Ethyl 3-[1-(5,5-dimethyl-2-oxo-1,3,2-dioxaphospho­rin-2-yl)propan-2-yl­idene]carbazate: a combined X-ray and density functional theory (DFT) study

In the title compound, C₁₁H₂₁N₂O₅P, one of the two carbazate N atoms is involved in the C=N double bond and the H atom of the second N atom is engaged in an intra­molecular hydrogen bond with an O atom from the dimethyl­phospho­rin-2-yl group, which is in an uncommon cis position with respect to the carbamate group. The cohesion of the crystal structure is also reinforced by weak inter­molecular hydrogen bonds. Density functional theory (DFT) calculations at the B3LYP/6-311++g(2d,2p) level revealed the lowest energy structure to have a Z configuration at the C=N bond, which is consistent with the configuration found in the X-ray crystal structure, as well as a less stable E counterpart which lies 2.0 kcal mol^-1 higher in potential energy. Correlations between the experimental and computational studies are discussed.

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1995); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1995); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: WinGX (Farrugia, 1999).

ethyl 3-[1-(5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorin-2-yl)propan-2-ylidene]carbazate

Crystal data

C11H21N2O5P	F(000) = 312
Mr = 292.27	Dx = 1.314 Mg m^−3
Monoclinic, P21	Melting point: 458 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 7.235 (2) Å	Cell parameters from 25 reflections
b = 10.823 (4) Å	θ = 10.9–14.7°
c = 9.545 (3) Å	µ = 0.20 mm^−1
β = 98.78 (2)°	T = 293 K
V = 738.7 (4) Å^3	Parallelipiped, colourless
Z = 2	0.30 × 0.20 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	1601 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 27.0°, θmin = 2.2°
ω/2θ scans	h = −9→2
Absorption correction: ψ scan (North et al., 1968)	k = −1→13
Tmin = 0.879, Tmax = 0.940	l = −12→12
2510 measured reflections	2 standard reflections every 120 min
1697 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0472P)^2 + 0.0725P] where P = (Fo^2 + 2Fc^2)/3
1697 reflections	(Δ/σ)max = 0.004
176 parameters	Δρmax = 0.24 e Å^−3
1 restraint	Δρmin = −0.12 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 (Ų)

