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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110020688/dn3143sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110020688/dn3143Isup2.hkl
Contains datablock I

CCDC reference: 786814

Computing details top

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 top
Crystal data top
C11H21N2O5PF(000) = 312
Mr = 292.27Dx = 1.314 Mg m3
Monoclinic, P21Melting point: 458 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 7.235 (2) ÅCell parameters from 25 reflections
b = 10.823 (4) Åθ = 10.9–14.7°
c = 9.545 (3) ŵ = 0.20 mm1
β = 98.78 (2)°T = 293 K
V = 738.7 (4) Å3Parallelipiped, colourless
Z = 20.30 × 0.20 × 0.18 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
1601 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
Graphite monochromatorθmax = 27.0°, θmin = 2.2°
ω/2θ scansh = 92
Absorption correction: ψ scan
(North et al., 1968)
k = 113
Tmin = 0.879, Tmax = 0.940l = 1212
2510 measured reflections2 standard reflections every 120 min
1697 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0472P)2 + 0.0725P]
where P = (Fo2 + 2Fc2)/3
1697 reflections(Δ/σ)max = 0.004
176 parametersΔρmax = 0.24 e Å3
1 restraintΔρmin = 0.12 e Å3
Special details top

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 (Å2) top
xyzUiso*/Ueq
P10.04992 (7)0.66630 (5)0.30691 (5)0.03698 (14)
O10.2095 (2)0.58971 (19)0.37039 (17)0.0512 (4)
O20.1425 (2)0.60535 (15)0.32494 (18)0.0463 (4)
O30.0527 (2)0.79856 (15)0.37721 (18)0.0450 (4)
O40.5594 (2)0.40053 (18)0.20640 (19)0.0526 (4)
O50.4282 (3)0.3386 (2)0.0138 (2)0.0663 (6)
N10.1249 (3)0.4844 (2)0.0193 (2)0.0450 (4)
N20.2948 (3)0.48799 (19)0.1106 (2)0.0435 (4)
H20.30220.51990.19410.052*
C10.0543 (3)0.6900 (2)0.1198 (2)0.0419 (5)
H110.03680.75310.08570.050*
H120.17660.72120.10800.050*
C20.0134 (3)0.5756 (2)0.0279 (2)0.0425 (5)
C30.1740 (4)0.5703 (4)0.0685 (3)0.0642 (8)
H310.17770.49900.12870.096*
H320.19010.64360.12580.096*
H330.27270.56500.01200.096*
C40.3132 (3)0.6803 (2)0.3199 (2)0.0443 (5)
H410.41100.63040.35060.053*
H420.35560.70600.22300.053*
C50.1215 (3)0.8707 (2)0.3669 (3)0.0425 (5)
H510.15900.89720.26970.051*
H520.09970.94390.42570.051*
C60.2789 (3)0.7943 (2)0.4145 (2)0.0407 (5)
C70.2287 (4)0.7563 (3)0.5707 (3)0.0553 (6)
H710.11700.70710.58260.083*
H720.32950.70910.59850.083*
H730.20820.82900.62870.083*
C80.4577 (3)0.8739 (3)0.3927 (3)0.0593 (7)
H810.48830.89570.29440.089*
H820.43720.94760.44880.089*
H830.55910.82780.42130.089*
C90.4263 (3)0.4013 (2)0.0900 (3)0.0435 (5)
C100.7240 (4)0.3234 (3)0.2004 (4)0.0601 (7)
H1010.82970.35750.26320.072*
H1020.75400.32480.10480.072*
C110.6942 (4)0.1934 (3)0.2420 (4)0.0666 (8)
H1110.59310.15810.17770.100*
H1120.66420.19150.33660.100*
H1130.80620.14650.23870.100*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0396 (3)0.0336 (2)0.0381 (2)0.0033 (2)0.00702 (18)0.0009 (2)
O10.0562 (9)0.0549 (11)0.0418 (8)0.0180 (9)0.0048 (7)0.0047 (8)
O20.0500 (9)0.0334 (8)0.0581 (9)0.0038 (7)0.0167 (7)0.0024 (7)
O30.0373 (8)0.0398 (9)0.0581 (10)0.0031 (7)0.0078 (7)0.0106 (8)
O40.0444 (9)0.0505 (10)0.0607 (10)0.0121 (8)0.0005 (8)0.0136 (8)
O50.0813 (14)0.0668 (13)0.0508 (10)0.0173 (12)0.0104 (10)0.0181 (10)
N10.0485 (10)0.0453 (11)0.0391 (9)0.0004 (9)0.0005 (8)0.0030 (8)
N20.0430 (10)0.0424 (10)0.0433 (9)0.0050 (8)0.0013 (7)0.0089 (8)
C10.0489 (11)0.0360 (12)0.0411 (10)0.0065 (9)0.0075 (9)0.0086 (9)
C20.0455 (11)0.0460 (12)0.0356 (10)0.0008 (10)0.0042 (9)0.0058 (10)
C30.0575 (15)0.077 (2)0.0529 (14)0.0089 (15)0.0096 (12)0.0019 (15)
C40.0416 (10)0.0441 (13)0.0473 (11)0.0037 (11)0.0068 (8)0.0015 (11)
C50.0423 (11)0.0329 (10)0.0532 (12)0.0011 (9)0.0102 (9)0.0050 (10)
C60.0368 (10)0.0420 (11)0.0433 (11)0.0016 (9)0.0058 (8)0.0025 (10)
C70.0557 (14)0.0698 (18)0.0411 (12)0.0024 (14)0.0096 (10)0.0017 (13)
C80.0411 (12)0.0623 (17)0.0737 (17)0.0114 (12)0.0066 (11)0.0088 (14)
C90.0501 (12)0.0351 (10)0.0466 (12)0.0003 (9)0.0114 (9)0.0047 (9)
C100.0430 (12)0.0492 (14)0.089 (2)0.0095 (12)0.0132 (13)0.0062 (14)
C110.0610 (16)0.0549 (18)0.084 (2)0.0131 (13)0.0102 (14)0.0054 (15)
Geometric parameters (Å, º) top
P1—O11.4745 (18)C4—C61.528 (3)
P1—O21.5736 (17)C4—H410.9700
P1—O31.5797 (18)C4—H420.9700
P1—C11.810 (2)C5—C61.531 (3)
O2—C41.472 (3)C5—H510.9700
O3—C51.473 (3)C5—H520.9700
O4—C91.354 (3)C6—C71.536 (3)
O4—C101.463 (3)C6—C81.541 (3)
O5—C91.203 (3)C7—H710.9600
N1—C21.286 (3)C7—H720.9600
N1—N21.394 (3)C7—H730.9600
N2—C91.372 (3)C8—H810.9600
N2—H20.8621C8—H820.9600
C1—C21.520 (3)C8—H830.9600
C1—H110.9700C10—C111.487 (4)
C1—H120.9700C10—H1010.9700
C2—C31.519 (3)C10—H1020.9700
C3—H310.9600C11—H1110.9600
C3—H320.9600C11—H1120.9600
C3—H330.9600C11—H1130.9600
O1—P1—O2111.71 (10)O3—C5—H52109.4
O1—P1—O3112.11 (10)C6—C5—H52109.4
O2—P1—O3106.71 (9)H51—C5—H52108.0
O1—P1—C1110.78 (10)C4—C6—C5108.76 (18)
O2—P1—C1108.43 (10)C4—C6—C7110.5 (2)
O3—P1—C1106.86 (10)C5—C6—C7110.9 (2)
C4—O2—P1121.16 (14)C4—C6—C8108.29 (19)
C5—O3—P1119.76 (13)C5—C6—C8107.8 (2)
C9—O4—C10116.9 (2)C7—C6—C8110.5 (2)
C2—N1—N2116.1 (2)C6—C7—H71109.5
C9—N2—N1117.09 (19)C6—C7—H72109.5
C9—N2—H2117.4H71—C7—H72109.5
N1—N2—H2120.9C6—C7—H73109.5
C2—C1—P1115.04 (15)H71—C7—H73109.5
C2—C1—H11108.5H72—C7—H73109.5
P1—C1—H11108.5C6—C8—H81109.5
C2—C1—H12108.5C6—C8—H82109.5
P1—C1—H12108.5H81—C8—H82109.5
H11—C1—H12107.5C6—C8—H83109.5
N1—C2—C3116.4 (2)H81—C8—H83109.5
N1—C2—C1126.4 (2)H82—C8—H83109.5
C3—C2—C1117.2 (2)O5—C9—O4125.2 (2)
C2—C3—H31109.5O5—C9—N2126.8 (2)
C2—C3—H32109.5O4—C9—N2107.97 (19)
H31—C3—H32109.5O4—C10—C11112.2 (2)
C2—C3—H33109.5O4—C10—H101109.2
H31—C3—H33109.5C11—C10—H101109.2
H32—C3—H33109.5O4—C10—H102109.2
O2—C4—C6111.48 (17)C11—C10—H102109.2
O2—C4—H41109.3H101—C10—H102107.9
C6—C4—H41109.3C10—C11—H111109.5
O2—C4—H42109.3C10—C11—H112109.5
C6—C4—H42109.3H111—C11—H112109.5
H41—C4—H42108.0C10—C11—H113109.5
O3—C5—C6111.23 (19)H111—C11—H113109.5
O3—C5—H51109.4H112—C11—H113109.5
C6—C5—H51109.4
O1—P1—O2—C4157.07 (16)P1—O2—C4—C648.3 (2)
O3—P1—O2—C434.21 (18)P1—O3—C5—C651.4 (2)
C1—P1—O2—C480.58 (18)O2—C4—C6—C557.8 (2)
O1—P1—O3—C5158.23 (16)O2—C4—C6—C764.1 (2)
O2—P1—O3—C535.62 (18)O2—C4—C6—C8174.71 (19)
C1—P1—O3—C580.22 (18)O3—C5—C6—C459.7 (2)
C2—N1—N2—C9171.1 (2)O3—C5—C6—C762.0 (3)
O1—P1—C1—C269.29 (19)O3—C5—C6—C8176.93 (19)
O2—P1—C1—C253.63 (18)C10—O4—C9—O54.4 (4)
O3—P1—C1—C2168.32 (16)C10—O4—C9—N2173.8 (2)
N2—N1—C2—C3178.4 (2)N1—N2—C9—O516.2 (4)
N2—N1—C2—C14.5 (3)N1—N2—C9—O4165.6 (2)
P1—C1—C2—N174.8 (3)C9—O4—C10—C1185.8 (3)
P1—C1—C2—C3108.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O10.862.052.865 (3)158
C4—H42···O5i0.972.453.380 (3)161
Symmetry code: (i) x, y+1/2, z.
Selected experimental and optimized bond lengths (Å) top
BondX-ray diffractionDFT-optimized Z conformation
C1-C21.5231.519
C2-N11.2871.277
N1-N21.3921.374
P-C11.8111.803
P-O11.4771.477
P-O31.5831.608
P-O21.5751.609
N2-C91.3751.382
N2-O12.8652.976
H2···O12.052.032
 

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