Ethyl N-[2-(4-phen­oxy­phen­oxy)eth­yl]carbamate

Karpinska, J.; Kuhs, M.; Rasmuson, A.; Erxleben, A.; McArdle, P.

doi:10.1107/S1600536812037105

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 10| October 2012| Pages o2834-o2835

https://doi.org/10.1107/S1600536812037105

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Ethyl N-[2-(4-phenoxyphenoxy)ethyl]carbamate

Jolanta Karpinska,^a Manuel Kuhs,^b Ake Rasmuson,^b Andrea Erxleben ^a and Patrick McArdle ^a ^*

^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

(Received 14 August 2012; accepted 28 August 2012; online 5 September 2012)

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 asymmetric unit. 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

C₁₇H₁₉NO₄
M_r = 301.33
Triclinic, $[P \overline 1]$
a = 5.9035 (3) Å
b = 7.5712 (4) Å
c = 35.373 (2) Å
α = 85.618 (5)°
β = 86.213 (5)°
γ = 89.046 (4)°
V = 1572.88 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 150 K
0.40 × 0.30 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur, Sapphire3 CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.894, T_max = 1.000
25379 measured reflections
5745 independent reflections
2937 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.126
S = 0.97
5745 reflections
399 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯Cg1^iv	0.93	2.84	3.583 (3)	137
C26—H26⋯Cg2^v	0.93	2.87	3.579 (3)	134
C29—H29⋯Cg2^vi	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.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812037105/zs2230sup1.cif

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

checkCIF report

Comment top

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.

Related literature top

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).

Experimental top

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.

Structure description top

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: 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).

Figures top

	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.

Ethyl N-[2-(4-phenoxyphenoxy)ethyl]carbamate top

Crystal data top

C₁₇H₁₉NO₄	Z = 4
M_r = 301.33	F(000) = 640
Triclinic, P1	D_x = 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

Data collection top

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	R_int = 0.074
Detector resolution: 16.1048 pixels mm^-1	θ_max = 25.4°, θ_min = 2.8°
ω scans	h = −6→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −9→9
T_min = 0.894, T_max = 1.000	l = −42→36
25379 measured reflections

Refinement top

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(F_o²) + (0.0202P)²] where P = (F_o² + 2F_c²)/3
5745 reflections	(Δ/σ)_max < 0.001
399 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₇H₁₉NO₄	γ = 89.046 (4)°
M_r = 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)°

Data collection top

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)
T_min = 0.894, T_max = 1.000	R_int = 0.074
25379 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 0.97	Δρ_max = 0.21 e Å⁻³
5745 reflections	Δρ_min = −0.22 e Å⁻³
399 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···Cg1^iv	0.93	2.84	3.583 (3)	137
C26—H26···Cg2^v	0.93	2.87	3.579 (3)	134
C29—H29···Cg2^vi	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
M_r	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)
T_min, T_max	0.894, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	25379, 5745, 2937
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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···Cg1^iv	0.93	2.84	3.583 (3)	137
C26—H26···Cg2^v	0.93	2.87	3.579 (3)	134
C29—H29···Cg2^vi	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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