	x	y	z	Uiso*/Ueq
P1	0.04992 (7)	0.66630 (5)	0.30691 (5)	0.03698 (14)
O1	0.2095 (2)	0.58971 (19)	0.37039 (17)	0.0512 (4)
O2	−0.1425 (2)	0.60535 (15)	0.32494 (18)	0.0463 (4)
O3	0.0527 (2)	0.79856 (15)	0.37721 (18)	0.0450 (4)
O4	0.5594 (2)	0.40053 (18)	0.20640 (19)	0.0526 (4)
O5	0.4282 (3)	0.3386 (2)	−0.0138 (2)	0.0663 (6)
N1	0.1249 (3)	0.4844 (2)	0.0193 (2)	0.0450 (4)
N2	0.2948 (3)	0.48799 (19)	0.1106 (2)	0.0435 (4)
H2	0.3022	0.5199	0.1941	0.052*
C1	0.0543 (3)	0.6900 (2)	0.1198 (2)	0.0419 (5)
H11	−0.0368	0.7531	0.0857	0.050*
H12	0.1766	0.7212	0.1080	0.050*
C2	0.0134 (3)	0.5756 (2)	0.0279 (2)	0.0425 (5)
C3	−0.1740 (4)	0.5703 (4)	−0.0685 (3)	0.0642 (8)
H31	−0.1777	0.4990	−0.1287	0.096*
H32	−0.1901	0.6436	−0.1258	0.096*
H33	−0.2727	0.5650	−0.0120	0.096*
C4	−0.3132 (3)	0.6803 (2)	0.3199 (2)	0.0443 (5)
H41	−0.4110	0.6304	0.3506	0.053*
H42	−0.3556	0.7060	0.2230	0.053*
C5	−0.1215 (3)	0.8707 (2)	0.3669 (3)	0.0425 (5)
H51	−0.1590	0.8972	0.2697	0.051*
H52	−0.0997	0.9439	0.4257	0.051*
C6	−0.2789 (3)	0.7943 (2)	0.4145 (2)	0.0407 (5)
C7	−0.2287 (4)	0.7563 (3)	0.5707 (3)	0.0553 (6)
H71	−0.1170	0.7071	0.5826	0.083*
H72	−0.3295	0.7091	0.5985	0.083*
H73	−0.2082	0.8290	0.6287	0.083*
C8	−0.4577 (3)	0.8739 (3)	0.3927 (3)	0.0593 (7)
H81	−0.4883	0.8957	0.2944	0.089*
H82	−0.4372	0.9476	0.4488	0.089*
H83	−0.5591	0.8278	0.4213	0.089*
C9	0.4263 (3)	0.4013 (2)	0.0900 (3)	0.0435 (5)
C10	0.7240 (4)	0.3234 (3)	0.2004 (4)	0.0601 (7)
H101	0.8297	0.3575	0.2632	0.072*
H102	0.7540	0.3248	0.1048	0.072*
C11	0.6942 (4)	0.1934 (3)	0.2420 (4)	0.0666 (8)
H111	0.5931	0.1581	0.1777	0.100*
H112	0.6642	0.1915	0.3366	0.100*
H113	0.8062	0.1465	0.2387	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0396 (3)	0.0336 (2)	0.0381 (2)	0.0033 (2)	0.00702 (18)	0.0009 (2)
O1	0.0562 (9)	0.0549 (11)	0.0418 (8)	0.0180 (9)	0.0048 (7)	0.0047 (8)
O2	0.0500 (9)	0.0334 (8)	0.0581 (9)	−0.0038 (7)	0.0167 (7)	−0.0024 (7)
O3	0.0373 (8)	0.0398 (9)	0.0581 (10)	−0.0031 (7)	0.0078 (7)	−0.0106 (8)
O4	0.0444 (9)	0.0505 (10)	0.0607 (10)	0.0121 (8)	0.0005 (8)	−0.0136 (8)
O5	0.0813 (14)	0.0668 (13)	0.0508 (10)	0.0173 (12)	0.0104 (10)	−0.0181 (10)
N1	0.0485 (10)	0.0453 (11)	0.0391 (9)	−0.0004 (9)	0.0005 (8)	−0.0030 (8)
N2	0.0430 (10)	0.0424 (10)	0.0433 (9)	0.0050 (8)	0.0013 (7)	−0.0089 (8)
C1	0.0489 (11)	0.0360 (12)	0.0411 (10)	0.0065 (9)	0.0075 (9)	0.0086 (9)
C2	0.0455 (11)	0.0460 (12)	0.0356 (10)	0.0008 (10)	0.0042 (9)	0.0058 (10)
C3	0.0575 (15)	0.077 (2)	0.0529 (14)	0.0089 (15)	−0.0096 (12)	0.0019 (15)
C4	0.0416 (10)	0.0441 (13)	0.0473 (11)	−0.0037 (11)	0.0068 (8)	−0.0015 (11)
C5	0.0423 (11)	0.0329 (10)	0.0532 (12)	0.0011 (9)	0.0102 (9)	−0.0050 (10)
C6	0.0368 (10)	0.0420 (11)	0.0433 (11)	0.0016 (9)	0.0058 (8)	−0.0025 (10)
C7	0.0557 (14)	0.0698 (18)	0.0411 (12)	0.0024 (14)	0.0096 (10)	−0.0017 (13)
C8	0.0411 (12)	0.0623 (17)	0.0737 (17)	0.0114 (12)	0.0066 (11)	−0.0088 (14)
C9	0.0501 (12)	0.0351 (10)	0.0466 (12)	−0.0003 (9)	0.0114 (9)	−0.0047 (9)
C10	0.0430 (12)	0.0492 (14)	0.089 (2)	0.0095 (12)	0.0132 (13)	−0.0062 (14)
C11	0.0610 (16)	0.0549 (18)	0.084 (2)	0.0131 (13)	0.0102 (14)	0.0054 (15)

Geometric parameters (Å, º)

