Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028838/lh2406sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028838/lh2406Isup2.hkl |
CCDC reference: 643520
To a solution of N, N-dimethyl phosphoramidochloridic acid 4-methyl phenyl ester (0.82 g, 3.5 mmol) in 30 ml dry acetonitrile KCN (0.45 g, 7 mmol) was added and stirred 4 h at 330 K. The mixture was cooled at room temperature, and filtered. The solvent was evaporated under vacuum. The solid product was washed with n-hexane and crystallized in hexane/ethyl acetate 9:1 at room temperature. 1H NMR (CDCl3), δ(p.p.m.): 2.34 (s, 3 H, p-CH3), 2.88 (d, 3JPNCH = 11.4 Hz, 6 H, NMe2), 7.10–7.21 (m, 4 H, Ar—H); 13C NMR (CDCl3), δ(p.p.m.): 20.71 (s, 1 C, p-CH3), 35.64 (s, 2 C, N(CH3)2), 114.34 (d, 1JP-C = 186.8 Hz, 2 C, CN), 120.12 (d, 3JP-C = 4.90 Hz, 1 C, Cortho), 130.70 (s, 1 C, Cmeta), 136.32 (s, 1 C, Cpara), 146.32 (d, 2JP-C = 7.4 Hz, 1 C, Cipso); 31P{1H} NMR δ (p.p.m.): -11.824 (s); 31P NMR, δ(p.p.m.): -11.94 to -11.71 (hept., 3JP-H = 11.3 Hz).
All hydrogen atoms were found in difference Fourier maps but were placed in calculated positions [C—H = 0.95–0.98 Å] and refined in the riding-model approximation with Uiso(H)=1.2Ueq(C) or 1.5Ueq(C) for methyl groups.
Organophosphorus compounds (henceforth OPs for convenience) are one of the most widely used classes of pesticides in the world (Fulton & Key, 2001). For some phosphoramido acid, esters inhibiting acetylcholinesterase (AChE) activity was reported, resulting in an accumulation of acetylcholine (ACh) in neural and non-neural tissues (Ghadimi et al., 2007). Tabun (O-ethyl N,N-dimethyl-phosphoramidocyanidate, (CH3)2NP(O)CN(OC2H5)) is one of the well known nerve agent with very high toxicity (Munro et al., 1994). The crystal structure of dimethyl N-phenylphosphoramidate has already been reported (du Plessis et al., 1982). In this work, the synthesis and crystal structure of (CH3)2NP(O)CN(p—OC6H4—CH3) is presented. The molecular structure of the title compound is shown in Fig. 1 Four different groups are linked to atom P1 giving a distorted tetrahedral configuration. The bond angles around P atom are in the range of 101.14 (8)° [O2—P1—C1] to 118.26 (7)° [O1—P1—O2]. The O atom (of the 4-CH3—C6H4—O group) has sp2 character (P1—O2—C2= 119.88 (10)°). The P1—O2 bond length (1.5799 (13) Å) is smaller than a P—O normal single bond length (1.64 Å, Corbridge, 1995). Also, the P—N bond length (1.6104 (15) Å) is shorter than the normal P—N single bond length (1.77 Å, Corbridge, 1995). The N atom in the title molecule indicates a slight deviation from planarity. This fact can be shown by the torsion angle P1—C9—C10—N1, which is ca 9.07°. Furthermore, sum of the surrounding angles around N atom is 358.01° which is less than that for an sp2 hybridized atom. The P1—C1 bond length is longer than the P—N and P—O bond lengths (1.8096 (18) Å) and the cyanide group has nearly linear configuration (N2—C1—P1 = 175.43 (17)°). Each molecule is surrounded with by neighboring molecules via weak C—H···O interactions leading to a 1-D chain in the network. A view of the unit cell packing of title compound is given in Figure 2.
For a review of organophosphorus compounds as used as pesticides, see: Fulton & Key (2001).
