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(R)-(1-Ammoniopropyl)phosphonate
aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal
*Correspondence e-mail: filipe.paz@ua.pt
The title compound, C3H10NO3P, crystallizes in its zwitterionic form, H3N+CH(C2H5)PO(O−)(OH), with the being composed by two of such entities (Z′ = 2). The crystal packing leads to a sequence of hydrophobic and hydrophilic layers. While the hydrophobic layer comprises the aliphatic substituent groups, the hydrophilic one is held together by a series of strong and rather directional N+—H⋯O and O—H⋯O hydrogen bonds.
Related literature
For a description of the graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999). For basic stereochemistry terminology, see: Moss (1996
). For the biological activity of the title compound, see: Hudson & Ismail (2001
). For the of a containing the title compound, see: Bashall et al. (2010
). For previous work from our research group on the assembly of coordination polymers using phosphonic-based molecules, see: Cunha-Silva, Ananias et al. (2009
); Cunha-Silva, Lima et al. (2009
); Cunha-Silva et al. (2007
); Rocha et al. (2009
); Shi, Cunha-Silva et al. (2008
); Shi, Trindade et al. (2008
). For a related structure, see: Fernandes et al. (2010
). For a description of the TOPOS software, see: Blatov & Proserpio (2009
).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2006); cell SAINT-Plus (Bruker, 2005
); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008
); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009
); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536810040304/pk2268sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810040304/pk2268Isup2.hkl
The title compound was purchased from Sigma-Aldrich (Aldrich, 98%) and was used as received without purification. Suitable single crystals were grown from an aqueous solution over a period of one month.
1H-NMR (300.13 MHz, D2O) δ: 0.91 (t, 3H, J(1H-1H) = 7.5 Hz, CH3), 1.56–1.63 and 1.75–1.86 (2 m, 2H, CH2) and 2.96–3.05 (m, 1H, CH).
13C-NMR (75.47 MHz, D2O) δ: 13.0 (d, J(13C-31P) = 9.7 Hz, CH3), 24.7 (d, J(13C-31P)= 1.6 Hz, CH2) and 53.5 (d, J(13C-31P)= 143.3 Hz, CH).
31P-NMR (121.49 MHz, D2O) δ: 14.1 (dt, J(31P-1H)= 12.1 and 23.1 Hz).
Hydrogen atoms bound to carbon were included in the final structural model using a riding-motion approximation with C—H = 1.00 Å (tertiary C—H), 0.99 Å (—CH2) or 0.98 Å (terminal —CH3). The isotropic thermal displacement parameters for these atoms were fixed at 1.2 (for the two former families) or 1.5 (for the terminal methyl group) times Ueq of the respective parent atom.
Hydrogen atoms associated with the protonated —NH3+ group or the pendant —OH moiety were directly located in difference Fourier maps and were included in the final structural model with the distances restrained to 0.95 (1) Å and Uiso=1.5×Ueq of the respective parent atom. The H···H distances of the —NH3+ terminal group have been further restrained to 1.55 (1) Å in order to ensure a chemically reasonable geometry.
A total of 1730 estimated Friedel pairs have not been merged and were used as independent data for the structure
The (Flack, 1983) converged to -0.03 (8), ultimately assuring a valid determination from the single-crystal data set.The
of the title compound is known as Ampropylfos and has been the object of several studies for its use as a pesticide (Hudson & Ismail, 2001), and its has been very recently reported (Bashall et al., 2010). Following our interest in the use of phosphonic acid molecules (Fernandes et al., 2010; Cunha-Silva, Ananias et al., 2009; Cunha-Silva, Lima et al., 2009; Rocha et al., 2009; Shi, Cunha-Silva et al., 2008; Shi, Trindade et al., 2008; Cunha-Silva et al., 2007) here we wish to describe the of the title compound (see Scheme).The
is composed by two entities of the title compound in their zwitterionic form, in which the acidic phosphonate moiety donates one proton to the amino group (Figure 1). The geometrical conformations of the two molecules are considerably different: in one unit the two torsion angles O3—P1—C1—C2 and P1—C1—C2—C3 are both +synclinal and in the other the analogous torsion angles (O6—P2—C4—C5 and P2—C4—C5—C6) are -synclinal and antiperiplanar, respectively (see Table 1; Moss, 1996). The two crystallographically unique molecules are organized in the into a supramolecular bilayer (in the ab plane) having the hydrophilic portion in the interior (composed by the amino, methyne and phosphonate moieties) and the hydrophobic in the outer position (formed by the pendant —CH2CH3 groups) (Figures 2 and 3).Inside the hydrophilic section, individual functional groups are disposed in a zigzag fashion along the [010] direction of the
leading to the formation of a supramolecular chain held together by a combination of four N+—H···O hydrogen bridges (green dashed bonds in Figure 2; Table 2) - graph set motif R34(10) (Grell et al., 1999). Supramolecular chains are, in turn, interconnected in the ab plane via the remanant N+—H···O (orange dashed lines in Figure 2) and O—H···O hydrogen bonds (violet dashed lines in Figure 2).Noteworthy, all hydrogen bonding interactions are rather strong with the internuclear D···A distances ranging from 2.583 (2) to 2.914 (2) Å. In addition, the 〈(DHA) angles range from ca 144 to 177°. One acceptor atom (O4) participates in a D13(7) graph set motif with all 〈(DHA) greater than ca 150°. Other acceptors (O1 and O2) are, in turn, involved in D12(5) motifs: N1—H2···O2 with 〈(DHA) of ca 144° and the other three interactions having angles larger than ca 171°. O5 is the only acceptor in a S11 graph set motif: N2—H5···O5 with 〈(DHA) of ca 162° (See Table 2).
