organic compounds
Ethyl N-[2-(4-phenoxyphenoxy)ethyl]carbamate
aSchool of Chemistry, National University of Ireland, Galway, University road, Galway, Ireland, and bSchool of Chemistry, Limerick, Ireland
*Correspondence e-mail: p.mcardle@nuigalway.ie
The title compound, C17H19NO4, which is a non-toxic insect growth regulator with the common name fenoxycarb, contains two independent and conformationally different molecules in the Although the inter-ring dihedral angles are similar [62.21 (15) and 63.00 (14)°], the side-chain orientations differ. In the crystal, the molecules are linked through N—H⋯O hydrogen-bonding associations, giving chains which extend along [110], while intra- and intermolecular aromatic C—H⋯π interactions give sheet structures parallel to [110].
Related literature
For studies on the role of fenoxycarb as an insect growth regulator, see: Paya et al. (2009); Sullivan (2010); Kavallieratos et al. (2012); Goncu & Parlak (2012). For related structures containing the phenyl ether motif, see: Ammon et al. (1983); Clayden et al. (1990); Glidewell et al. (2005). For hydrogen-bond data, see Lifson et al. (1979).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SORTX (McArdle, 1995); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536812037105/zs2230sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037105/zs2230Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812037105/zs2230Isup3.cml
The title compound of high purity (>98.8%) was obtained from Syngenta, Switzerland. Colourless, lath shaped crystals were grown from a solution in ethanol by slow evaporation at room temperature.
All H atoms were included in the
in calculated positions [N—H = 0.88 Å, C—H(aromatic) = 0.93 Å, C—H(methylene) = 0.97 Å or C—H(methyl) = 0.96 Å] and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq (C, N) or 1.5Ueq(C methyl).The title compound fenoxycarb, C17H19NO4 is an insect growth regulator with juvenile hormone activity (Paya et al., 2009; Sullivan et al., 2010; Kavallieratos et al., 2012; Goncu & Parlak, 2012). As part of our studies on the crystallization behaviour of this compound the
of fenocarb has been determined.There are two chemically identical but conformationally different molecules in the π contacts. With the aromatic ring centroids numbered in order of carbon number the distances for the interactions H26···Cg2, H29···Cg2, H9···Cg4 and H12···Cg4 are 2.87, 2.80, 2.86 and 2.86 Å respectively. The one-dimensional chains are built into two-dimensional sheets by further C—H···π contacts involving H19···Cg1, H22···Cg1, H2···Cg3 and H5···Cg3 are 2.92, 2.84, 2.85 and 2.85 Å respectively (Fig. 4). There are no π-π contacts involving the aromatic rings as adjacent rings are non-coplanar. The packing is shown in Fig.5.
(Fig. 1). Although the two benzene rings adopt similar orientations [inter-ring dihedral angles, 62.21 (15) and 63.00 (14)°], the side chains differ in the region associated with the intermolecular N—H···O hydrogen-bonding interactions between the two molecules, with torsion angles O2—C13—C14—N1 and C13—C14—N1—C15 [-64.6 (4) and -85.2 (4)° in molecule 1] and O6—C30—C31—N2 and C30—C31—N2—C32 [57.4 (3) and -151.2 (3)° in molecule 2] (Fig. 2). The N2—H···O3 and N1—H···O3i hydrogen bonds bonds (Table 1) generate a one-dimensional motif that is parallel to [110] (Fig. 3). The hydrogen bonds are estimated to be of moderate strength at 8 kcal/mol (Lifson et al., 1979) and they are supported by weaker C—H···For studies on the role of fenoxycarb as an insect growth regulator, see: Paya et al. (2009); Sullivan et al. (2010); Kavallieratos et al. (2012); Goncu & Parlak (2012). For related structures containing the phenyl ether motif, see: Ammon et al. (1983); Clayden et al. (1990); Glidewell et al. (2005). For hydrogen-bond data, see Lifson et al. (1979).
