(E)-N-Butyl-3-(3,4-dihy-droxy-phen-yl)acryl-amide hemihydrate.

In the title compound, C(13)H(17)NO(3)·0.5H(2)O, a new caffeic acid amide derivative, the solvent water mol-ecule lies on a twofold axis and the terminal ethyl group appears disordered with occupancy factors of 0.525 (6) and 0.475 (6). The benzene ring makes an angle of 17.3 (2)° with the C=C-C-O linker. The presence of an ethyl-enic spacer in the caffeic acid amide mol-ecule allows the formation of a conjugated system, strongly stabilized through π-electron delocalization. The C=C double bond in the linker is trans, similar to those previously reported in caffeic esters. The crystal is stabilized by O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds. The mol-ecules of the caffeic acid amide form a supermolecular planar structure through O-H⋯O hydrogen bonds between a hy-droxy group of one caffeic acid mol-ecule and a carbonyl O atom of another. These planes inter-act via C-H⋯O, O-H⋯O and N-H⋯O hydrogen bonds to form a three-dimensional network.

Related literature

For phenolic acid compounds used in biology and medicine, see: Altuğ et al. (2008 ▶). For synthetic work on the similar compounds, see: Bylov et al. (1999 ▶). For compounds with similar properties, see: Son & Lewis (2002 ▶); Menezes et al. (2001 ▶); Lee et al. (2005 ▶). For the structure analysis of a similar compound, see: Xia et al. (2008 ▶).

Experimental

Crystal data

C13H17NO3·0.5H2O

M = 244.29

Monoclinic,

a = 12.860 (7) Å

b = 14.928 (8) Å

c = 15.015 (11) Å

β = 113.967 (6)°

V = 2634 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.28 × 0.22 × 0.19 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T min = 0.977, T max = 0.983

7822 measured reflections

2581 independent reflections

1895 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.120

S = 1.04

2581 reflections

180 parameters

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812005570/bg2440sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005570/bg2440Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812005570/bg2440Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536812005570/bg2440Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H17NO3·0.5H2O	F(000) = 1048
Mr = 244.29	Dx = 1.232 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2581 reflections
a = 12.860 (7) Å	θ = 2.2–26.0°
b = 14.928 (8) Å	µ = 0.09 mm−1
c = 15.015 (11) Å	T = 296 K
β = 113.967 (6)°	Block, yellow
V = 2634 (3) Å3	0.28 × 0.22 × 0.19 mm
Z = 8

Bruker SMART APEX CCD diffractometer	2581 independent reflections
Radiation source: fine-focus sealed tube	1895 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −15→15
Tmin = 0.977, Tmax = 0.983	k = −18→15
7822 measured reflections	l = −18→18