The crystal can be better described by employing a topological approach for the description of the aforementioned hydrogen bonding interactions. Taking the geometrical centre of each molecular unit as a node, and being the hydrogen bonding interactions the connections between nodes, the structure can be simplified into a two-dimensional uninodal 7-connected single-penetrated planar (4,4)IIIb network, with total Schläfli symbol 36.412.53 (Blatov & Proserpio, 2009).
For a description of the graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999). For basic stereochemistry terminology, see: Moss (1996). For the biological activity of the title compound, see: Hudson & Ismail (2001). For the
of a containing the title compound, see: Bashall et al. (2010). For previous work from our research group on the assembly of coordination polymers using phosphonic-based molecules, see: Cunha-Silva, Ananias et al. (2009); Cunha-Silva, Lima et al. (2009); Cunha-Silva et al. (2007); Rocha et al. (2009); Shi, Cunha-Silva et al. (2008); Shi, Trindade et al. (2008). For a related structure, see: Fernandes et al. (2010). For a description of the TOPOS software, see: Blatov & Proserpio (2009).Data collection: APEX2 (Bruker, 2006); cell
SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C3H10NO3P | F(000) = 296 |
Mr = 139.09 | Dx = 1.505 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 6291 reflections |
a = 9.3988 (13) Å | θ = 2.3–32.1° |
b = 6.2511 (8) Å | µ = 0.37 mm−1 |
c = 10.8575 (15) Å | T = 150 K |
β = 105.731 (9)° | Plate, colourless |
V = 614.02 (14) Å3 | 0.16 × 0.08 × 0.02 mm |
Z = 4 |
Bruker X8 Kappa CCD APEXII diffractometer | 4196 independent reflections |
Radiation source: fine-focus sealed tube | 3465 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ω and φ scans | θmax = 33.1°, θmin = 3.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | h = −14→14 |
Tmin = 0.943, Tmax = 0.993 | k = −7→9 |
23447 measured reflections | l = −16→16 |
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)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0396P)2 + 0.1217P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
4196 reflections | Δρmax = 0.38 e Å−3 |
171 parameters | Δρmin = −0.55 e Å−3 |
15 restraints | Absolute structure: Flack (1983), 1730 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (8) |
C3H10NO3P | V = 614.02 (14) Å3 |
Mr = 139.09 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.3988 (13) Å | µ = 0.37 mm−1 |
b = 6.2511 (8) Å | T = 150 K |
c = 10.8575 (15) Å | 0.16 × 0.08 × 0.02 mm |
β = 105.731 (9)° |