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell
CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SORTX (McArdle, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The atom numbering scheme for the two independent molecules in the asymmetric unit of fenoxycarb. Displacement ellipsoids for non-H atoms are are drawn at the 30% probability level. | |
Fig. 2. Molecular overlay of the two conformationally different fenoxycarb molecules. | |
Fig. 3. The one-dimensional hydrogen-bonded chains in the crystal structure of fenoxycarb. | |
Fig. 4. A view down the H-bonded chains showing C—H···π interactions. | |
Fig. 5. The unit cell packing of fenoxycarb viewed down a. |
C17H19NO4 | Z = 4 |
Mr = 301.33 | F(000) = 640 |
Triclinic, P1 | Dx = 1.273 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.7107 Å |
a = 5.9035 (3) Å | Cell parameters from 2643 reflections |
b = 7.5712 (4) Å | θ = 2.8–29.2° |
c = 35.373 (2) Å | µ = 0.09 mm−1 |
α = 85.618 (5)° | T = 150 K |
β = 86.213 (5)° | Parallelepiped, colourless |
γ = 89.046 (4)° | 0.40 × 0.30 × 0.15 mm |
V = 1572.88 (15) Å3 |
Oxford Diffraction Xcalibur, Sapphire3 CCD-detector diffractometer | 5745 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2937 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
Detector resolution: 16.1048 pixels mm-1 | θmax = 25.4°, θmin = 2.8° |
ω scans | h = −6→7 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −9→9 |
Tmin = 0.894, Tmax = 1.000 | l = −42→36 |
25379 measured reflections |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0202P)2] where P = (Fo2 + 2Fc2)/3 |
5745 reflections | (Δ/σ)max < 0.001 |
399 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C17H19NO4 | γ = 89.046 (4)° |
Mr = 301.33 | V = 1572.88 (15) Å3 |
Triclinic, P1 | Z = 4 |
a = 5.9035 (3) Å | Mo Kα radiation |
b = 7.5712 (4) Å | µ = 0.09 mm−1 |
c = 35.373 (2) Å | T = 150 K |
α = 85.618 (5)° | 0.40 × 0.30 × 0.15 mm |
β = 86.213 (5)° |
Oxford Diffraction Xcalibur, Sapphire3 CCD-detector diffractometer | 5745 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 2937 reflections with I > 2σ(I) |
Tmin = 0.894, Tmax = 1.000 | Rint = 0.074 |
25379 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.21 e Å−3 |
5745 reflections | Δρmin = −0.22 e Å−3 |
399 parameters |
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 | ||
O1 | −0.0999 (3) | 0.0094 (3) | 0.14727 (6) | 0.0292 (6) | |
O2 | 0.2377 (3) | −0.0627 (3) | 0.28990 (6) | 0.0284 (6) | |
O4 | 0.2198 (4) | 0.1319 (3) | 0.41170 (6) | 0.0397 (7) | |
N1 | 0.3603 (5) | −0.0324 (4) | 0.36637 (8) | 0.0341 (7) | |
H1N1 | 0.2510 | −0.1030 | 0.3739 | 0.044* | |
O3 | 0.5364 (4) | 0.2199 (3) | 0.37656 (8) | 0.0543 (8) | |
C1 | 0.0310 (5) | 0.0155 (4) | 0.11300 (9) | 0.0229 (8) | |
C2 | −0.0716 (5) | 0.1035 (4) | 0.08305 (9) | 0.0260 (8) | |
H2 | −0.2109 | 0.1606 | 0.0871 | 0.034* | |
C3 | 0.0335 (6) | 0.1065 (4) | 0.04699 (10) | 0.0329 (9) | |
H3 | −0.0349 | 0.1651 | 0.0266 | 0.043* | |
C4 | 0.2414 (6) | 0.0216 (4) | 0.04128 (10) | 0.0330 (9) | |
H4 | 0.3129 | 0.0235 | 0.0170 | 0.043* | |