For related literature, see: Corbridge (1995); Ghadimi et al. (2007); Munro et al. (1994); du Plessis et al. (1982).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C10H13N2O2P | Z = 1 |
Mr = 224.19 | F(000) = 118 |
Triclinic, P1 | Dx = 1.349 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.0322 (9) Å | Cell parameters from 1809 reflections |
b = 6.8532 (10) Å | θ = 2.9–33.7° |
c = 7.3820 (11) Å | µ = 0.23 mm−1 |
α = 105.604 (3)° | T = 100 K |
β = 95.800 (3)° | Prism, colourless |
γ = 106.802 (3)° | 0.60 × 0.12 × 0.10 mm |
V = 276.03 (7) Å3 |
Bruker APEX II diffractometer | 2688 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 29.0°, θmin = 2.9° |
ω scans | h = −8→8 |
3289 measured reflections | k = −9→9 |
2791 independent reflections | l = −9→10 |
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)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.0486P)2 + ] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
2791 reflections | Δρmax = 0.48 e Å−3 |
139 parameters | Δρmin = −0.41 e Å−3 |
3 restraints | Absolute structure: Flack (1983), 1332 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (7) |
C10H13N2O2P | γ = 106.802 (3)° |
Mr = 224.19 | V = 276.03 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.0322 (9) Å | Mo Kα radiation |
b = 6.8532 (10) Å | µ = 0.23 mm−1 |
c = 7.3820 (11) Å | T = 100 K |
α = 105.604 (3)° | 0.60 × 0.12 × 0.10 mm |
β = 95.800 (3)° |
Bruker APEX II diffractometer | 2688 reflections with I > 2σ(I) |
3289 measured reflections | Rint = 0.020 |
2791 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.084 | Δρmax = 0.48 e Å−3 |
S = 1.04 | Δρmin = −0.41 e Å−3 |
2791 reflections | Absolute structure: Flack (1983), 1332 Friedel pairs |
139 parameters | Absolute structure parameter: −0.03 (7) |
3 restraints |
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 | 0.82244 (6) | 0.58868 (5) | 0.72672 (5) | 0.01572 (11) | |
O1 | 1.0453 (2) | 0.5443 (2) | 0.7274 (2) | 0.0239 (3) | |
O2 | 0.6317 (2) | 0.48682 (18) | 0.53457 (17) | 0.0175 (2) | |
N1 | 0.8366 (2) | 0.8366 (2) | 0.7906 (2) | 0.0186 (3) | |
N2 | 0.5735 (3) | 0.4022 (3) | 0.9964 (2) | 0.0244 (3) | |
C1 | 0.6641 (3) | 0.4674 (3) | 0.8858 (3) | 0.0180 (3) | |
C2 | 0.5178 (3) | 0.2614 (3) | 0.4632 (2) | 0.0157 (3) | |
C3 | 0.6336 (3) | 0.1317 (3) | 0.3651 (2) | 0.0177 (3) | |
H3A | 0.7893 | 0.1921 | 0.3468 | 0.021* | |
C4 | 0.5173 (3) | −0.0891 (3) | 0.2938 (3) | 0.0193 (3) | |
H4A | 0.5943 | −0.1799 | 0.2255 | 0.023* | |
C5 | 0.2882 (3) | −0.1790 (3) | 0.3214 (2) | 0.0175 (3) | |
C6 | 0.1780 (3) | −0.0424 (3) | 0.4193 (3) | 0.0189 (3) | |
H6A | 0.0219 | −0.1013 | 0.4375 | 0.023* | |
C7 | 0.2907 (3) | 0.1783 (3) | 0.4912 (2) | 0.0179 (3) | |
H7A | 0.2136 | 0.2699 | 0.5580 | 0.021* | |
C8 | 0.1680 (4) | −0.4192 (3) | 0.2471 (3) | 0.0246 (4) | |
H8A | 0.0071 | −0.4544 | 0.2726 | 0.037* | |
H8B | 0.2569 | −0.4885 | 0.3119 | 0.037* | |
H8C | 0.1618 | −0.4704 | 0.1087 | 0.037* | |
C9 | 0.6234 (3) | 0.8978 (3) | 0.7893 (3) | 0.0208 (4) | |
H9A | 0.6312 | 0.9986 | 0.7160 | 0.031* | |
H9B | 0.6118 | 0.9661 | 0.9213 | 0.031* | |
H9C | 0.4844 | 0.7695 | 0.7299 | 0.031* | |
C10 | 1.0552 (3) | 1.0079 (3) | 0.9003 (3) | 0.0246 (4) | |
H10A | 1.0802 | 1.1293 | 0.8498 | 0.037* | |