Bruker X8 Kappa CCD APEXII diffractometer | 4196 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | 3465 reflections with I > 2σ(I) |
Tmin = 0.943, Tmax = 0.993 | Rint = 0.053 |
23447 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.088 | Δρmax = 0.38 e Å−3 |
S = 1.06 | Δρmin = −0.55 e Å−3 |
4196 reflections | Absolute structure: Flack (1983), 1730 Friedel pairs |
171 parameters | Absolute structure parameter: −0.03 (8) |
15 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 | 0.17626 (5) | 0.89317 (8) | 0.65337 (5) | 0.01280 (11) | |
O1 | 0.29018 (16) | 0.7215 (2) | 0.69950 (15) | 0.0197 (3) | |
O2 | 0.10172 (14) | 0.8923 (3) | 0.51232 (13) | 0.0182 (3) | |
O3 | 0.06166 (16) | 0.8928 (3) | 0.73443 (14) | 0.0272 (4) | |
H3D | −0.0346 (16) | 0.837 (4) | 0.707 (3) | 0.041* | |
N1 | 0.1977 (2) | 1.3190 (3) | 0.60484 (18) | 0.0159 (4) | |
H1 | 0.231 (2) | 1.455 (2) | 0.6360 (19) | 0.024* | |
H2 | 0.0945 (11) | 1.307 (4) | 0.595 (2) | 0.024* | |
H3 | 0.217 (2) | 1.294 (4) | 0.5245 (13) | 0.024* | |
C1 | 0.2726 (2) | 1.1499 (4) | 0.69718 (19) | 0.0162 (4) | |
H1A | 0.3742 | 1.1320 | 0.6863 | 0.019* | |
C2 | 0.2910 (3) | 1.2237 (4) | 0.8348 (2) | 0.0218 (5) | |
H2A | 0.3340 | 1.3693 | 0.8453 | 0.026* | |
H2B | 0.1924 | 1.2317 | 0.8509 | 0.026* | |
C3 | 0.3897 (3) | 1.0758 (4) | 0.9338 (2) | 0.0248 (5) | |
H3A | 0.3438 | 0.9341 | 0.9287 | 0.037* | |
H3B | 0.4021 | 1.1351 | 1.0196 | 0.037* | |
H3C | 0.4865 | 1.0631 | 0.9167 | 0.037* | |
P2 | 0.64788 (6) | 0.66572 (8) | 0.65107 (5) | 0.01273 (11) | |
O4 | 0.78570 (16) | 0.7909 (2) | 0.65226 (15) | 0.0177 (3) | |
O5 | 0.54723 (16) | 0.6182 (2) | 0.52207 (13) | 0.0180 (3) | |
O6 | 0.57135 (16) | 0.7875 (2) | 0.74254 (14) | 0.0169 (3) | |
H6A | 0.4679 (11) | 0.771 (5) | 0.725 (2) | 0.025* | |
N2 | 0.71494 (19) | 0.2456 (3) | 0.63228 (17) | 0.0144 (4) | |
H4 | 0.744 (2) | 0.109 (2) | 0.6697 (19) | 0.022* | |
H5 | 0.6217 (12) | 0.230 (3) | 0.5709 (16) | 0.022* | |
H6 | 0.7853 (16) | 0.289 (3) | 0.5885 (18) | 0.022* | |
C4 | 0.6989 (2) | 0.4063 (3) | 0.72982 (18) | 0.0133 (4) | |
H4A | 0.6149 | 0.3588 | 0.7634 | 0.016* | |
C5 | 0.8369 (2) | 0.4151 (4) | 0.8428 (2) | 0.0208 (4) | |
H5A | 0.8269 | 0.5351 | 0.8994 | 0.025* | |
H5B | 0.9237 | 0.4449 | 0.8103 | 0.025* | |
C6 | 0.8649 (3) | 0.2079 (4) | 0.9217 (2) | 0.0298 (6) | |
H6B | 0.7746 | 0.1666 | 0.9443 | 0.045* | |
H6C | 0.9448 | 0.2312 | 0.9999 | 0.045* | |
H6D | 0.8932 | 0.0938 | 0.8711 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0114 (2) | 0.0102 (2) | 0.0176 (2) | −0.0005 (2) | 0.00522 (17) | −0.0016 (2) |
O1 | 0.0169 (7) | 0.0114 (8) | 0.0292 (8) | 0.0003 (6) | 0.0034 (6) | 0.0005 (6) |
O2 | 0.0167 (6) | 0.0171 (7) | 0.0207 (7) | −0.0024 (7) | 0.0049 (5) | −0.0027 (7) |
O3 | 0.0165 (7) | 0.0427 (10) | 0.0238 (8) | −0.0090 (9) | 0.0079 (6) | −0.0080 (9) |
N1 | 0.0193 (9) | 0.0098 (8) | 0.0178 (9) | 0.0005 (7) | 0.0035 (7) | −0.0007 (7) |
C1 | 0.0172 (9) | 0.0099 (9) | 0.0200 (10) | 0.0010 (8) | 0.0025 (7) | 0.0007 (8) |
C2 | 0.0295 (12) | 0.0170 (11) | 0.0175 (10) | −0.0027 (9) | 0.0040 (9) | −0.0034 (8) |
C3 | 0.0323 (13) | 0.0226 (12) | 0.0177 (11) | −0.0008 (10) | 0.0037 (9) | −0.0007 (9) |
P2 | 0.0117 (2) | 0.0087 (2) | 0.0174 (2) | 0.0009 (2) | 0.00322 (18) | 0.0000 (2) |
O4 | 0.0141 (7) | 0.0133 (7) | 0.0261 (8) | −0.0006 (6) | 0.0063 (6) | −0.0003 (6) |
O5 | 0.0214 (8) | 0.0124 (8) | 0.0173 (7) | 0.0038 (6) | 0.0002 (6) | −0.0011 (6) |
O6 | 0.0162 (7) | 0.0130 (7) | 0.0212 (8) | 0.0013 (6) | 0.0046 (6) | −0.0041 (6) |
N2 | 0.0155 (8) | 0.0094 (8) | 0.0163 (9) | 0.0010 (7) | 0.0006 (7) | −0.0016 (7) |
C4 | 0.0142 (8) | 0.0090 (9) | 0.0164 (8) | 0.0006 (8) | 0.0034 (7) | −0.0028 (8) |
C5 | 0.0195 (10) | 0.0186 (12) | 0.0203 (10) | 0.0030 (9) | −0.0014 (8) | −0.0004 (10) |
C6 | 0.0359 (13) | 0.0264 (14) | 0.0217 (11) | 0.0088 (10) | −0.0015 (10) | 0.0037 (9) |
P1—O2 | 1.5014 (15) | P2—O5 | 1.4921 (15) |
P1—O1 | 1.5029 (15) | P2—O4 | 1.5105 (15) |
P1—O3 | 1.5649 (15) | P2—O6 | 1.5718 (16) |
P1—C1 | 1.841 (2) | P2—C4 | 1.836 (2) |
O3—H3D | 0.939 (10) | O6—H6A | 0.944 (10) |
N1—C1 | 1.495 (3) | N2—C4 | 1.496 (3) |
N1—H1 | 0.939 (9) | N2—H4 | 0.952 (9) |
N1—H2 | 0.950 (9) | N2—H5 | 0.951 (9) |
N1—H3 | 0.950 (9) | N2—H6 | 0.953 (9) |
C1—C2 | 1.528 (3) | C4—C5 | 1.525 (3) |
C1—H1A | 1.0000 | C4—H4A | 1.0000 |
C2—C3 | 1.527 (3) | C5—C6 | 1.536 (3) |
C2—H2A | 0.9900 | C5—H5A | 0.9900 |
C2—H2B | 0.9900 | C5—H5B | 0.9900 |
C3—H3A | 0.9800 | C6—H6B | 0.9800 |
C3—H3B | 0.9800 | C6—H6C | 0.9800 |
C3—H3C | 0.9800 | C6—H6D | 0.9800 |
O2—P1—O1 | 115.51 (9) | O5—P2—O4 | 115.80 (9) |
O2—P1—O3 | 111.82 (8) | O5—P2—O6 | 114.03 (8) |
O1—P1—O3 | 110.39 (10) | O4—P2—O6 | 106.37 (9) |
O2—P1—C1 | 109.12 (9) | O5—P2—C4 | 106.28 (8) |
O1—P1—C1 | 106.29 (9) | O4—P2—C4 | 109.81 (9) |
O3—P1—C1 | 102.78 (10) | O6—P2—C4 | 103.89 (8) |
P1—O3—H3D | 124.9 (18) | P2—O6—H6A | 116.1 (16) |
C1—N1—H1 | 110.3 (14) | C4—N2—H4 | 111.8 (14) |
C1—N1—H2 | 107.5 (15) | C4—N2—H5 | 108.2 (14) |
H1—N1—H2 | 110.3 (12) | H4—N2—H5 | 108.1 (12) |
C1—N1—H3 | 109.2 (14) | C4—N2—H6 | 112.1 (14) |
H1—N1—H3 | 110.3 (12) | H4—N2—H6 | 108.3 (12) |
H2—N1—H3 | 109.2 (12) | H5—N2—H6 | 108.1 (11) |
N1—C1—C2 | 110.49 (17) | N2—C4—C5 | 111.50 (17) |
N1—C1—P1 | 109.52 (13) | N2—C4—P2 | 109.09 (13) |
C2—C1—P1 | 115.69 (16) | C5—C4—P2 | 113.58 (15) |