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0532P)2 + 1.0544P] where P = (Fo2 + 2Fc2)/3
2581 reflections	(Δ/σ)max < 0.001
180 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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. The terminal C13 and methylene C12 have been treated disorderd.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O4	0.5000	0.79934 (9)	0.7500	0.0471 (4)
H4A	0.5047	0.7659	0.7973	0.057*	0.50
H4B	0.4953	0.7659	0.7027	0.057*	0.50
N1	0.63571 (12)	0.56741 (9)	−0.01730 (9)	0.0517 (4)
H1B	0.6878	0.5587	0.0401	0.062*
O1	0.83466 (10)	0.95089 (8)	0.33417 (8)	0.0653 (4)
H1A	0.8785	0.9099	0.3375	0.098*
O2	0.67900 (9)	1.07499 (8)	0.30337 (8)	0.0558 (3)
H2A	0.6254	1.1101	0.2869	0.084*
O3	0.51295 (9)	0.66595 (7)	−0.12054 (7)	0.0493 (3)
C1	0.53067 (15)	0.93015 (13)	0.09233 (13)	0.0656 (6)
H1	0.4611	0.9268	0.0388	0.079*
C2	0.55145 (15)	1.00043 (13)	0.15684 (13)	0.0638 (5)
H2	0.4962	1.0443	0.1459	0.077*
C3	0.65313 (13)	1.00632 (11)	0.23735 (11)	0.0491 (4)
C4	0.73642 (13)	0.94036 (11)	0.25296 (11)	0.0479 (4)
C5	0.71557 (13)	0.87094 (11)	0.18753 (11)	0.0498 (4)
H5	0.7713	0.8277	0.1977	0.060*
C6	0.61164 (14)	0.86440 (12)	0.10578 (11)	0.0522 (4)
C7	0.58305 (13)	0.79218 (12)	0.03400 (12)	0.0520 (4)
H7	0.5189	0.8017	−0.0233	0.062*
C8	0.63569 (13)	0.71565 (11)	0.03940 (11)	0.0483 (4)
H8	0.7026	0.7038	0.0935	0.058*
C9	0.59066 (12)	0.64825 (10)	−0.03873 (10)	0.0410 (4)
C10	0.60274 (16)	0.49214 (12)	−0.08466 (13)	0.0608 (5)
H10A	0.5750	0.5145	−0.1509	0.073*
H10B	0.5411	0.4598	−0.0776	0.073*
C11	0.69973 (18)	0.42951 (12)	−0.06711 (14)	0.0678 (5)
H11A	0.7326	0.4095	0.0002	0.081*
H11B	0.7585	0.4582	−0.0819	0.081*
C12	0.6467 (8)	0.3505 (6)	−0.1365 (8)	0.077 (2)	0.525 (6)
H12A	0.5909	0.3206	−0.1188	0.093*	0.525 (6)
H12B	0.6088	0.3720	−0.2029	0.093*	0.525 (6)
C13	0.7411 (5)	0.2857 (3)	−0.1286 (4)	0.097 (2)	0.525 (6)
H13A	0.7933	0.3148	−0.1503	0.146*	0.525 (6)
H13B	0.7089	0.2342	−0.1686	0.146*	0.525 (6)
H13C	0.7808	0.2673	−0.0620	0.146*	0.525 (6)
C12'	0.6881 (7)	0.3529 (8)	−0.1425 (9)	0.073 (2)	0.475 (6)
H12C	0.6553	0.3766	−0.2083	0.088*	0.475 (6)
H12D	0.7624	0.3283	−0.1305	0.088*	0.475 (6)
C13'	0.6133 (5)	0.2818 (4)	−0.1313 (4)	0.098 (2)	0.475 (6)
H13D	0.6453	0.2599	−0.0655	0.147*	0.475 (6)
H13E	0.6074	0.2334	−0.1752	0.147*	0.475 (6)
H13F	0.5391	0.3061	−0.1458	0.147*	0.475 (6)

