N-(4-Ethoxy­phenyl)-2-[(4-ethoxy­phenyl­carbamoyl)­methoxy]­acet­amide monohydrate, a supramolecular chain structure formed by hydrogen bonds

In the title compound, C₂₀H₂₄N₂O₅·H₂O, the mol­ecules are linked to each other by hydrogen bonds, and form a supramolecular chain structure. The organic and water mol­ecules lie on crystallographic twofold rotation axes.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• H-atom completeness 93%
• R factor = 0.049
• wR factor = 0.124
• Data-to-parameter ratio = 13.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and the formula from the _atom_site* data.
          Atom count from _chemical_formula_sum:C20 H26 N2 O6
          Atom count from the _atom_site data:  C20 H24 N2 O6

CELLZ_01
         From the CIF: _cell_formula_units_Z    4
         From the CIF: _chemical_formula_sum  C20 H26 N2 O6
         TEST: Compare cell contents of formula and atom_site data

         atom    Z*formula  cif sites diff
         C         80.00     80.00    0.00
         H        104.00     96.00    8.00
         N          8.00      8.00    0.00
         O         24.00     24.00    0.00
          Difference between formula and atom_site contents detected.
          WARNING: H atoms missing from atom site list. Is this intentional?

---

S1. Comment

Hydrogen-bonding interactions are regarded as among the most important driving forces in crystal engineering (Ranganaham et al., 1999). Whitesides et al. (1995) have designed a family of self-assembled aggregates by hydrogen bonding between cyanuric acid and melamine. Recently, this method was also introduced for the construction of supramolecular nanostructures (Kosonen et al., 2000). In this work, hydrogen bonds between water and the O atoms of C₂₀H₂₄N₂O₅ were used to form a novel supramolecular cavity.

In the title compound, (I), the water molecule (O4) forms two hydrogen bonds with O2 and a symmetry-equivalent O2, the O4···O2 distance being 2.813 (3) Å, and the angle at O4 being 103.7 (2) Å. N—H forms a hydrogen bond with an O atom of another molecule (Table 2).

The molecules are linked by O···O and N···O hydrogen bonds and construct a one-dimensional supramolecular chain structure (Fig. 2). Adjacent molecules adopt opposite orientations due to the bulk of the benzene rings. A cavity formed by hydrogen bonds is observed (Fig. 3).

S2. Experimental

The title compound was prepared by the direct reaction of chlorocarbonylmethoxyacetyl chloride with 4-ethoxyphenylamine in pyridine. The resulting mixture was separated by flash chromatography (ethyl acetate/benzene, 1:4). Suitable crystals were obtained by evaporation of an ethanol solution. Spectroscopic analysis, IR (KBr, ν, cm⁻¹): 1666, 1117, 1235; ¹H NMR (CDCl₃, δ): 4.24 (s, 2H), 8.23 (s, 1H), 6.81–7.53 (d, 1H), 3.87–4.13 (d, 2H), 1.25–1.42 (d, 3H); analysis, calculated for C₂₀H₂₆N₂O₆: C 61.53, H 6.71, N 7.17%; found: C 61.94, H 6.44, N 7.06%.

S3. Refinement

All H atoms were positioned geometrically and refined with riding model constraints, except for those on the water molecule, which were not included.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. Dashed lines indicate the hydrogen-bonding interactions.
	Fig. 2. The chain-like supramolecular structure of (I). H atoms have been omitted for clarity. Dashed lines indicate the hydrogen-bonding interactions.
	Fig. 3. Supramolecular cavity formed by hydrogen bonds. H atoms are omitted for clarity. Dashed lines indicate the hydrogen bonding interactions.

N-(4-Ethoxyphenyl)-2-[(4-ethoxyphenylcarbamoyl)methoxy]acetamide monohydrate

Crystal data

C20H24N2O5·H2O	F(000) = 832
Mr = 390.43	Dx = 1.285 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 30.575 (5) Å	Cell parameters from 25 reflections
b = 7.929 (1) Å	θ = 2.7–12.1°
c = 8.356 (2) Å	µ = 0.10 mm^−1
β = 95.09 (2)°	T = 294 K
V = 2017.7 (6) Å^3	Rhomboidal plate, colourless
Z = 4	0.70 × 0.52 × 0.06 mm

Data collection

Siemens P4 diffractometer	Rint = 0.034
Radiation source: normal-focus sealed tube	θmax = 25.0°, θmin = 2.7°
Graphite monochromator	h = 0→36
ω scans	k = 0→9
2017 measured reflections	l = −9→9
1771 independent reflections	3 standard reflections every 97 reflections
880 reflections with I > 2σ(I)	intensity decay: 4.4%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.124	w = 1/[σ^2(Fo^2) + (0.0559P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.84	(Δ/σ)max < 0.001
1771 reflections	Δρmax = 0.15 e Å^−3
130 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0027 (6)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.0000	0.1183 (3)	1.2500	0.0469 (7)
O2	0.06068 (6)	0.1831 (2)	0.9153 (2)	0.0536 (6)
O3	0.18409 (7)	−0.4539 (3)	0.8299 (3)	0.0700 (7)
N	0.06454 (7)	−0.0315 (3)	1.0971 (3)	0.0458 (6)
H0N	0.0543	−0.0663	1.1838	0.055*
C1	0.02234 (9)	0.2202 (3)	1.1447 (3)	0.0451 (7)
H1A	0.0405	0.3010	1.2074	0.054*
H1B	0.0010	0.2829	1.0756	0.054*
C2	0.05087 (8)	0.1196 (3)	1.0418 (3)	0.0423 (7)
C3	0.09447 (9)	−0.1403 (3)	1.0260 (3)	0.0438 (7)
C4	0.09012 (9)	−0.3115 (3)	1.0404 (3)	0.0497 (8)
H4	0.0673	−0.3546	1.0947	0.060*
C5	0.11898 (9)	−0.4216 (3)	0.9759 (3)	0.0531 (8)
H5	0.1155	−0.5374	0.9869	0.064*
C6	0.15272 (9)	−0.3593 (4)	0.8956 (3)	0.0531 (8)
C7	0.15682 (10)	−0.1875 (4)	0.8780 (4)	0.0672 (10)
H7	0.1794	−0.1448	0.8221	0.081*
C8	0.12789 (9)	−0.0774 (4)	0.9423 (4)	0.0620 (9)
H8	0.1309	0.0383	0.9292	0.074*
C9	0.18480 (10)	−0.6306 (4)	0.8604 (4)	0.0674 (10)
H9A	0.1582	−0.6831	0.8115	0.081*
H9B	0.1868	−0.6521	0.9751	0.081*
C10	0.22438 (11)	−0.7002 (4)	0.7884 (4)	0.0916 (12)
H10A	0.2215	−0.6816	0.6745	0.110*
H10B	0.2266	−0.8190	0.8097	0.110*
H10C	0.2503	−0.6444	0.8352	0.110*
O4	0.0000	0.4023 (4)	0.7500	0.0973 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0530 (16)	0.0415 (15)	0.0502 (16)	0.000	0.0261 (14)	0.000
O2	0.0674 (13)	0.0465 (12)	0.0507 (12)	0.0014 (10)	0.0269 (10)	0.0053 (10)
O3	0.0613 (14)	0.0569 (14)	0.0966 (17)	0.0119 (11)	0.0335 (12)	0.0005 (12)
N	0.0504 (15)	0.0452 (14)	0.0445 (14)	0.0027 (12)	0.0184 (12)	0.0052 (12)
C1	0.0542 (17)	0.0384 (16)	0.0450 (15)	−0.0022 (14)	0.0175 (14)	0.0004 (14)
C2	0.0394 (15)	0.0439 (17)	0.0442 (16)	−0.0052 (14)	0.0081 (13)	−0.0038 (15)
C3	0.0433 (16)	0.0445 (17)	0.0450 (16)	0.0016 (14)	0.0123 (13)	0.0023 (14)
C4	0.0441 (17)	0.0450 (17)	0.0623 (19)	−0.0005 (15)	0.0175 (15)	0.0075 (16)
C5	0.0516 (18)	0.0377 (17)	0.072 (2)	0.0021 (15)	0.0134 (16)	0.0011 (15)
C6	0.0466 (17)	0.0506 (19)	0.0641 (19)	0.0053 (16)	0.0164 (15)	−0.0034 (16)
C7	0.054 (2)	0.061 (2)	0.092 (2)	0.0011 (18)	0.0368 (18)	0.009 (2)
C8	0.0539 (19)	0.0441 (18)	0.092 (2)	0.0013 (15)	0.0295 (18)	0.0070 (17)
C9	0.059 (2)	0.059 (2)	0.085 (2)	0.0143 (17)	0.0084 (18)	−0.0059 (19)
C10	0.086 (3)	0.089 (3)	0.102 (3)	0.040 (2)	0.024 (2)	−0.005 (2)
O4	0.111 (3)	0.077 (2)	0.108 (3)	0.000	0.033 (2)	0.000

Geometric parameters (Å, º)

O1—C1^i	1.414 (3)	C1—C2	1.506 (3)
O1—C1	1.414 (3)	C3—C4	1.371 (3)
O2—C2	1.232 (3)	C3—C8	1.381 (3)
O2—O4	2.813 (3)	C4—C5	1.384 (3)
O3—C6	1.370 (3)	C5—C6	1.371 (3)
O3—C9	1.424 (3)	C6—C7	1.377 (4)
N—C2	1.338 (3)	C7—C8	1.384 (4)
N—C3	1.425 (3)	C9—C10	1.503 (4)
C1^i—O1—C1	110.3 (3)	C8—C3—N	121.6 (2)
C2—O2—O4	118.28 (16)	C3—C4—C5	121.3 (3)
C6—O3—C9	117.8 (2)	C6—C5—C4	119.8 (3)
C2—N—C3	126.2 (2)	O3—C6—C5	125.6 (3)
O1—C1—C2	112.9 (2)	O3—C6—C7	115.2 (3)
O2—C2—N	124.8 (2)	C5—C6—C7	119.2 (3)
O2—C2—C1	118.1 (2)	C6—C7—C8	121.0 (3)
N—C2—C1	117.1 (2)	C3—C8—C7	119.7 (3)
C4—C3—C8	118.9 (3)	O3—C9—C10	106.8 (3)
C4—C3—N	119.5 (2)
C1^i—O1—C1—C2	173.6 (3)	C3—C4—C5—C6	0.0 (5)
O4—O2—C2—N	149.7 (2)	C9—O3—C6—C5	−6.7 (5)
O4—O2—C2—C1	−31.8 (3)	C9—O3—C6—C7	172.7 (3)
C3—N—C2—O2	3.9 (4)	C4—C5—C6—O3	178.2 (3)
C3—N—C2—C1	−174.5 (2)	C4—C5—C6—C7	−1.2 (5)
O1—C1—C2—O2	157.7 (2)	O3—C6—C7—C8	−178.4 (3)
O1—C1—C2—N	−23.7 (3)	C5—C6—C7—C8	1.1 (5)
C2—N—C3—C4	−148.3 (3)	C4—C3—C8—C7	−1.4 (5)
C2—N—C3—C8	31.7 (4)	N—C3—C8—C7	178.6 (3)
C8—C3—C4—C5	1.3 (5)	C6—C7—C8—C3	0.3 (5)
N—C3—C4—C5	−178.7 (3)	C6—O3—C9—C10	−174.9 (3)

Symmetry code: (i) −x, y, −z+5/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H0N···O2^ii	0.86	2.14	2.930 (3)	153
C4—H4···O4^iii	0.93	2.56	3.469 (3)	167

Symmetry codes: (ii) x, −y, z+1/2; (iii) −x, −y, −z+2.