1-[5-Acetyl-4-(4-bromo-phen-yl)-2,6-dimethyl-1,4-dihydro-pyridin-3-yl]ethanone monohydrate.

The 1,4-dihydro-pyridine ring in the title hydrate, C(17)H(18)BrNO(2)·H(2)O, has a flattened-boat conformation, and the benzene ring is occupies a position orthogonal to this [dihedral angle: 82.19 (16)°]. In the crystal packing, supra-molecular arrays mediated by N-H⋯O(water) and O(water)-H⋯O(carbon-yl) hydrogen bonding are formed in the bc plane. A highly disordered solvent mol-ecule is present within a mol-ecular cavity defined by the organic and water mol-ecules. Its contribution to the electron density was removed from the observed data in the final cycles of refinement and the formula, mol-ecular weight and density are given without taking into account the contribution of the solvent mol-ecule.

Related literature

For background to the pharmacological potential of Hantzsch 4-dihydro­pyridines, see: Gaudio et al. (1994 ▶); Böcker & Guengerich (1986 ▶); Gordeev et al. (1996 ▶); Sunkel et al. (1992 ▶); Vo et al. (1995 ▶); Cooper et al. (1992 ▶). For the synthesis, see: Rathore et al. (2009 ▶). For a related structure, see: de Armas et al. (2000 ▶). For additional geometric analysis, see: Cremer & Pople, (1975 ▶).

Experimental

Crystal data

C17H18BrNO2·H2O

M = 366.25

Monoclinic,

a = 13.5236 (3) Å

b = 10.3866 (2) Å

c = 15.0939 (3) Å

β = 102.112 (1)°

V = 2072.96 (7) Å3

Z = 4

Mo Kα radiation

μ = 1.99 mm−1

T = 293 K

0.21 × 0.11 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.768, T max = 0.819

27847 measured reflections

3658 independent reflections

2611 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.147

S = 1.08

3658 reflections

212 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.56 e Å−3

Δρmin = −0.75 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks general, I. DOI: 10.1107/S1600536810006124/hg2647sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810006124/hg2647Isup2.hkl

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

C17H18BrNO2·H2O	F(000) = 752
Mr = 366.25	Dx = 1.174 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7408 reflections
a = 13.5236 (3) Å	θ = 2.4–22.7°
b = 10.3866 (2) Å	µ = 1.99 mm−1
c = 15.0939 (3) Å	T = 293 K
β = 102.112 (1)°	Block, colourless
V = 2072.96 (7) Å3	0.21 × 0.11 × 0.10 mm
Z = 4

Bruker SMART APEX CCD diffractometer	3658 independent reflections
Radiation source: fine-focus sealed tube	2611 reflections with I > 2σ(I)
graphite	Rint = 0.032
ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −16→15
Tmin = 0.768, Tmax = 0.819	k = 0→12
27847 measured reflections	l = 0→17

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.071P)2 + 1.0899P] where P = (Fo2 + 2Fc2)/3
3658 reflections	(Δ/σ)max = 0.001
212 parameters	Δρmax = 0.56 e Å−3
4 restraints	Δρmin = −0.75 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Br	−0.15936 (3)	0.08244 (7)	0.77808 (4)	0.1238 (3)
O1	0.3468 (2)	0.35143 (19)	0.87926 (13)	0.0640 (6)
O2	0.3961 (2)	−0.2324 (2)	0.88848 (14)	0.0691 (7)
N1	0.35579 (19)	0.0281 (2)	1.09364 (14)	0.0423 (5)
H1N	0.367 (2)	0.001 (3)	1.1502 (7)	0.051*
C1	0.3493 (2)	0.1585 (2)	1.07651 (16)	0.0388 (6)
C2	0.33562 (19)	0.1993 (2)	0.98949 (16)	0.0350 (6)
C3	0.3071 (2)	0.1007 (2)	0.91317 (16)	0.0356 (6)
H3	0.3358	0.1303	0.8623	0.043*
C4	0.3524 (2)	−0.0305 (2)	0.94161 (16)	0.0365 (6)
C5	0.3691 (2)	−0.0629 (2)	1.03099 (17)	0.0389 (6)
C6	0.3600 (3)	0.2362 (3)	1.16203 (18)	0.0559 (8)
H6A	0.4253	0.2768	1.1752	0.084*
H6B	0.3535	0.1805	1.2113	0.084*
H6C	0.3082	0.3008	1.1542	0.084*
C7	0.3489 (2)	0.3316 (2)	0.96005 (17)	0.0425 (6)
C8	0.3688 (3)	0.4445 (3)	1.0225 (2)	0.0683 (10)
H8A	0.3782	0.5201	0.9886	0.102*
H8B	0.4287	0.4289	1.0681	0.102*
H8C	0.3123	0.4570	1.0508	0.102*
C9	0.3687 (2)	−0.1214 (3)	0.87207 (19)	0.0463 (7)
C10	0.3516 (3)	−0.0759 (3)	0.7756 (2)	0.0723 (11)
H10A	0.3597	−0.1469	0.7370	0.108*
H10B	0.3997	−0.0099	0.7705	0.108*
H10C	0.2843	−0.0420	0.7577	0.108*
C11	0.4025 (3)	−0.1911 (3)	1.07260 (19)	0.0558 (8)
H11A	0.3465	−0.2500	1.0612	0.084*
H11B	0.4262	−0.1811	1.1368	0.084*
H11C	0.4561	−0.2243	1.0464	0.084*
C12	0.1926 (2)	0.0954 (3)	0.88046 (17)	0.0417 (6)
C13	0.1332 (2)	0.0057 (3)	0.9125 (2)	0.0638 (9)
H13	0.1640	−0.0542	0.9553	0.077*
C14	0.0291 (3)	0.0023 (4)	0.8828 (3)	0.0778 (11)
H14	−0.0092	−0.0592	0.9054	0.093*
C15	−0.0166 (3)	0.0895 (4)	0.8205 (3)	0.0766 (10)
C16	0.0384 (3)	0.1807 (4)	0.7877 (3)	0.0858 (12)
H16	0.0063	0.2406	0.7456	0.103*
C17	0.1432 (3)	0.1839 (4)	0.8176 (2)	0.0686 (9)
H17	0.1805	0.2465	0.7951	0.082*
O1W	0.40559 (17)	−0.05147 (18)	1.28219 (12)	0.0510 (5)
H1w	0.392 (3)	0.0100 (17)	1.3139 (18)	0.076*
H2w	0.397 (3)	−0.1227 (12)	1.3060 (19)	0.076*

	U11	U22	U33	U12	U13	U23
Br	0.0512 (3)	0.1686 (6)	0.1423 (5)	−0.0066 (3)	−0.0009 (3)	0.0017 (4)
O1	0.1159 (19)	0.0375 (11)	0.0411 (11)	−0.0092 (11)	0.0222 (11)	0.0047 (9)
O2	0.117 (2)	0.0393 (12)	0.0529 (12)	0.0149 (12)	0.0218 (12)	−0.0105 (10)
N1	0.0692 (15)	0.0318 (12)	0.0288 (11)	0.0016 (11)	0.0171 (11)	0.0033 (9)
C1	0.0527 (16)	0.0324 (14)	0.0334 (13)	−0.0002 (12)	0.0141 (11)	−0.0015 (11)
C2	0.0460 (14)	0.0276 (13)	0.0329 (13)	0.0004 (11)	0.0114 (11)	−0.0029 (10)
C3	0.0488 (15)	0.0305 (13)	0.0289 (12)	−0.0032 (11)	0.0115 (11)	−0.0018 (10)
C4	0.0500 (15)	0.0261 (13)	0.0345 (13)	−0.0033 (11)	0.0112 (11)	−0.0032 (10)
C5	0.0489 (15)	0.0315 (14)	0.0384 (14)	−0.0017 (11)	0.0139 (12)	−0.0024 (11)
C6	0.094 (2)	0.0406 (16)	0.0359 (15)	0.0006 (16)	0.0212 (15)	−0.0059 (12)
C7	0.0553 (16)	0.0337 (14)	0.0383 (15)	0.0002 (12)	0.0095 (12)	−0.0004 (11)
C8	0.119 (3)	0.0339 (16)	0.0524 (19)	−0.0096 (17)	0.019 (2)	−0.0023 (14)
C9	0.0599 (18)	0.0373 (16)	0.0431 (15)	−0.0024 (13)	0.0142 (13)	−0.0079 (12)
C10	0.128 (4)	0.053 (2)	0.0389 (17)	0.0131 (19)	0.026 (2)	−0.0095 (14)
C11	0.089 (2)	0.0354 (15)	0.0454 (16)	0.0085 (15)	0.0189 (16)	0.0056 (12)
C12	0.0522 (16)	0.0400 (14)	0.0342 (13)	−0.0012 (13)	0.0123 (12)	−0.0037 (11)
C13	0.057 (2)	0.064 (2)	0.069 (2)	−0.0095 (16)	0.0116 (16)	0.0129 (17)
C14	0.061 (2)	0.088 (3)	0.087 (3)	−0.019 (2)	0.020 (2)	0.005 (2)
C15	0.0472 (19)	0.097 (3)	0.082 (3)	−0.005 (2)	0.0069 (18)	−0.005 (2)
C16	0.061 (2)	0.093 (3)	0.093 (3)	0.011 (2)	−0.005 (2)	0.028 (2)
C17	0.059 (2)	0.076 (2)	0.067 (2)	−0.0011 (18)	0.0042 (16)	0.0236 (18)
O1w	0.0796 (15)	0.0376 (10)	0.0379 (11)	0.0059 (10)	0.0170 (10)	0.0048 (8)

Br—C15	1.904 (4)	C8—H8B	0.9600
O1—C7	1.231 (3)	C8—H8C	0.9600
O2—C9	1.221 (3)	C9—C10	1.501 (4)
N1—C5	1.375 (3)	C10—H10A	0.9600
N1—C1	1.378 (3)	C10—H10B	0.9600
N1—H1n	0.881 (14)	C10—H10C	0.9600
C1—C2	1.355 (3)	C11—H11A	0.9600
C1—C6	1.503 (4)	C11—H11B	0.9600
C2—C7	1.467 (4)	C11—H11C	0.9600
C2—C3	1.530 (3)	C12—C13	1.383 (4)
C3—C4	1.519 (3)	C12—C17	1.388 (4)
C3—C12	1.523 (4)	C13—C14	1.385 (5)
C3—H3	0.9800	C13—H13	0.9300
C4—C5	1.363 (4)	C14—C15	1.358 (6)
C4—C9	1.462 (4)	C14—H14	0.9300
C5—C11	1.501 (4)	C15—C16	1.360 (6)
C6—H6A	0.9600	C16—C17	1.394 (5)
C6—H6B	0.9600	C16—H16	0.9300
C6—H6C	0.9600	C17—H17	0.9300
C7—C8	1.492 (4)	O1w—H1w	0.84 (2)
C8—H8A	0.9600	O1w—H2w	0.841 (18)
C5—N1—C1	124.0 (2)	H8B—C8—H8C	109.5
C5—N1—H1N	115 (2)	O2—C9—C4	123.3 (3)
C1—N1—H1N	119 (2)	O2—C9—C10	118.2 (2)
C2—C1—N1	118.7 (2)	C4—C9—C10	118.5 (2)
C2—C1—C6	129.3 (2)	C9—C10—H10A	109.5
N1—C1—C6	112.0 (2)	C9—C10—H10B	109.5
C1—C2—C7	125.9 (2)	H10A—C10—H10B	109.5
C1—C2—C3	118.8 (2)	C9—C10—H10C	109.5
C7—C2—C3	115.3 (2)	H10A—C10—H10C	109.5
C4—C3—C12	112.4 (2)	H10B—C10—H10C	109.5
C4—C3—C2	111.4 (2)	C5—C11—H11A	109.5
C12—C3—C2	110.3 (2)	C5—C11—H11B	109.5
C4—C3—H3	107.5	H11A—C11—H11B	109.5
C12—C3—H3	107.5	C5—C11—H11C	109.5
C2—C3—H3	107.5	H11A—C11—H11C	109.5
C5—C4—C9	122.2 (2)	H11B—C11—H11C	109.5
C5—C4—C3	118.3 (2)	C13—C12—C17	116.9 (3)
C9—C4—C3	119.3 (2)	C13—C12—C3	122.5 (3)
C4—C5—N1	119.5 (2)	C17—C12—C3	120.6 (3)
C4—C5—C11	127.3 (2)	C12—C13—C14	122.0 (3)
N1—C5—C11	113.2 (2)	C12—C13—H13	119.0
C1—C6—H6A	109.5	C14—C13—H13	119.0
C1—C6—H6B	109.5	C15—C14—C13	119.4 (3)
H6A—C6—H6B	109.5	C15—C14—H14	120.3
C1—C6—H6C	109.5	C13—C14—H14	120.3
H6A—C6—H6C	109.5	C14—C15—C16	120.8 (3)
H6B—C6—H6C	109.5	C14—C15—Br	119.3 (3)
O1—C7—C2	118.6 (2)	C16—C15—Br	119.9 (3)
O1—C7—C8	117.2 (2)	C15—C16—C17	119.7 (4)
C2—C7—C8	124.2 (2)	C15—C16—H16	120.1
C7—C8—H8A	109.5	C17—C16—H16	120.1
C7—C8—H8B	109.5	C12—C17—C16	121.1 (3)
H8A—C8—H8B	109.5	C12—C17—H17	119.5
C7—C8—H8C	109.5	C16—C17—H17	119.5
H8A—C8—H8C	109.5	H1w—O1w—H2w	111 (3)
C5—N1—C1—C2	13.2 (4)	C3—C2—C7—O1	−7.3 (4)
C5—N1—C1—C6	−166.2 (3)	C1—C2—C7—C8	−7.1 (5)
N1—C1—C2—C7	−165.8 (3)	C3—C2—C7—C8	175.0 (3)
C6—C1—C2—C7	13.5 (5)	C5—C4—C9—O2	1.6 (5)
N1—C1—C2—C3	12.1 (4)	C3—C4—C9—O2	−173.2 (3)
C6—C1—C2—C3	−168.6 (3)	C5—C4—C9—C10	−178.1 (3)
C1—C2—C3—C4	−31.5 (3)	C3—C4—C9—C10	7.2 (4)
C7—C2—C3—C4	146.5 (2)	C4—C3—C12—C13	29.6 (3)
C1—C2—C3—C12	94.1 (3)	C2—C3—C12—C13	−95.5 (3)
C7—C2—C3—C12	−87.9 (3)	C4—C3—C12—C17	−151.8 (3)
C12—C3—C4—C5	−95.4 (3)	C2—C3—C12—C17	83.1 (3)
C2—C3—C4—C5	29.0 (3)	C17—C12—C13—C14	0.9 (5)
C12—C3—C4—C9	79.5 (3)	C3—C12—C13—C14	179.5 (3)
C2—C3—C4—C9	−156.1 (2)	C12—C13—C14—C15	−0.1 (6)
C9—C4—C5—N1	177.7 (3)	C13—C14—C15—C16	−0.7 (6)
C3—C4—C5—N1	−7.5 (4)	C13—C14—C15—Br	178.7 (3)
C9—C4—C5—C11	−1.8 (5)	C14—C15—C16—C17	0.7 (7)
C3—C4—C5—C11	173.0 (3)	Br—C15—C16—C17	−178.7 (3)
C1—N1—C5—C4	−15.7 (4)	C13—C12—C17—C16	−0.8 (5)
C1—N1—C5—C11	163.9 (3)	C3—C12—C17—C16	−179.5 (3)
C1—C2—C7—O1	170.6 (3)	C15—C16—C17—C12	0.0 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O1w	0.881 (14)	2.025 (13)	2.904 (3)	174 (2)
O1W—H1w···O1i	0.84 (2)	1.92 (3)	2.754 (3)	174 (4)
O1W—H2w···O2ii	0.84 (2)	1.96 (2)	2.778 (3)	166 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯O1w	0.88 (1)	2.03 (1)	2.904 (3)	174 (2)
O1W—H1w⋯O1i	0.84 (2)	1.92 (3)	2.754 (3)	174 (4)
O1W—H2w⋯O2ii	0.84 (2)	1.96 (2)	2.778 (3)	166 (2)

Symmetry codes: (i) ; (ii) .