxo-4-thio­xo-1,3,2-ox­aza­phospho­lidino­[3,2-a][1,3,2]­benzodi­aza­phospho­rine

Supporting information

Key indicators

checkCIF results

5-Ethyl-6-oxo-4-thioxo-1,3,2-oxazaphospholidino[3,2-a][1,3,2]benzodiazaphosphorine