H10B | 1.1886 | 0.9538 | 0.8889 | 0.037* | |
H10C | 1.0430 | 1.0549 | 1.0354 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.01261 (18) | 0.01389 (19) | 0.0204 (2) | 0.00529 (14) | 0.00426 (14) | 0.00354 (15) |
O1 | 0.0163 (6) | 0.0243 (7) | 0.0313 (7) | 0.0107 (5) | 0.0062 (5) | 0.0044 (6) |
O2 | 0.0189 (6) | 0.0122 (5) | 0.0206 (6) | 0.0049 (5) | 0.0032 (5) | 0.0045 (5) |
N1 | 0.0151 (7) | 0.0142 (7) | 0.0258 (8) | 0.0049 (6) | 0.0048 (6) | 0.0050 (6) |
N2 | 0.0245 (8) | 0.0232 (8) | 0.0241 (8) | 0.0062 (6) | 0.0058 (6) | 0.0066 (6) |
C1 | 0.0168 (8) | 0.0139 (8) | 0.0213 (8) | 0.0056 (6) | 0.0010 (6) | 0.0027 (6) |
C2 | 0.0168 (8) | 0.0140 (7) | 0.0159 (7) | 0.0046 (6) | 0.0018 (6) | 0.0052 (6) |
C3 | 0.0152 (8) | 0.0181 (8) | 0.0188 (8) | 0.0047 (6) | 0.0050 (6) | 0.0045 (6) |
C4 | 0.0211 (9) | 0.0180 (8) | 0.0193 (8) | 0.0084 (7) | 0.0054 (7) | 0.0038 (6) |
C5 | 0.0173 (8) | 0.0173 (8) | 0.0168 (8) | 0.0051 (6) | −0.0006 (6) | 0.0056 (6) |
C6 | 0.0130 (8) | 0.0210 (8) | 0.0224 (8) | 0.0049 (6) | 0.0028 (6) | 0.0076 (7) |
C7 | 0.0163 (8) | 0.0193 (8) | 0.0187 (8) | 0.0085 (7) | 0.0024 (6) | 0.0046 (6) |
C8 | 0.0222 (9) | 0.0156 (8) | 0.0311 (10) | 0.0030 (7) | −0.0009 (7) | 0.0050 (7) |
C9 | 0.0209 (9) | 0.0184 (8) | 0.0247 (9) | 0.0111 (7) | 0.0031 (7) | 0.0048 (7) |
C10 | 0.0168 (8) | 0.0197 (9) | 0.0293 (10) | 0.0011 (7) | 0.0036 (7) | 0.0005 (7) |
P1—O1 | 1.4613 (13) | C5—C6 | 1.390 (2) |
P1—O2 | 1.5799 (13) | C5—C8 | 1.510 (2) |
P1—N1 | 1.6104 (15) | C6—C7 | 1.390 (2) |
P1—C1 | 1.8096 (18) | C6—H6A | 0.9500 |
O2—C2 | 1.4181 (19) | C7—H7A | 0.9500 |
N1—C9 | 1.463 (2) | C8—H8A | 0.9800 |
N1—C10 | 1.467 (2) | C8—H8B | 0.9800 |
N2—C1 | 1.145 (2) | C8—H8C | 0.9800 |
C2—C7 | 1.383 (2) | C9—H9A | 0.9800 |
C2—C3 | 1.385 (2) | C9—H9B | 0.9800 |
C3—C4 | 1.394 (2) | C9—H9C | 0.9800 |
C3—H3A | 0.9500 | C10—H10A | 0.9800 |
C4—C5 | 1.401 (2) | C10—H10B | 0.9800 |
C4—H4A | 0.9500 | C10—H10C | 0.9800 |
O1—P1—O2 | 118.26 (7) | C5—C6—H6A | 119.2 |
O1—P1—N1 | 117.32 (7) | C7—C6—H6A | 119.2 |
O2—P1—N1 | 102.87 (7) | C2—C7—C6 | 118.46 (16) |
O1—P1—C1 | 108.72 (8) | C2—C7—H7A | 120.8 |
O2—P1—C1 | 101.14 (8) | C6—C7—H7A | 120.8 |
N1—P1—C1 | 106.88 (8) | C5—C8—H8A | 109.5 |
C2—O2—P1 | 119.88 (10) | C5—C8—H8B | 109.5 |
C9—N1—C10 | 115.30 (14) | H8A—C8—H8B | 109.5 |
C9—N1—P1 | 121.52 (11) | C5—C8—H8C | 109.5 |
C10—N1—P1 | 121.19 (13) | H8A—C8—H8C | 109.5 |
N2—C1—P1 | 175.43 (17) | H8B—C8—H8C | 109.5 |
C7—C2—C3 | 121.95 (15) | N1—C9—H9A | 109.5 |
C7—C2—O2 | 118.45 (15) | N1—C9—H9B | 109.5 |
C3—C2—O2 | 119.60 (15) | H9A—C9—H9B | 109.5 |
C2—C3—C4 | 118.69 (16) | N1—C9—H9C | 109.5 |
C2—C3—H3A | 120.7 | H9A—C9—H9C | 109.5 |
C4—C3—H3A | 120.7 | H9B—C9—H9C | 109.5 |
C3—C4—C5 | 120.86 (16) | N1—C10—H10A | 109.5 |
C3—C4—H4A | 119.6 | N1—C10—H10B | 109.5 |
C5—C4—H4A | 119.6 | H10A—C10—H10B | 109.5 |
C6—C5—C4 | 118.46 (16) | N1—C10—H10C | 109.5 |
C6—C5—C8 | 121.62 (17) | H10A—C10—H10C | 109.5 |
C4—C5—C8 | 119.92 (17) | H10B—C10—H10C | 109.5 |
C5—C6—C7 | 121.58 (16) | ||
O1—P1—O2—C2 | 67.61 (14) | C7—C2—C3—C4 | −0.3 (3) |
N1—P1—O2—C2 | −161.29 (12) | O2—C2—C3—C4 | −179.12 (15) |
C1—P1—O2—C2 | −50.89 (13) | C2—C3—C4—C5 | −0.4 (3) |
O1—P1—N1—C9 | 178.18 (13) | C3—C4—C5—C6 | 0.9 (3) |