C5 | 0.3429 (6) | −0.0661 (4) | 0.07175 (10) | 0.0336 (9) | |
H5 | 0.4828 | −0.1224 | 0.0679 | 0.044* | |
C6 | 0.2356 (5) | −0.0698 (4) | 0.10793 (9) | 0.0266 (8) | |
H6 | 0.3019 | −0.1295 | 0.1284 | 0.035* | |
C7 | 0.0047 (5) | −0.0086 (4) | 0.18145 (9) | 0.0222 (8) | |
C8 | 0.1958 (5) | 0.0809 (4) | 0.18832 (9) | 0.0268 (8) | |
H8 | 0.2701 | 0.1513 | 0.1688 | 0.035* | |
C9 | 0.2801 (5) | 0.0672 (4) | 0.22452 (9) | 0.0270 (8) | |
H9 | 0.4104 | 0.1276 | 0.2290 | 0.035* | |
C10 | 0.1681 (5) | −0.0371 (4) | 0.25359 (9) | 0.0239 (8) | |
C11 | −0.0258 (5) | −0.1266 (4) | 0.24658 (9) | 0.0241 (8) | |
H11 | −0.1013 | −0.1966 | 0.2660 | 0.031* | |
C12 | −0.1071 (5) | −0.1122 (4) | 0.21074 (9) | 0.0246 (8) | |
H12 | −0.2376 | −0.1722 | 0.2062 | 0.032* | |
C13 | 0.4498 (5) | 0.0105 (4) | 0.29752 (9) | 0.0306 (9) | |
H13A | 0.4353 | 0.1378 | 0.2987 | 0.040* | |
H13B | 0.5647 | −0.0137 | 0.2776 | 0.040* | |
C14 | 0.5151 (5) | −0.0751 (4) | 0.33510 (9) | 0.0339 (9) | |
H14A | 0.5202 | −0.2026 | 0.3338 | 0.044* | |
H14B | 0.6662 | −0.0372 | 0.3398 | 0.044* | |
C15 | 0.3848 (6) | 0.1153 (5) | 0.38376 (10) | 0.0326 (9) | |
C16 | 0.2336 (6) | 0.2855 (5) | 0.43345 (11) | 0.0469 (11) | |
H16A | 0.2367 | 0.3934 | 0.4168 | 0.061* | |
H16B | 0.3700 | 0.2795 | 0.4474 | 0.061* | |
C17 | 0.0265 (7) | 0.2828 (5) | 0.46030 (10) | 0.0620 (13) | |
H17A | −0.1068 | 0.2913 | 0.4461 | 0.087* | |
H17B | 0.0295 | 0.3811 | 0.4758 | 0.087* | |
H17C | 0.0239 | 0.1741 | 0.4762 | 0.087* | |
O5 | 0.4018 (3) | 0.4830 (3) | 0.14990 (6) | 0.0274 (6) | |
O6 | 0.7396 (3) | 0.4935 (3) | 0.29179 (6) | 0.0293 (6) | |
O8 | 0.6720 (4) | 0.6213 (3) | 0.41569 (7) | 0.0368 (6) | |
N2 | 0.8499 (4) | 0.4950 (4) | 0.36737 (8) | 0.0337 (7) | |
H2N2 | 0.7451 | 0.4168 | 0.3709 | 0.044* | |
O7 | 0.9987 (4) | 0.7375 (3) | 0.38924 (7) | 0.0562 (8) | |
C18 | 0.5324 (5) | 0.5007 (4) | 0.11550 (9) | 0.0236 (8) | |
C19 | 0.4372 (5) | 0.4303 (4) | 0.08561 (9) | 0.0256 (8) | |
H19 | 0.3003 | 0.3704 | 0.0894 | 0.033* | |
C20 | 0.5461 (5) | 0.4492 (4) | 0.05006 (9) | 0.0285 (8) | |
H20 | 0.4841 | 0.3999 | 0.0298 | 0.037* | |
C21 | 0.7470 (5) | 0.5407 (4) | 0.04410 (9) | 0.0310 (9) | |
H21 | 0.8186 | 0.5553 | 0.0199 | 0.040* | |
C22 | 0.8410 (5) | 0.6104 (4) | 0.07428 (9) | 0.0296 (9) | |
H22 | 0.9779 | 0.6702 | 0.0704 | 0.039* | |
C23 | 0.7322 (5) | 0.5919 (4) | 0.11049 (9) | 0.0243 (8) | |
H23 | 0.7938 | 0.6404 | 0.1308 | 0.032* | |
C24 | 0.5056 (5) | 0.4846 (4) | 0.18424 (9) | 0.0218 (8) | |
C25 | 0.6998 (5) | 0.3895 (4) | 0.19176 (9) | 0.0251 (8) | |
H25 | 0.7755 | 0.3277 | 0.1729 | 0.033* | |
C26 | 0.7829 (5) | 0.3860 (4) | 0.22775 (9) | 0.0241 (8) | |
H26 | 0.9151 | 0.3227 | 0.2329 | 0.031* | |
C27 | 0.6686 (5) | 0.4770 (4) | 0.25594 (9) | 0.0226 (8) | |
C28 | 0.4693 (5) | 0.5692 (4) | 0.24816 (9) | 0.0252 (8) | |
H28 | 0.3905 | 0.6286 | 0.2671 | 0.033* | |
C29 | 0.3880 (5) | 0.5730 (4) | 0.21237 (9) | 0.0240 (8) | |
H29 | 0.2548 | 0.6348 | 0.2072 | 0.031* | |
C30 | 0.9338 (5) | 0.3936 (4) | 0.30377 (9) | 0.0307 (9) | |
H30A | 1.0497 | 0.3917 | 0.2830 | 0.040* | |