	U11	U22	U33	U12	U13	U23
O4	0.0635 (10)	0.0324 (8)	0.0410 (8)	0.000	0.0166 (7)	0.000
N1	0.0572 (8)	0.0449 (8)	0.0358 (7)	0.0049 (6)	0.0011 (6)	0.0003 (6)
O1	0.0455 (6)	0.0695 (9)	0.0532 (7)	0.0148 (6)	−0.0085 (5)	−0.0213 (6)
O2	0.0493 (6)	0.0568 (7)	0.0478 (7)	0.0099 (5)	0.0059 (5)	−0.0159 (5)
O3	0.0523 (6)	0.0427 (7)	0.0359 (6)	−0.0050 (5)	0.0005 (5)	0.0034 (5)
C1	0.0442 (9)	0.0799 (14)	0.0484 (10)	0.0186 (9)	−0.0062 (8)	−0.0193 (9)
C2	0.0478 (9)	0.0726 (13)	0.0521 (10)	0.0236 (9)	0.0006 (8)	−0.0175 (9)
C3	0.0446 (8)	0.0536 (10)	0.0400 (8)	0.0058 (7)	0.0079 (7)	−0.0120 (7)
C4	0.0378 (8)	0.0562 (10)	0.0373 (8)	0.0061 (7)	0.0024 (6)	−0.0053 (7)
C5	0.0412 (8)	0.0523 (10)	0.0447 (9)	0.0120 (7)	0.0060 (7)	−0.0071 (7)
C6	0.0457 (9)	0.0580 (11)	0.0399 (9)	0.0090 (7)	0.0042 (7)	−0.0110 (8)
C7	0.0413 (8)	0.0614 (11)	0.0389 (8)	0.0057 (7)	0.0015 (7)	−0.0087 (7)
C8	0.0424 (8)	0.0521 (10)	0.0372 (8)	0.0028 (7)	0.0025 (7)	−0.0036 (7)
C9	0.0393 (7)	0.0435 (9)	0.0344 (8)	−0.0038 (6)	0.0092 (6)	0.0020 (6)
C10	0.0609 (11)	0.0474 (11)	0.0547 (10)	−0.0030 (8)	0.0033 (9)	−0.0042 (8)
C11	0.0828 (14)	0.0510 (11)	0.0556 (11)	0.0111 (10)	0.0138 (10)	0.0000 (9)
C12	0.096 (6)	0.048 (4)	0.090 (4)	−0.003 (4)	0.040 (4)	−0.018 (3)
C13	0.141 (5)	0.061 (3)	0.106 (4)	0.029 (3)	0.067 (3)	−0.009 (2)
C12'	0.076 (5)	0.066 (5)	0.089 (4)	−0.003 (4)	0.044 (4)	−0.008 (3)
C13'	0.113 (5)	0.074 (4)	0.109 (4)	−0.002 (3)	0.046 (4)	0.001 (3)