O2—P1—N1—C9 | 46.52 (14) | C3—C4—C5—C8 | −178.47 (15) |
C1—P1—N1—C9 | −59.52 (15) | C4—C5—C6—C7 | −0.8 (3) |
O1—P1—N1—C10 | −18.64 (18) | C8—C5—C6—C7 | 178.61 (16) |
O2—P1—N1—C10 | −150.30 (15) | C3—C2—C7—C6 | 0.5 (3) |
C1—P1—N1—C10 | 103.65 (16) | O2—C2—C7—C6 | 179.28 (14) |
P1—O2—C2—C7 | 101.96 (16) | C5—C6—C7—C2 | 0.1 (3) |
P1—O2—C2—C3 | −79.22 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O1i | 0.95 | 2.50 | 3.441 (2) | 174 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C10H13N2O2P |
Mr | 224.19 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 6.0322 (9), 6.8532 (10), 7.3820 (11) |
α, β, γ (°) | 105.604 (3), 95.800 (3), 106.802 (3) |
V (Å3) | 276.03 (7) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.60 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Bruker APEX II |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3289, 2791, 2688 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.084, 1.04 |
No. of reflections | 2791 |
No. of parameters | 139 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.41 |
Absolute structure | Flack (1983), 1332 Friedel pairs |
Absolute structure parameter | −0.03 (7) |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SAINT, SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O1i | 0.95 | 2.50 | 3.441 (2) | 174 |
Symmetry code: (i) x−1, y, z. |
Organophosphorus compounds (henceforth OPs for convenience) are one of the most widely used classes of pesticides in the world (Fulton & Key, 2001). For some phosphoramido acid, esters inhibiting acetylcholinesterase (AChE) activity was reported, resulting in an accumulation of acetylcholine (ACh) in neural and non-neural tissues (Ghadimi et al., 2007). Tabun (O-ethyl N,N-dimethyl-phosphoramidocyanidate, (CH3)2NP(O)CN(OC2H5)) is one of the well known nerve agent with very high toxicity (Munro et al., 1994). The crystal structure of dimethyl N-phenylphosphoramidate has already been reported (du Plessis et al., 1982). In this work, the synthesis and crystal structure of (CH3)2NP(O)CN(p—OC6H4—CH3) is presented. The molecular structure of the title compound is shown in Fig. 1 Four different groups are linked to atom P1 giving a distorted tetrahedral configuration. The bond angles around P atom are in the range of 101.14 (8)° [O2—P1—C1] to 118.26 (7)° [O1—P1—O2]. The O atom (of the 4-CH3—C6H4—O group) has sp2 character (P1—O2—C2= 119.88 (10)°). The P1—O2 bond length (1.5799 (13) Å) is smaller than a P—O normal single bond length (1.64 Å, Corbridge, 1995). Also, the P—N bond length (1.6104 (15) Å) is shorter than the normal P—N single bond length (1.77 Å, Corbridge, 1995). The N atom in the title molecule indicates a slight deviation from planarity. This fact can be shown by the torsion angle P1—C9—C10—N1, which is ca 9.07°. Furthermore, sum of the surrounding angles around N atom is 358.01° which is less than that for an sp2 hybridized atom. The P1—C1 bond length is longer than the P—N and P—O bond lengths (1.8096 (18) Å) and the cyanide group has nearly linear configuration (N2—C1—P1 = 175.43 (17)°). Each molecule is surrounded with by neighboring molecules via weak C—H···O interactions leading to a 1-D chain in the network. A view of the unit cell packing of title compound is given in Figure 2.