N,N'-(Phenyl-imino-dimethyl-ene)di-prop-2-enamide hemihydrate.

In the title compound, C(14)H(17)N(3)O(2)·0.5H(2)O, the asymmetric unit consists of an N,N'-(phenyl-imino-dimethyl-ene)diprop-2-enamide mol-ecule and one half-mol-ecule of water, with the O atom of the latter having 2 site symmetry. The supra-molecular architecture is framed by the inter-play of two-dimensional networks of both O-H⋯O and N-H⋯O inter-actions supported by C-H⋯O and edge-to-face C-H⋯π inter-actions.

Related literature

For a detailed description of Mannich bases and their applications, see: Friedrich et al. (1991 ▶); Bohme & Mannich (1955 ▶); Afsah et al. (2008 ▶); Terzioglu et al. (2006 ▶); Ravichandran et al. (2007 ▶); Pandeya et al. (2000 ▶). For hydrogen bonds, see: Desiraju & Steiner (1999 ▶); Jeffrey (1997 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Etter (1990 ▶).

Experimental

Crystal data

C14H17N3O2·0.5H2O

M = 268.31

Orthorhombic,

a = 17.074 (2) Å

b = 9.8366 (15) Å

c = 16.316 (2) Å

V = 2740.3 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.09 mm−1

T = 90 K

0.30 × 0.23 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler

Absorption correction: none

9467 measured reflections

5065 independent reflections

3885 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.120

S = 1.02

5065 reflections

249 parameters

All H-atom parameters refined

Δρmax = 0.39 e Å−3

Δρmin = −0.28 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017784/lh2820sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017784/lh2820Isup2.hkl

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

C14H17N3O2·0.5H2O	Dx = 1.301 Mg m−3
Mr = 268.31	Melting point: 398 K
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 34434 reflections
a = 17.074 (2) Å	θ = 2.5–33.0°
b = 9.8366 (15) Å	µ = 0.09 mm−1
c = 16.316 (2) Å	T = 90 K
V = 2740.3 (6) Å3	Fragment, colorless
Z = 8	0.30 × 0.23 × 0.12 mm
F(000) = 1144

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler	3885 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
graphite	θmax = 33.0°, θmin = 2.7°
ω and φ scans	h = −26→26
9467 measured reflections	k = −15→15
5065 independent reflections	l = −24→24

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)] = 0.045	Hydrogen site location: difference Fourier map
wR(F2) = 0.120	All H-atom parameters refined
S = 1.02	w = 1/[σ2(Fo2) + (0.0597P)2 + 0.7128P] where P = (Fo2 + 2Fc2)/3
5065 reflections	(Δ/σ)max = 0.001
249 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.28 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.

	x	y	z	Uiso*/Ueq
N1	0.80007 (5)	0.89440 (8)	0.13232 (5)	0.01594 (16)
C2	0.88056 (6)	0.84769 (10)	0.12071 (6)	0.01569 (17)
N3	0.89921 (5)	0.80690 (8)	0.03825 (5)	0.01545 (16)
C4	0.91579 (6)	0.66584 (10)	0.02225 (6)	0.01665 (18)
N5	0.85082 (5)	0.59623 (8)	−0.01804 (5)	0.01671 (16)
C6	0.85921 (6)	0.52348 (9)	−0.08750 (6)	0.01635 (18)
O7	0.92364 (4)	0.50903 (8)	−0.12139 (5)	0.02232 (17)
C8	0.78566 (6)	0.46251 (11)	−0.11941 (6)	0.0210 (2)
C9	0.78569 (7)	0.37886 (13)	−0.18250 (7)	0.0267 (2)
C10	0.73876 (5)	0.80842 (9)	0.13486 (5)	0.01421 (17)
O11	0.74626 (4)	0.68455 (7)	0.12367 (4)	0.01761 (15)
C12	0.66234 (6)	0.87457 (10)	0.15303 (6)	0.01837 (19)
C13	0.59676 (6)	0.80534 (12)	0.16321 (7)	0.0247 (2)
C14	0.90493 (5)	0.90267 (10)	−0.02424 (6)	0.01502 (17)
C15	0.91823 (5)	0.86297 (11)	−0.10565 (6)	0.01785 (19)
C16	0.92620 (6)	0.96063 (12)	−0.16649 (6)	0.0226 (2)
C17	0.92139 (6)	1.09817 (12)	−0.14964 (7)	0.0249 (2)
C18	0.90668 (6)	1.13762 (11)	−0.06939 (7)	0.0229 (2)
C19	0.89752 (6)	1.04206 (10)	−0.00757 (7)	0.01868 (19)
OW	1.0000	0.37093 (12)	−0.2500	0.0356 (3)
H1	0.7899 (9)	0.9829 (15)	0.1371 (9)	0.028 (4)*
H2A	0.8901 (7)	0.7705 (14)	0.1559 (8)	0.018 (3)*
H2B	0.9140 (7)	0.9206 (14)	0.1393 (8)	0.015 (3)*
H4A	0.9616 (8)	0.6566 (13)	−0.0140 (8)	0.018 (3)*
H4B	0.9274 (7)	0.6225 (13)	0.0743 (8)	0.017 (3)*
H5	0.8046 (9)	0.6058 (14)	0.0045 (9)	0.027 (3)*
H8	0.7378 (9)	0.4864 (15)	−0.0914 (10)	0.035 (4)*
H9A	0.7377 (8)	0.3357 (15)	−0.2005 (9)	0.029 (4)*
H9B	0.8348 (9)	0.3542 (15)	−0.2119 (10)	0.036 (4)*
H12	0.6636 (9)	0.9714 (16)	0.1589 (10)	0.034 (4)*
H13A	0.5471 (8)	0.8504 (15)	0.1751 (8)	0.027 (3)*
H13B	0.5952 (10)	0.7040 (19)	0.1577 (11)	0.045 (5)*
H15	0.9212 (7)	0.7696 (15)	−0.1208 (8)	0.018 (3)*
H16	0.9353 (9)	0.9338 (15)	−0.2219 (9)	0.031 (4)*
H17	0.9294 (9)	1.1688 (16)	−0.1936 (10)	0.038 (4)*
H18	0.9027 (8)	1.2309 (16)	−0.0557 (9)	0.029 (4)*
H19	0.8871 (8)	1.0736 (14)	0.0458 (9)	0.022 (3)*
HW	1.0232 (10)	0.4232 (17)	−0.2832 (11)	0.048 (5)*

	U11	U22	U33	U12	U13	U23
N1	0.0168 (4)	0.0121 (3)	0.0189 (4)	−0.0001 (3)	0.0009 (3)	−0.0017 (3)
C2	0.0163 (4)	0.0169 (4)	0.0138 (4)	0.0001 (3)	−0.0014 (3)	−0.0017 (3)
N3	0.0195 (4)	0.0131 (3)	0.0137 (3)	0.0013 (3)	0.0007 (3)	−0.0011 (3)
C4	0.0184 (4)	0.0141 (4)	0.0175 (4)	0.0024 (3)	−0.0011 (3)	−0.0010 (3)
N5	0.0166 (4)	0.0167 (4)	0.0168 (4)	−0.0006 (3)	0.0038 (3)	−0.0035 (3)
C6	0.0181 (4)	0.0153 (4)	0.0157 (4)	0.0014 (3)	0.0026 (3)	−0.0010 (3)
O7	0.0176 (3)	0.0259 (4)	0.0235 (4)	0.0004 (3)	0.0054 (3)	−0.0080 (3)
C8	0.0177 (4)	0.0243 (5)	0.0210 (5)	−0.0002 (4)	0.0027 (3)	−0.0048 (4)
C9	0.0219 (5)	0.0343 (6)	0.0241 (5)	0.0014 (4)	−0.0020 (4)	−0.0094 (4)
C10	0.0172 (4)	0.0133 (4)	0.0122 (4)	−0.0002 (3)	−0.0010 (3)	0.0001 (3)
O11	0.0213 (3)	0.0118 (3)	0.0197 (3)	0.0002 (2)	0.0004 (3)	−0.0009 (2)
C12	0.0191 (4)	0.0148 (4)	0.0212 (5)	0.0011 (3)	0.0008 (3)	−0.0012 (3)
C13	0.0204 (5)	0.0241 (5)	0.0294 (5)	−0.0018 (4)	0.0037 (4)	−0.0072 (4)
C14	0.0119 (4)	0.0163 (4)	0.0169 (4)	−0.0010 (3)	−0.0011 (3)	0.0011 (3)
C15	0.0154 (4)	0.0199 (5)	0.0182 (4)	0.0000 (3)	0.0031 (3)	0.0010 (4)
C16	0.0184 (4)	0.0305 (6)	0.0189 (5)	−0.0014 (4)	0.0038 (4)	0.0055 (4)
C17	0.0208 (5)	0.0264 (5)	0.0274 (5)	−0.0039 (4)	0.0000 (4)	0.0116 (4)
C18	0.0206 (5)	0.0177 (5)	0.0305 (6)	−0.0034 (3)	−0.0044 (4)	0.0054 (4)
C19	0.0180 (4)	0.0164 (4)	0.0216 (5)	−0.0016 (3)	−0.0032 (3)	−0.0002 (3)
OW	0.0567 (8)	0.0170 (5)	0.0330 (7)	0.000	0.0289 (6)	0.000

N1—C10	1.3465 (12)	C10—O11	1.2387 (11)
N1—C2	1.4613 (13)	C10—C12	1.4878 (14)
N1—H1	0.891 (15)	C12—C13	1.3210 (15)
C2—N3	1.4397 (12)	C12—H12	0.957 (16)
C2—H2A	0.966 (13)	C13—H13A	0.976 (14)
C2—H2B	0.966 (13)	C13—H13B	1.001 (19)
N3—C14	1.3915 (12)	C14—C15	1.4030 (14)
N3—C4	1.4400 (12)	C14—C19	1.4036 (14)
C4—N5	1.4599 (12)	C15—C16	1.3880 (14)
C4—H4A	0.984 (13)	C15—H15	0.953 (14)
C4—H4B	0.970 (13)	C16—C17	1.3830 (17)
N5—C6	1.3480 (12)	C16—H16	0.954 (15)
N5—H5	0.876 (15)	C17—C18	1.3886 (17)
C6—O7	1.2394 (12)	C17—H17	1.008 (16)
C6—C8	1.4859 (14)	C18—C19	1.3876 (15)
C8—C9	1.3178 (15)	C18—H18	0.947 (16)
C8—H8	0.966 (16)	C19—H19	0.942 (14)
C9—H9A	0.969 (14)	OW—HW	0.845 (17)
C9—H9B	0.996 (16)
C10—N1—C2	122.52 (8)	H9A—C9—H9B	117.4 (12)
C10—N1—H1	117.3 (10)	O11—C10—N1	122.20 (9)
C2—N1—H1	120.2 (10)	O11—C10—C12	123.38 (9)
N3—C2—N1	114.64 (8)	N1—C10—C12	114.41 (8)
N3—C2—H2A	107.4 (8)	C13—C12—C10	122.88 (9)
N1—C2—H2A	109.2 (8)	C13—C12—H12	121.3 (9)
N3—C2—H2B	111.7 (8)	C10—C12—H12	115.8 (9)
N1—C2—H2B	106.4 (8)	C12—C13—H13A	121.8 (9)
H2A—C2—H2B	107.3 (11)	C12—C13—H13B	121.6 (10)
C14—N3—C2	120.77 (8)	H13A—C13—H13B	116.6 (13)
C14—N3—C4	120.38 (8)	N3—C14—C15	121.10 (9)
C2—N3—C4	118.78 (8)	N3—C14—C19	120.87 (9)
N3—C4—N5	112.59 (8)	C15—C14—C19	118.03 (9)
N3—C4—H4A	110.7 (7)	C16—C15—C14	120.02 (10)
N5—C4—H4A	106.8 (7)	C16—C15—H15	118.5 (8)
N3—C4—H4B	107.8 (8)	C14—C15—H15	121.5 (8)
N5—C4—H4B	110.0 (8)	C17—C16—C15	121.95 (10)
H4A—C4—H4B	108.8 (11)	C17—C16—H16	118.0 (9)
C6—N5—C4	123.15 (8)	C15—C16—H16	120.1 (9)
C6—N5—H5	120.4 (10)	C16—C17—C18	118.13 (10)
C4—N5—H5	116.4 (9)	C16—C17—H17	121.7 (9)
O7—C6—N5	122.03 (9)	C18—C17—H17	120.2 (9)
O7—C6—C8	123.19 (9)	C19—C18—C17	121.10 (10)
N5—C6—C8	114.78 (8)	C19—C18—H18	118.4 (9)
C9—C8—C6	121.70 (9)	C17—C18—H18	120.5 (9)
C9—C8—H8	121.4 (9)	C18—C19—C14	120.72 (10)
C6—C8—H8	116.9 (9)	C18—C19—H19	118.1 (8)
C8—C9—H9A	120.7 (9)	C14—C19—H19	121.2 (8)
C8—C9—H9B	121.9 (9)
C10—N1—C2—N3	75.00 (12)	N1—C10—C12—C13	−175.46 (10)
N1—C2—N3—C14	70.15 (11)	C2—N3—C14—C15	−175.96 (8)
N1—C2—N3—C4	−112.95 (9)	C4—N3—C14—C15	7.19 (13)
C14—N3—C4—N5	−78.90 (10)	C2—N3—C14—C19	4.02 (13)
C2—N3—C4—N5	104.19 (10)	C4—N3—C14—C19	−172.83 (8)
N3—C4—N5—C6	127.89 (10)	N3—C14—C15—C16	−177.94 (9)
C4—N5—C6—O7	1.15 (15)	C19—C14—C15—C16	2.09 (13)
C4—N5—C6—C8	−179.03 (9)	C14—C15—C16—C17	−0.07 (15)
O7—C6—C8—C9	5.99 (17)	C15—C16—C17—C18	−1.19 (16)
N5—C6—C8—C9	−173.83 (11)	C16—C17—C18—C19	0.39 (15)
C2—N1—C10—O11	−3.45 (14)	C17—C18—C19—C14	1.67 (15)
C2—N1—C10—C12	175.89 (8)	N3—C14—C19—C18	177.14 (9)
O11—C10—C12—C13	3.88 (16)	C15—C14—C19—C18	−2.88 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O11	0.876 (15)	2.318 (15)	3.0476 (11)	140.8 (12)
C4—H4A···O7	0.984 (13)	2.366 (13)	2.8089 (12)	106.5 (9)
C15—H15···O7	0.953 (14)	2.563 (14)	3.4922 (14)	165.1 (10)
OW—HW···O7i	0.845 (17)	1.990 (17)	2.8193 (9)	166.7 (16)
N1—H1···O11ii	0.891 (15)	2.089 (15)	2.9651 (11)	167.4 (14)
C2—H2B···Cg1iii	0.966 (13)	3.178	3.874	130.40
C8—H8···Cg1iv	0.966 (16)	2.571	3.444	150.57

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯O11	0.876 (15)	2.318 (15)	3.0476 (11)	140.8 (12)
C4—H4A⋯O7	0.984 (13)	2.366 (13)	2.8089 (12)	106.5 (9)
C15—H15⋯O7	0.953 (14)	2.563 (14)	3.4922 (14)	165.1 (10)
OW—HW⋯O7i	0.845 (17)	1.990 (17)	2.8193 (9)	166.7 (16)
N1—H1⋯O11ii	0.891 (15)	2.089 (15)	2.9651 (11)	167.4 (14)
C2—H2B⋯Cg1iii	0.966 (13)	3.178	3.874	130.40
C8—H8⋯Cg1iv	0.966 (16)	2.571 (15)	3.4444 (12)	150.6 (13)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . Cg1 is the centroid of the C14–C19 ring.