N1—C1—H1A | 106.9 | N2—C4—H4A | 107.5 |
C2—C1—H1A | 106.9 | C5—C4—H4A | 107.5 |
P1—C1—H1A | 106.9 | P2—C4—H4A | 107.5 |
C3—C2—C1 | 113.07 (19) | C4—C5—C6 | 113.4 (2) |
C3—C2—H2A | 109.0 | C4—C5—H5A | 108.9 |
C1—C2—H2A | 109.0 | C6—C5—H5A | 108.9 |
C3—C2—H2B | 109.0 | C4—C5—H5B | 108.9 |
C1—C2—H2B | 109.0 | C6—C5—H5B | 108.9 |
H2A—C2—H2B | 107.8 | H5A—C5—H5B | 107.7 |
C2—C3—H3A | 109.5 | C5—C6—H6B | 109.5 |
C2—C3—H3B | 109.5 | C5—C6—H6C | 109.5 |
H3A—C3—H3B | 109.5 | H6B—C6—H6C | 109.5 |
C2—C3—H3C | 109.5 | C5—C6—H6D | 109.5 |
H3A—C3—H3C | 109.5 | H6B—C6—H6D | 109.5 |
H3B—C3—H3C | 109.5 | H6C—C6—H6D | 109.5 |
O2—P1—C1—N1 | 26.71 (17) | O5—P2—C4—N2 | 36.46 (15) |
O1—P1—C1—N1 | 151.89 (14) | O4—P2—C4—N2 | −89.49 (14) |
O3—P1—C1—N1 | −92.10 (15) | O6—P2—C4—N2 | 157.07 (12) |
O2—P1—C1—C2 | 152.35 (15) | O5—P2—C4—C5 | 161.50 (14) |
O1—P1—C1—C2 | −82.47 (17) | O4—P2—C4—C5 | 35.56 (17) |
O3—P1—C1—C2 | 33.53 (18) | O6—P2—C4—C5 | −77.88 (16) |
N1—C1—C2—C3 | −170.11 (19) | N2—C4—C5—C6 | −65.7 (2) |
P1—C1—C2—C3 | 64.8 (2) | P2—C4—C5—C6 | 170.61 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3D···O4i | 0.94 (1) | 1.66 (1) | 2.583 (2) | 168 (3) |
N1—H1···O1ii | 0.94 (1) | 1.83 (1) | 2.767 (2) | 178 (2) |
N1—H2···O2iii | 0.95 (1) | 1.97 (2) | 2.794 (2) | 144 (2) |
N1—H3···O4iv | 0.95 (1) | 1.91 (1) | 2.843 (3) | 166 (2) |
O6—H6A···O1 | 0.94 (1) | 1.65 (1) | 2.589 (2) | 175 (3) |
N2—H4···O4v | 0.95 (1) | 2.05 (2) | 2.914 (2) | 151 (2) |
N2—H5···O5vi | 0.95 (1) | 1.78 (1) | 2.697 (2) | 162 (2) |
N2—H6···O2vi | 0.95 (1) | 1.84 (1) | 2.783 (2) | 172 (2) |
Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z; (iii) −x, y+1/2, −z+1; (iv) −x+1, y+1/2, −z+1; (v) x, y−1, z; (vi) −x+1, y−1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C3H10NO3P |
Mr | 139.09 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 150 |
a, b, c (Å) | 9.3988 (13), 6.2511 (8), 10.8575 (15) |
β (°) | 105.731 (9) |
V (Å3) | 614.02 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.16 × 0.08 × 0.02 |
Data collection | |
Diffractometer | Bruker X8 Kappa CCD APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1998) |
Tmin, Tmax | 0.943, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23447, 4196, 3465 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.767 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.088, 1.06 |
No. of reflections | 4196 |
No. of parameters | 171 |
No. of restraints | 15 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.55 |
Absolute structure | Flack (1983), 1730 Friedel pairs |
Absolute structure parameter | −0.03 (8) |
Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).
O3—P1—C1—C2 | 33.53 (18) | O6—P2—C4—C5 | −77.88 (16) |
P1—C1—C2—C3 | 64.8 (2) | P2—C4—C5—C6 | 170.61 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3D···O4i | 0.939 (10) | 1.657 (11) | 2.583 (2) | 168 (3) |
N1—H1···O1ii | 0.939 (9) | 1.829 (9) | 2.767 (2) | 177.5 (19) |
N1—H2···O2iii | 0.950 (9) | 1.969 (17) | 2.794 (2) | 144.1 (19) |
N1—H3···O4iv | 0.950 (9) | 1.913 (11) | 2.843 (3) | 166 (2) |
O6—H6A···O1 | 0.944 (10) | 1.647 (10) | 2.589 (2) | 175 (3) |
N2—H4···O4v | 0.952 (9) | 2.046 (15) | 2.914 (2) | 150.6 (19) |
N2—H5···O5vi | 0.951 (9) | 1.778 (11) | 2.697 (2) | 161.5 (18) |
N2—H6···O2vi | 0.953 (9) | 1.836 (9) | 2.783 (2) | 171.8 (17) |
Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z; (iii) −x, y+1/2, −z+1; (iv) −x+1, y+1/2, −z+1; (v) x, y−1, z; (vi) −x+1, y−1/2, −z+1. |
Acknowledgements
We are grateful to the Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their general financial support (R&D project PTDC/QUI-QUI/098098/2008), for the post-doctoral and PhD research grants Nos. SFRH/BPD/63736/2009 (to JAF) and SFRH/BD/66371/2009 (to SMFV), and for specific funding toward the purchase of the diffractometer.
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The racemic mixture of the title compound is known as Ampropylfos and has been the object of several studies for its use as a pesticide (Hudson & Ismail, 2001), and its crystal structure has been very recently reported (Bashall et al., 2010). Following our interest in the use of phosphonic acid molecules (Fernandes et al., 2010; Cunha-Silva, Ananias et al., 2009; Cunha-Silva, Lima et al., 2009; Rocha et al., 2009; Shi, Cunha-Silva et al., 2008; Shi, Trindade et al., 2008; Cunha-Silva et al., 2007) here we wish to describe the crystal structure of the title compound (see Scheme).
The asymmetric unit is composed by two entities of the title compound in their zwitterionic form, in which the acidic phosphonate moiety donates one proton to the amino group (Figure 1). The geometrical conformations of the two molecules are considerably different: in one unit the two torsion angles O3—P1—C1—C2 and P1—C1—C2—C3 are both +synclinal and in the other the analogous torsion angles (O6—P2—C4—C5 and P2—C4—C5—C6) are -synclinal and antiperiplanar, respectively (see Table 1; Moss, 1996). The two crystallographically unique molecules are organized in the crystal structure into a supramolecular bilayer (in the ab plane) having the hydrophilic portion in the interior (composed by the amino, methyne and phosphonate moieties) and the hydrophobic in the outer position (formed by the pendant —CH2CH3 groups) (Figures 2 and 3).
Inside the hydrophilic section, individual functional groups are disposed in a zigzag fashion along the [010] direction of the unit cell, leading to the formation of a supramolecular chain held together by a combination of four N+—H···O hydrogen bridges (green dashed bonds in Figure 2; Table 2) - graph set motif R34(10) (Grell et al., 1999). Supramolecular chains are, in turn, interconnected in the ab plane via the remanant N+—H···O (orange dashed lines in Figure 2) and O—H···O hydrogen bonds (violet dashed lines in Figure 2).
Noteworthy, all hydrogen bonding interactions are rather strong with the internuclear D···A distances ranging from 2.583 (2) to 2.914 (2) Å. In addition, the 〈(DHA) angles range from ca 144 to 177°. One acceptor atom (O4) participates in a D13(7) graph set motif with all 〈(DHA) greater than ca 150°. Other acceptors (O1 and O2) are, in turn, involved in D12(5) motifs: N1—H2···O2 with 〈(DHA) of ca 144° and the other three interactions having angles larger than ca 171°. O5 is the only acceptor in a S11 graph set motif: N2—H5···O5 with 〈(DHA) of ca 162° (See Table 2).
The crystal can be better described by employing a topological approach for the description of the aforementioned hydrogen bonding interactions. Taking the geometrical centre of each molecular unit as a node, and being the hydrogen bonding interactions the connections between nodes, the structure can be simplified into a two-dimensional uninodal 7-connected single-penetrated planar (4,4)IIIb network, with total Schläfli symbol 36.412.53 (Blatov & Proserpio, 2009).