H30B | 0.8916 | 0.2726 | 0.3118 | 0.040* | |
C31 | 1.0216 (5) | 0.4823 (5) | 0.33638 (9) | 0.0366 (9) | |
H31A | 1.1511 | 0.4156 | 0.3456 | 0.048* | |
H31B | 1.0726 | 0.6003 | 0.3275 | 0.048* | |
C32 | 0.8522 (6) | 0.6256 (5) | 0.39035 (10) | 0.0343 (9) | |
C33 | 0.6632 (6) | 0.7599 (5) | 0.44188 (10) | 0.0467 (11) | |
H33A | 0.6760 | 0.8752 | 0.4280 | 0.061* | |
H33B | 0.7870 | 0.7452 | 0.4586 | 0.061* | |
C34 | 0.4383 (6) | 0.7456 (5) | 0.46465 (10) | 0.0549 (12) | |
H34A | 0.3173 | 0.7534 | 0.4477 | 0.077* | |
H34B | 0.4230 | 0.8402 | 0.4813 | 0.077* | |
H34C | 0.4314 | 0.6339 | 0.4795 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0267 (13) | 0.0378 (15) | 0.0230 (14) | 0.0023 (11) | −0.0034 (10) | −0.0012 (11) |
O2 | 0.0311 (14) | 0.0302 (14) | 0.0238 (14) | −0.0025 (11) | −0.0039 (10) | 0.0008 (11) |
O4 | 0.0506 (17) | 0.0392 (16) | 0.0299 (16) | −0.0070 (13) | 0.0029 (13) | −0.0109 (12) |
N1 | 0.0404 (19) | 0.0306 (18) | 0.0310 (19) | −0.0116 (15) | 0.0027 (14) | −0.0018 (14) |
O3 | 0.0543 (18) | 0.0398 (17) | 0.069 (2) | −0.0240 (15) | 0.0118 (15) | −0.0133 (15) |
C1 | 0.0230 (19) | 0.0206 (18) | 0.025 (2) | 0.0017 (15) | −0.0006 (15) | −0.0030 (15) |
C2 | 0.026 (2) | 0.0239 (19) | 0.028 (2) | 0.0029 (16) | −0.0054 (15) | −0.0003 (16) |
C3 | 0.040 (2) | 0.028 (2) | 0.031 (2) | −0.0004 (18) | −0.0102 (17) | 0.0003 (17) |
C4 | 0.035 (2) | 0.034 (2) | 0.030 (2) | −0.0045 (18) | 0.0020 (17) | −0.0077 (17) |
C5 | 0.032 (2) | 0.030 (2) | 0.040 (2) | 0.0057 (17) | −0.0042 (18) | −0.0065 (18) |
C6 | 0.027 (2) | 0.0239 (19) | 0.029 (2) | 0.0033 (16) | −0.0048 (16) | −0.0033 (16) |
C7 | 0.027 (2) | 0.0185 (18) | 0.0217 (19) | 0.0059 (15) | −0.0040 (15) | −0.0054 (15) |
C8 | 0.031 (2) | 0.0200 (19) | 0.028 (2) | 0.0001 (16) | 0.0019 (15) | 0.0026 (16) |
C9 | 0.027 (2) | 0.0198 (19) | 0.033 (2) | 0.0002 (16) | −0.0024 (16) | 0.0009 (16) |
C10 | 0.025 (2) | 0.0218 (19) | 0.024 (2) | 0.0077 (16) | −0.0020 (15) | −0.0018 (15) |
C11 | 0.027 (2) | 0.0189 (18) | 0.026 (2) | 0.0015 (15) | 0.0045 (15) | −0.0020 (15) |
C12 | 0.0228 (19) | 0.0198 (19) | 0.031 (2) | 0.0023 (15) | 0.0022 (15) | −0.0040 (16) |
C13 | 0.028 (2) | 0.036 (2) | 0.028 (2) | −0.0001 (17) | −0.0012 (15) | −0.0051 (17) |
C14 | 0.037 (2) | 0.036 (2) | 0.029 (2) | 0.0015 (18) | −0.0076 (17) | −0.0024 (18) |
C15 | 0.040 (2) | 0.026 (2) | 0.032 (2) | −0.0031 (19) | −0.0043 (18) | 0.0004 (17) |
C16 | 0.065 (3) | 0.037 (2) | 0.041 (3) | 0.005 (2) | −0.012 (2) | −0.014 (2) |
C17 | 0.088 (4) | 0.064 (3) | 0.033 (3) | 0.016 (3) | 0.001 (2) | −0.008 (2) |
O5 | 0.0264 (13) | 0.0333 (14) | 0.0226 (14) | −0.0003 (11) | −0.0027 (10) | −0.0021 (11) |
O6 | 0.0344 (14) | 0.0284 (14) | 0.0259 (14) | 0.0044 (11) | −0.0061 (10) | −0.0040 (11) |
O8 | 0.0417 (16) | 0.0343 (15) | 0.0355 (16) | −0.0025 (13) | −0.0021 (12) | −0.0097 (12) |
N2 | 0.0393 (19) | 0.0333 (18) | 0.0290 (19) | −0.0151 (15) | −0.0020 (14) | −0.0027 (15) |
O7 | 0.0579 (18) | 0.0566 (19) | 0.056 (2) | −0.0336 (16) | 0.0018 (14) | −0.0151 (15) |
C18 | 0.029 (2) | 0.0190 (19) | 0.022 (2) | 0.0051 (16) | −0.0019 (15) | 0.0034 (15) |
C19 | 0.027 (2) | 0.0247 (19) | 0.025 (2) | −0.0003 (16) | −0.0047 (15) | 0.0028 (16) |
C20 | 0.037 (2) | 0.027 (2) | 0.023 (2) | 0.0020 (17) | −0.0100 (16) | −0.0037 (16) |
C21 | 0.035 (2) | 0.030 (2) | 0.026 (2) | 0.0056 (18) | 0.0002 (16) | 0.0062 (17) |
C22 | 0.027 (2) | 0.027 (2) | 0.034 (2) | 0.0011 (16) | 0.0000 (16) | 0.0015 (17) |
C23 | 0.031 (2) | 0.0177 (18) | 0.025 (2) | 0.0017 (16) | −0.0052 (15) | −0.0056 (15) |
C24 | 0.0215 (19) | 0.0222 (18) | 0.0219 (19) | −0.0054 (15) | −0.0032 (15) | −0.0008 (15) |
C25 | 0.033 (2) | 0.0215 (19) | 0.0206 (19) | 0.0036 (16) | 0.0019 (15) | −0.0045 (15) |
C26 | 0.026 (2) | 0.0194 (18) | 0.027 (2) | 0.0048 (15) | −0.0021 (15) | −0.0029 (15) |
C27 | 0.031 (2) | 0.0164 (18) | 0.0206 (19) | −0.0041 (15) | −0.0032 (15) | 0.0014 (14) |
C28 | 0.028 (2) | 0.0211 (19) | 0.026 (2) | 0.0004 (16) | 0.0031 (15) | −0.0048 (15) |
C29 | 0.0223 (19) | 0.0155 (18) | 0.034 (2) | 0.0015 (15) | −0.0011 (15) | −0.0030 (15) |
C30 | 0.033 (2) | 0.035 (2) | 0.025 (2) | 0.0031 (17) | −0.0075 (16) | 0.0015 (17) |
C31 | 0.035 (2) | 0.046 (2) | 0.029 (2) | −0.0075 (19) | −0.0038 (17) | −0.0005 (18) |
C32 | 0.035 (2) | 0.039 (2) | 0.028 (2) | −0.005 (2) | −0.0076 (18) | 0.0056 (18) |
C33 | 0.061 (3) | 0.043 (3) | 0.040 (3) | 0.003 (2) | −0.013 (2) | −0.018 (2) |
C34 | 0.066 (3) | 0.056 (3) | 0.044 (3) | 0.014 (2) | −0.005 (2) | −0.011 (2) |
O1—C7 | 1.390 (3) | O5—C18 | 1.396 (3) |
O1—C1 | 1.392 (3) | O5—C24 | 1.397 (3) |
O2—C10 | 1.373 (3) | O6—C27 | 1.377 (3) |
O2—C13 | 1.428 (3) | O6—C30 | 1.432 (3) |
O4—C15 | 1.352 (4) | O8—C32 | 1.344 (4) |
O4—C16 | 1.449 (4) | O8—C33 | 1.450 (4) |
N1—C15 | 1.331 (4) | N2—C32 | 1.328 (4) |
N1—C14 | 1.440 (4) | N2—C31 | 1.450 (4) |
N1—H1N1 | 0.8600 | N2—H2N2 | 0.8600 |
O3—C15 | 1.206 (4) | O7—C32 | 1.218 (4) |
C1—C6 | 1.368 (4) | C18—C23 | 1.372 (4) |
C1—C2 | 1.377 (4) | C18—C19 | 1.376 (4) |
C2—C3 | 1.380 (4) | C19—C20 | 1.373 (4) |
C2—H2 | 0.9300 | C19—H19 | 0.9300 |
C3—C4 | 1.386 (4) | C20—C21 | 1.380 (4) |
C3—H3 | 0.9300 | C20—H20 | 0.9300 |
C4—C5 | 1.387 (4) | C21—C22 | 1.378 (4) |
C4—H4 | 0.9300 | C21—H21 | 0.9300 |
C5—C6 | 1.389 (4) | C22—C23 | 1.393 (4) |
C5—H5 | 0.9300 | C22—H22 | 0.9300 |
C6—H6 | 0.9300 | C23—H23 | 0.9300 |
C7—C8 | 1.370 (4) | C24—C25 | 1.374 (4) |
C7—C12 | 1.388 (4) | C24—C29 | 1.384 (4) |
C8—C9 | 1.400 (4) | C25—C26 | 1.392 (4) |
C8—H8 | 0.9300 | C25—H25 | 0.9300 |
C9—C10 | 1.386 (4) | C26—C27 | 1.387 (4) |
C9—H9 | 0.9300 | C26—H26 | 0.9300 |
C10—C11 | 1.386 (4) | C27—C28 | 1.391 (4) |
C11—C12 | 1.381 (4) | C28—C29 | 1.381 (4) |
C11—H11 | 0.9300 | C28—H28 | 0.9300 |
C12—H12 | 0.9300 | C29—H29 | 0.9300 |
C13—C14 | 1.504 (4) | C30—C31 | 1.503 (4) |
C13—H13A | 0.9700 | C30—H30A | 0.9700 |
C13—H13B | 0.9700 | C30—H30B | 0.9700 |
C14—H14A | 0.9700 | C31—H31A | 0.9700 |
C14—H14B | 0.9700 | C31—H31B | 0.9700 |
C16—C17 | 1.497 (5) | C33—C34 | 1.508 (5) |
C16—H16A | 0.9700 | C33—H33A | 0.9700 |
C16—H16B | 0.9700 | C33—H33B | 0.9700 |
C17—H17A | 0.9600 | C34—H34A | 0.9600 |
C17—H17B | 0.9600 | C34—H34B | 0.9600 |
C17—H17C | 0.9600 | C34—H34C | 0.9600 |
C7—O1—C1 | 120.0 (2) | C18—O5—C24 | 120.2 (2) |
C10—O2—C13 | 117.9 (2) | C27—O6—C30 | 119.1 (2) |
C15—O4—C16 | 116.0 (3) | C32—O8—C33 | 115.3 (3) |
C15—N1—C14 | 120.6 (3) | C32—N2—C31 | 121.0 (3) |
C15—N1—H1N1 | 119.7 | C32—N2—H2N2 | 119.5 |
C14—N1—H1N1 | 119.7 | C31—N2—H2N2 | 119.5 |
C6—C1—C2 | 121.6 (3) | C23—C18—C19 | 121.5 (3) |
C6—C1—O1 | 124.1 (3) | C23—C18—O5 | 123.6 (3) |
C2—C1—O1 | 114.1 (3) | C19—C18—O5 | 114.8 (3) |
C1—C2—C3 | 119.5 (3) | C20—C19—C18 | 119.4 (3) |
C1—C2—H2 | 120.2 | C20—C19—H19 | 120.3 |
C3—C2—H2 | 120.2 | C18—C19—H19 | 120.3 |
C2—C3—C4 | 119.8 (3) | C19—C20—C21 | 120.5 (3) |
C2—C3—H3 | 120.1 | C19—C20—H20 | 119.8 |
C4—C3—H3 | 120.1 | C21—C20—H20 | 119.8 |
C3—C4—C5 | 120.0 (3) | C22—C21—C20 | 119.6 (3) |
C3—C4—H4 | 120.0 | C22—C21—H21 | 120.2 |
C5—C4—H4 | 120.0 | C20—C21—H21 | 120.2 |
C4—C5—C6 | 120.0 (3) | C21—C22—C23 | 120.4 (3) |
C4—C5—H5 | 120.0 | C21—C22—H22 | 119.8 |
C6—C5—H5 | 120.0 | C23—C22—H22 | 119.8 |
C1—C6—C5 | 119.0 (3) | C18—C23—C22 | 118.6 (3) |
C1—C6—H6 | 120.5 | C18—C23—H23 | 120.7 |
C5—C6—H6 | 120.5 | C22—C23—H23 | 120.7 |
C8—C7—C12 | 119.6 (3) | C25—C24—C29 | 120.7 (3) |
C8—C7—O1 | 123.9 (3) | C25—C24—O5 | 123.0 (3) |
C12—C7—O1 | 116.2 (3) | C29—C24—O5 | 116.0 (3) |
C7—C8—C9 | 120.5 (3) | C24—C25—C26 | 119.7 (3) |
C7—C8—H8 | 119.7 | C24—C25—H25 | 120.1 |
C9—C8—H8 | 119.7 | C26—C25—H25 | 120.1 |
C10—C9—C8 | 119.5 (3) | C27—C26—C25 | 120.0 (3) |
C10—C9—H9 | 120.2 | C27—C26—H26 | 120.0 |
C8—C9—H9 | 120.2 | C25—C26—H26 | 120.0 |
O2—C10—C11 | 115.7 (3) | O6—C27—C26 | 125.9 (3) |
O2—C10—C9 | 124.5 (3) | O6—C27—C28 | 114.5 (3) |
C11—C10—C9 | 119.8 (3) | C26—C27—C28 | 119.6 (3) |
C12—C11—C10 | 120.1 (3) | C29—C28—C27 | 120.2 (3) |
C12—C11—H11 | 119.9 | C29—C28—H28 | 119.9 |
C10—C11—H11 | 119.9 | C27—C28—H28 | 119.9 |
C11—C12—C7 | 120.4 (3) | C28—C29—C24 | 119.8 (3) |
C11—C12—H12 | 119.8 | C28—C29—H29 | 120.1 |
C7—C12—H12 | 119.8 | C24—C29—H29 | 120.1 |
O2—C13—C14 | 107.1 (3) | O6—C30—C31 | 107.3 (3) |
O2—C13—H13A | 110.3 | O6—C30—H30A | 110.3 |
C14—C13—H13A | 110.3 | C31—C30—H30A | 110.3 |
O2—C13—H13B | 110.3 | O6—C30—H30B | 110.3 |
C14—C13—H13B | 110.3 | C31—C30—H30B | 110.3 |
H13A—C13—H13B | 108.6 | H30A—C30—H30B | 108.5 |
N1—C14—C13 | 113.0 (3) | N2—C31—C30 | 112.0 (3) |
N1—C14—H14A | 109.0 | N2—C31—H31A | 109.2 |
C13—C14—H14A | 109.0 | C30—C31—H31A | 109.2 |
N1—C14—H14B | 109.0 | N2—C31—H31B | 109.2 |
C13—C14—H14B | 109.0 | C30—C31—H31B | 109.2 |
H14A—C14—H14B | 107.8 | H31A—C31—H31B | 107.9 |
O3—C15—N1 | 125.2 (4) | O7—C32—N2 | 125.0 (4) |
O3—C15—O4 | 123.6 (3) | O7—C32—O8 | 122.8 (4) |
N1—C15—O4 | 111.1 (3) | N2—C32—O8 | 112.2 (3) |
O4—C16—C17 | 106.3 (3) | O8—C33—C34 | 107.3 (3) |
O4—C16—H16A | 110.5 | O8—C33—H33A | 110.2 |
C17—C16—H16A | 110.5 | C34—C33—H33A | 110.2 |
O4—C16—H16B | 110.5 | O8—C33—H33B | 110.2 |
C17—C16—H16B | 110.5 | C34—C33—H33B | 110.2 |
H16A—C16—H16B | 108.7 | H33A—C33—H33B | 108.5 |
C16—C17—H17A | 109.5 | C33—C34—H34A | 109.5 |
C16—C17—H17B | 109.5 | C33—C34—H34B | 109.5 |
H17A—C17—H17B | 109.5 | H34A—C34—H34B | 109.5 |
C16—C17—H17C | 109.5 | C33—C34—H34C | 109.5 |
H17A—C17—H17C | 109.5 | H34A—C34—H34C | 109.5 |
H17B—C17—H17C | 109.5 | H34B—C34—H34C | 109.5 |
C7—O1—C1—C6 | 30.9 (4) | C24—O5—C18—C23 | −29.0 (4) |
C7—O1—C1—C2 | −154.4 (3) | C24—O5—C18—C19 | 155.6 (3) |
C6—C1—C2—C3 | −0.1 (5) | C23—C18—C19—C20 | 1.0 (5) |
O1—C1—C2—C3 | −174.9 (3) | O5—C18—C19—C20 | 176.5 (3) |
C1—C2—C3—C4 | −0.3 (5) | C18—C19—C20—C21 | −1.2 (5) |
C2—C3—C4—C5 | 0.1 (5) | C19—C20—C21—C22 | 1.3 (5) |
C3—C4—C5—C6 | 0.4 (5) | C20—C21—C22—C23 | −1.3 (5) |
C2—C1—C6—C5 | 0.6 (5) | C19—C18—C23—C22 | −0.9 (4) |
O1—C1—C6—C5 | 174.9 (3) | O5—C18—C23—C22 | −176.0 (3) |
C4—C5—C6—C1 | −0.7 (5) | C21—C22—C23—C18 | 1.0 (5) |
C1—O1—C7—C8 | 42.6 (4) | C18—O5—C24—C25 | −45.6 (4) |
C1—O1—C7—C12 | −143.3 (3) | C18—O5—C24—C29 | 141.2 (3) |
C12—C7—C8—C9 | 0.6 (5) | C29—C24—C25—C26 | −1.8 (5) |
O1—C7—C8—C9 | 174.5 (3) | O5—C24—C25—C26 | −174.7 (3) |
C7—C8—C9—C10 | −0.4 (5) | C24—C25—C26—C27 | 0.6 (5) |
C13—O2—C10—C11 | 173.2 (3) | C30—O6—C27—C26 | −7.7 (4) |
C13—O2—C10—C9 | −5.6 (4) | C30—O6—C27—C28 | 175.5 (3) |
C8—C9—C10—O2 | 178.8 (3) | C25—C26—C27—O6 | −175.7 (3) |
C8—C9—C10—C11 | 0.0 (4) | C25—C26—C27—C28 | 0.9 (5) |
O2—C10—C11—C12 | −178.8 (3) | O6—C27—C28—C29 | 175.8 (3) |
C9—C10—C11—C12 | 0.0 (5) | C26—C27—C28—C29 | −1.2 (4) |
C10—C11—C12—C7 | 0.2 (5) | C27—C28—C29—C24 | 0.0 (5) |
C8—C7—C12—C11 | −0.6 (5) | C25—C24—C29—C28 | 1.5 (5) |
O1—C7—C12—C11 | −174.9 (3) | O5—C24—C29—C28 | 174.9 (3) |
C10—O2—C13—C14 | −165.2 (3) | C27—O6—C30—C31 | 160.0 (3) |
C15—N1—C14—C13 | −85.2 (4) | C32—N2—C31—C30 | −151.2 (3) |
O2—C13—C14—N1 | −64.6 (4) | O6—C30—C31—N2 | 57.3 (4) |
C14—N1—C15—O3 | −3.0 (5) | C31—N2—C32—O7 | −4.1 (5) |
C14—N1—C15—O4 | 178.8 (3) | C31—N2—C32—O8 | 176.0 (3) |
C16—O4—C15—O3 | −0.2 (5) | C33—O8—C32—O7 | 0.0 (5) |
C16—O4—C15—N1 | 178.1 (3) | C33—O8—C32—N2 | 179.9 (3) |
C15—O4—C16—C17 | 175.8 (3) | C32—O8—C33—C34 | 173.6 (3) |
Cg1, Cg2, Cg3 and Cg4 are the centroids of the C1–C6, C7–C12, C18–C23 and C24–C29 rings,respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O7i | 0.86 | 1.96 | 2.815 (4) | 178 |
N2—H2N2···O3 | 0.86 | 1.94 | 2.795 (4) | 173 |
C2—H2···Cg3ii | 0.93 | 2.85 | 3.562 (3) | 134 |
C5—H5···Cg3iii | 0.93 | 2.85 | 3.562 (3) | 134 |
C9—H9···Cg4 | 0.93 | 2.86 | 3.622 (3) | 139 |
C12—H12···Cg4i | 0.93 | 2.84 | 3.590 (3) | 138 |
C19—H19···Cg1 | 0.93 | 2.92 | 3.657 (3) | 137 |
C22—H22···Cg1iv | 0.93 | 2.84 | 3.583 (3) | 137 |
C26—H26···Cg2v | 0.93 | 2.87 | 3.579 (3) | 134 |
C29—H29···Cg2vi | 0.93 | 2.80 | 3.527 (3) | 135 |
Symmetry codes: (i) x−1, y−1, z; (ii) x−1, y, z; (iii) x, y−1, z; (iv) x+1, y+1, z; (v) x+1, y, z; (vi) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C17H19NO4 |
Mr | 301.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 5.9035 (3), 7.5712 (4), 35.373 (2) |
α, β, γ (°) | 85.618 (5), 86.213 (5), 89.046 (4) |
V (Å3) | 1572.88 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.30 × 0.15 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur, Sapphire3 CCD-detector |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.894, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25379, 5745, 2937 |
Rint | 0.074 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.126, 0.97 |
No. of reflections | 5745 |
No. of parameters | 399 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.22 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SORTX (McArdle, 1995).
Cg1, Cg2, Cg3 and Cg4 are the centroids of the C1–C6, C7–C12, C18–C23 and C24–C29 rings,respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O7i | 0.86 | 1.96 | 2.815 (4) | 178 |
N2—H2N2···O3 | 0.86 | 1.94 | 2.795 (4) | 173 |
C2—H2···Cg3ii | 0.93 | 2.85 | 3.562 (3) | 134 |
C5—H5···Cg3iii | 0.93 | 2.85 | 3.562 (3) | 134 |
C9—H9···Cg4 | 0.93 | 2.86 | 3.622 (3) | 139 |
C12—H12···Cg4i | 0.93 | 2.84 | 3.590 (3) | 138 |
C19—H19···Cg1 | 0.93 | 2.92 | 3.657 (3) | 137 |
C22—H22···Cg1iv | 0.93 | 2.84 | 3.583 (3) | 137 |
C26—H26···Cg2v | 0.93 | 2.87 | 3.579 (3) | 134 |
C29—H29···Cg2vi | 0.93 | 2.80 | 3.527 (3) | 135 |
Symmetry codes: (i) x−1, y−1, z; (ii) x−1, y, z; (iii) x, y−1, z; (iv) x+1, y+1, z; (v) x+1, y, z; (vi) x, y+1, z. |
Acknowledgements
The authors thank Science Foundation Ireland (SFI) for funding for the Solid State Pharmaceuticals Cluster (SSPC).
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound fenoxycarb, C17H19NO4 is an insect growth regulator with juvenile hormone activity (Paya et al., 2009; Sullivan et al., 2010; Kavallieratos et al., 2012; Goncu & Parlak, 2012). As part of our studies on the crystallization behaviour of this compound the crystal structure of fenocarb has been determined.
There are two chemically identical but conformationally different molecules in the asymmetric unit (Fig. 1). Although the two benzene rings adopt similar orientations [inter-ring dihedral angles, 62.21 (15) and 63.00 (14)°], the side chains differ in the region associated with the intermolecular N—H···O hydrogen-bonding interactions between the two molecules, with torsion angles O2—C13—C14—N1 and C13—C14—N1—C15 [-64.6 (4) and -85.2 (4)° in molecule 1] and O6—C30—C31—N2 and C30—C31—N2—C32 [57.4 (3) and -151.2 (3)° in molecule 2] (Fig. 2). The N2—H···O3 and N1—H···O3i hydrogen bonds bonds (Table 1) generate a one-dimensional motif that is parallel to [110] (Fig. 3). The hydrogen bonds are estimated to be of moderate strength at 8 kcal/mol (Lifson et al., 1979) and they are supported by weaker C—H···π contacts. With the aromatic ring centroids numbered in order of carbon number the distances for the interactions H26···Cg2, H29···Cg2, H9···Cg4 and H12···Cg4 are 2.87, 2.80, 2.86 and 2.86 Å respectively. The one-dimensional chains are built into two-dimensional sheets by further C—H···π contacts involving H19···Cg1, H22···Cg1, H2···Cg3 and H5···Cg3 are 2.92, 2.84, 2.85 and 2.85 Å respectively (Fig. 4). There are no π-π contacts involving the aromatic rings as adjacent rings are non-coplanar. The unit cell packing is shown in Fig.5.