P1—O1	1.4745 (18)	C4—C6	1.528 (3)
P1—O2	1.5736 (17)	C4—H41	0.9700
P1—O3	1.5797 (18)	C4—H42	0.9700
P1—C1	1.810 (2)	C5—C6	1.531 (3)
O2—C4	1.472 (3)	C5—H51	0.9700
O3—C5	1.473 (3)	C5—H52	0.9700
O4—C9	1.354 (3)	C6—C7	1.536 (3)
O4—C10	1.463 (3)	C6—C8	1.541 (3)
O5—C9	1.203 (3)	C7—H71	0.9600
N1—C2	1.286 (3)	C7—H72	0.9600
N1—N2	1.394 (3)	C7—H73	0.9600
N2—C9	1.372 (3)	C8—H81	0.9600
N2—H2	0.8621	C8—H82	0.9600
C1—C2	1.520 (3)	C8—H83	0.9600
C1—H11	0.9700	C10—C11	1.487 (4)
C1—H12	0.9700	C10—H101	0.9700
C2—C3	1.519 (3)	C10—H102	0.9700
C3—H31	0.9600	C11—H111	0.9600
C3—H32	0.9600	C11—H112	0.9600
C3—H33	0.9600	C11—H113	0.9600
O1—P1—O2	111.71 (10)	O3—C5—H52	109.4
O1—P1—O3	112.11 (10)	C6—C5—H52	109.4
O2—P1—O3	106.71 (9)	H51—C5—H52	108.0
O1—P1—C1	110.78 (10)	C4—C6—C5	108.76 (18)
O2—P1—C1	108.43 (10)	C4—C6—C7	110.5 (2)
O3—P1—C1	106.86 (10)	C5—C6—C7	110.9 (2)
C4—O2—P1	121.16 (14)	C4—C6—C8	108.29 (19)
C5—O3—P1	119.76 (13)	C5—C6—C8	107.8 (2)
C9—O4—C10	116.9 (2)	C7—C6—C8	110.5 (2)
C2—N1—N2	116.1 (2)	C6—C7—H71	109.5
C9—N2—N1	117.09 (19)	C6—C7—H72	109.5
C9—N2—H2	117.4	H71—C7—H72	109.5
N1—N2—H2	120.9	C6—C7—H73	109.5
C2—C1—P1	115.04 (15)	H71—C7—H73	109.5
C2—C1—H11	108.5	H72—C7—H73	109.5
P1—C1—H11	108.5	C6—C8—H81	109.5
C2—C1—H12	108.5	C6—C8—H82	109.5
P1—C1—H12	108.5	H81—C8—H82	109.5
H11—C1—H12	107.5	C6—C8—H83	109.5
N1—C2—C3	116.4 (2)	H81—C8—H83	109.5
N1—C2—C1	126.4 (2)	H82—C8—H83	109.5
C3—C2—C1	117.2 (2)	O5—C9—O4	125.2 (2)
C2—C3—H31	109.5	O5—C9—N2	126.8 (2)
C2—C3—H32	109.5	O4—C9—N2	107.97 (19)
H31—C3—H32	109.5	O4—C10—C11	112.2 (2)
C2—C3—H33	109.5	O4—C10—H101	109.2
H31—C3—H33	109.5	C11—C10—H101	109.2
H32—C3—H33	109.5	O4—C10—H102	109.2
O2—C4—C6	111.48 (17)	C11—C10—H102	109.2
O2—C4—H41	109.3	H101—C10—H102	107.9
C6—C4—H41	109.3	C10—C11—H111	109.5
O2—C4—H42	109.3	C10—C11—H112	109.5
C6—C4—H42	109.3	H111—C11—H112	109.5
H41—C4—H42	108.0	C10—C11—H113	109.5
O3—C5—C6	111.23 (19)	H111—C11—H113	109.5
O3—C5—H51	109.4	H112—C11—H113	109.5
C6—C5—H51	109.4
O1—P1—O2—C4	157.07 (16)	P1—O2—C4—C6	−48.3 (2)
O3—P1—O2—C4	34.21 (18)	P1—O3—C5—C6	51.4 (2)
C1—P1—O2—C4	−80.58 (18)	O2—C4—C6—C5	57.8 (2)
O1—P1—O3—C5	−158.23 (16)	O2—C4—C6—C7	−64.1 (2)
O2—P1—O3—C5	−35.62 (18)	O2—C4—C6—C8	174.71 (19)
C1—P1—O3—C5	80.22 (18)	O3—C5—C6—C4	−59.7 (2)
C2—N1—N2—C9	−171.1 (2)	O3—C5—C6—C7	62.0 (3)
O1—P1—C1—C2	69.29 (19)	O3—C5—C6—C8	−176.93 (19)
O2—P1—C1—C2	−53.63 (18)	C10—O4—C9—O5	4.4 (4)
O3—P1—C1—C2	−168.32 (16)	C10—O4—C9—N2	−173.8 (2)
N2—N1—C2—C3	−178.4 (2)	N1—N2—C9—O5	16.2 (4)
N2—N1—C2—C1	4.5 (3)	N1—N2—C9—O4	−165.6 (2)
P1—C1—C2—N1	−74.8 (3)	C9—O4—C10—C11	−85.8 (3)
P1—C1—C2—C3	108.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.05	2.865 (3)	158
C4—H42···O5^i	0.97	2.45	3.380 (3)	161

Symmetry code: (i) −x, y+1/2, −z.