O4—H4A	0.8501	C8—C9	1.474 (2)
O4—H4B	0.8501	C8—H8	0.9300
N1—C9	1.321 (2)	C10—C11	1.494 (3)
N1—C10	1.455 (2)	C10—H10A	0.9700
N1—H1B	0.8600	C10—H10B	0.9700
O1—C4	1.3624 (19)	C11—C12	1.537 (9)
O1—H1A	0.8200	C11—C12'	1.574 (11)
O2—C3	1.3699 (19)	C11—H11A	0.9700
O2—H2A	0.8200	C11—H11B	0.9700
O3—C9	1.2571 (18)	C12—C13	1.519 (10)
C1—C2	1.378 (2)	C12—H12A	0.9700
C1—C6	1.385 (2)	C12—H12B	0.9700
C1—H1	0.9300	C13—H13A	0.9600
C2—C3	1.377 (2)	C13—H13B	0.9600
C2—H2	0.9300	C13—H13C	0.9600
C3—C4	1.403 (2)	C12'—C13'	1.487 (11)
C4—C5	1.377 (2)	C12'—H12C	0.9700
C5—C6	1.403 (2)	C12'—H12D	0.9700
C5—H5	0.9300	C13'—H13D	0.9600
C6—C7	1.462 (2)	C13'—H13E	0.9600
C7—C8	1.314 (2)	C13'—H13F	0.9600
C7—H7	0.9300
H4A—O4—H4B	108.0	N1—C10—C11	111.97 (15)
C9—N1—C10	124.15 (14)	N1—C10—H10A	109.2
C9—N1—H1B	117.9	C11—C10—H10A	109.2
C10—N1—H1B	117.9	N1—C10—H10B	109.2
C4—O1—H1A	109.5	C11—C10—H10B	109.2
C3—O2—H2A	109.5	H10A—C10—H10B	107.9
C2—C1—C6	121.15 (15)	C10—C11—C12	104.6 (4)
C2—C1—H1	119.4	C10—C11—C12'	120.0 (4)
C6—C1—H1	119.4	C10—C11—H11A	110.8
C3—C2—C1	120.63 (15)	C12—C11—H11A	110.8
C3—C2—H2	119.7	C12'—C11—H11A	113.6
C1—C2—H2	119.7	C10—C11—H11B	110.8
O2—C3—C2	123.23 (14)	C12—C11—H11B	110.8
O2—C3—C4	117.38 (14)	C12'—C11—H11B	90.6
C2—C3—C4	119.37 (15)	H11A—C11—H11B	108.9
O1—C4—C5	124.49 (14)	C13—C12—C11	108.4 (6)
O1—C4—C3	115.86 (14)	C13—C12—H12A	110.0
C5—C4—C3	119.65 (14)	C11—C12—H12A	110.0
C4—C5—C6	121.09 (14)	C13—C12—H12B	110.0
C4—C5—H5	119.5	C11—C12—H12B	110.0
C6—C5—H5	119.5	H12A—C12—H12B	108.4
C1—C6—C5	118.09 (15)	C13'—C12'—C11	108.3 (6)
C1—C6—C7	117.78 (15)	C13'—C12'—H12C	110.0
C5—C6—C7	124.13 (15)	C11—C12'—H12C	110.0
C8—C7—C6	128.82 (15)	C13'—C12'—H12D	110.0
C8—C7—H7	115.6	C11—C12'—H12D	110.0
C6—C7—H7	115.6	H12C—C12'—H12D	108.4
C7—C8—C9	121.24 (15)	C12'—C13'—H13D	109.5
C7—C8—H8	119.4	C12'—C13'—H13E	109.5
C9—C8—H8	119.4	H13D—C13'—H13E	109.5
O3—C9—N1	121.73 (14)	C12'—C13'—H13F	109.5
O3—C9—C8	122.27 (14)	H13D—C13'—H13F	109.5
N1—C9—C8	116.00 (13)	H13E—C13'—H13F	109.5
C6—C1—C2—C3	−0.9 (3)	C5—C6—C7—C8	12.7 (3)
C1—C2—C3—O2	179.32 (18)	C6—C7—C8—C9	176.70 (16)
C1—C2—C3—C4	0.6 (3)	C10—N1—C9—O3	1.0 (2)
O2—C3—C4—O1	1.2 (2)	C10—N1—C9—C8	−179.89 (15)
C2—C3—C4—O1	179.99 (17)	C7—C8—C9—O3	12.8 (2)
O2—C3—C4—C5	−178.59 (15)	C7—C8—C9—N1	−166.28 (16)
C2—C3—C4—C5	0.2 (3)	C9—N1—C10—C11	148.87 (17)
O1—C4—C5—C6	179.54 (17)	N1—C10—C11—C12	174.2 (4)
C3—C4—C5—C6	−0.7 (3)	N1—C10—C11—C12'	−169.8 (4)
C2—C1—C6—C5	0.4 (3)	C10—C11—C12—C13	176.3 (5)
C2—C1—C6—C7	−179.91 (18)	C12'—C11—C12—C13	37.4 (19)
C4—C5—C6—C1	0.4 (3)	C10—C11—C12'—C13'	−74.3 (8)
C4—C5—C6—C7	−179.25 (17)	C12—C11—C12'—C13'	−27.1 (17)
C1—C6—C7—C8	−166.91 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3i	0.85	1.91	2.7402 (19)	165
O4—H4B···O3ii	0.85	1.91	2.7402 (19)	165
N1—H1B···O2iii	0.86	2.29	3.129 (2)	165
N1—H1B···O1iii	0.86	2.58	3.143 (3)	124
O1—H1A···O3iv	0.82	1.94	2.7378 (19)	162
O2—H2A···O4v	0.82	2.00	2.8217 (18)	177
C7—H7···O3	0.93	2.48	2.837 (2)	103
C8—H8···O2iii	0.93	2.55	3.330 (2)	142

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3i	0.85	1.91	2.7402 (19)	165
O4—H4B⋯O3ii	0.85	1.91	2.7402 (19)	165
N1—H1B⋯O2iii	0.86	2.29	3.129 (2)	165
N1—H1B⋯O1iii	0.86	2.58	3.143 (3)	124
O1—H1A⋯O3iv	0.82	1.94	2.7378 (19)	162
O2—H2A⋯O4v	0.82	2.00	2.8217 (18)	177
C7—H7⋯O3	0.93	2.48	2.837 (2)	103
C8—H8⋯O2iii	0.93	2.55	3.330 (2)	142

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .