Crystal structure of 4-bromo-2-[(E)-N-(2,2,6,6-tetra-methyl-piperidin-4-yl)carboximido-yl]phenol dihydrate.

In the title hydrate, C16H23BrN2O·2H2O, the organic mol-ecule features a strong intra-molecular O-H⋯N hydrogen bond. The piperidine ring, in addition, adopts a chair conformation with the exocyclic C-N bond in an equatorial orientation. The water molecules of crystallization are disordered (each over two sets of sites with half occupancy. In the crystal, they associate into corrugated (100) sheets of (H2O)4 tetra-mers linked by O-H⋯O hydrogen bonds. The organic mol-ecules, in turn, are arranged at both sides of these sheets, linked by water-piperidine O-H⋯N hydrogen bonds.

Related literature

For various biological applications of piperidine-containing compounds, see: Sánchez-Sancho & Herrandón (1998 ▸); Nithiya et al. (2011 ▸); Adger et al. (1996 ▸); Kozikowski et al. (1998 ▸); Brau et al. (2000 ▸).

Experimental

Crystal data

C16H23BrN2O·2H2O

M = 375.30

Monoclinic,

a = 39.6126 (7) Å

b = 6.0497 (1) Å

c = 14.8673 (3) Å

β = 98.889 (1)°

V = 3520.07 (11) Å3

Z = 8

Cu Kα radiation

μ = 3.30 mm−1

T = 150 K

0.34 × 0.09 × 0.08 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer

Absorption correction: numerical (SADABS; Bruker, 2014 ▸) T min = 0.54, T max = 0.77

12901 measured reflections

3428 independent reflections

3113 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.077

S = 1.10

3428 reflections

204 parameters

H-atom parameters constrained

Δρmax = 0.56 e Å−3

Δρmin = −0.67 e Å−3

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015007471/bg2553sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015007471/bg2553Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015007471/bg2553fig1.tif

The the asymmetric unit showing the intra- and inter­molecular O—H⋯N hydrogen bonds as dotted lines. Only one set of the disordered hydrogen atoms is shown.

Click here for additional data file.

b . DOI: 10.1107/S2056989015007471/bg2553fig2.tif

Packing viewed down the b axis with inter­molecular O—H⋯N and O—H⋯O hydrogen bonds shown, respectively, as purple and red dotted lines. Only one set of the disordered hydrogen atoms is shown.

Click here for additional data file.

. DOI: 10.1107/S2056989015007471/bg2553fig3.tif

A portion of the layer of lattice water mol­ecules. Only one set of the disordered hydrogen atoms is shown.

CCDC reference: 1059897

Additional supporting information: crystallographic information; 3D view; checkCIF report

C16H23BrN2O·2H2O	F(000) = 1568
Mr = 375.30	Dx = 1.416 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 39.6126 (7) Å	Cell parameters from 9702 reflections
b = 6.0497 (1) Å	θ = 6.0–72.1°
c = 14.8673 (3) Å	µ = 3.30 mm−1
β = 98.889 (1)°	T = 150 K
V = 3520.07 (11) Å3	Column, pale yellow
Z = 8	0.34 × 0.09 × 0.08 mm

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3428 independent reflections
Radiation source: INCOATEC IµS micro–focus source	3113 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.025
Detector resolution: 10.4167 pixels mm-1	θmax = 72.2°, θmin = 6.0°
ω scans	h = −48→45
Absorption correction: numerical (SADABS; Bruker, 2014)	k = −7→6
Tmin = 0.54, Tmax = 0.77	l = −18→15
12901 measured reflections

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)] = 0.031	Hydrogen site location: mixed
wR(F2) = 0.077	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0323P)2 + 4.9527P] where P = (Fo2 + 2Fc2)/3
3428 reflections	(Δ/σ)max = 0.002
204 parameters	Δρmax = 0.56 e Å−3
0 restraints	Δρmin = −0.67 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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.98 Å) while those attached to nitrogen and oxygen were placed in locations derived from a difference map and their parameters adjusted to give N—H = 0.91 Å and O—H = 0.84 Å. All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. Each lattice water molecule is disordered over two sites with the oxygen and one hydrogen in common. Based on peak heights for the disordered H atoms, the two sites for these atoms were judged to be equally occupied.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.82893 (2)	0.47282 (5)	0.33146 (2)	0.04137 (10)
O1	0.69904 (4)	0.0570 (2)	0.41569 (10)	0.0300 (3)
H1A	0.6835	0.1527	0.4080	0.056 (9)*
N1	0.66823 (4)	0.4316 (3)	0.36510 (11)	0.0236 (3)
N2	0.56827 (4)	0.6877 (2)	0.37146 (10)	0.0191 (3)
H2A	0.5586	0.5638	0.3912	0.023*
C1	0.72738 (5)	0.3664 (3)	0.35750 (12)	0.0224 (4)
C2	0.72757 (5)	0.1514 (3)	0.39411 (12)	0.0251 (4)
C3	0.75833 (6)	0.0340 (3)	0.40982 (13)	0.0301 (4)
H3	0.7587	−0.1111	0.4344	0.036*
C4	0.78818 (5)	0.1262 (4)	0.39007 (13)	0.0335 (5)
H4	0.8089	0.0450	0.4008	0.040*
C5	0.78768 (5)	0.3385 (4)	0.35440 (13)	0.0288 (4)
C6	0.75773 (5)	0.4580 (3)	0.33731 (12)	0.0249 (4)
H6	0.7577	0.6021	0.3119	0.030*
C7	0.69657 (5)	0.5031 (3)	0.34611 (12)	0.0215 (4)
H7	0.6977	0.6497	0.3239	0.026*
C8	0.63930 (4)	0.5860 (3)	0.35583 (12)	0.0210 (4)
H8	0.6465	0.7326	0.3343	0.025*
C9	0.62799 (5)	0.6125 (3)	0.44904 (12)	0.0215 (4)
H9A	0.6469	0.6795	0.4917	0.026*
H9B	0.6233	0.4646	0.4728	0.026*
C10	0.59592 (4)	0.7571 (3)	0.44580 (12)	0.0200 (4)
C11	0.57716 (4)	0.6334 (3)	0.28012 (11)	0.0196 (3)
C12	0.60997 (5)	0.4941 (3)	0.28757 (12)	0.0213 (4)
H12A	0.6049	0.3418	0.3058	0.026*
H12B	0.6173	0.4862	0.2269	0.026*
C13	0.60480 (5)	1.0012 (3)	0.43633 (14)	0.0249 (4)
H13A	0.6170	1.0200	0.3844	0.037*
H13B	0.6193	1.0512	0.4920	0.037*
H13C	0.5837	1.0889	0.4265	0.037*
C14	0.58145 (5)	0.7278 (3)	0.53433 (12)	0.0269 (4)
H14A	0.5617	0.8258	0.5342	0.040*
H14B	0.5990	0.7650	0.5860	0.040*
H14C	0.5743	0.5740	0.5397	0.040*
C15	0.58037 (5)	0.8434 (3)	0.22423 (12)	0.0247 (4)
H15A	0.5606	0.9394	0.2272	0.037*
H15B	0.5811	0.8031	0.1607	0.037*
H15C	0.6014	0.9218	0.2491	0.037*
C16	0.54701 (5)	0.4976 (3)	0.23218 (13)	0.0252 (4)
H16A	0.5435	0.3684	0.2694	0.038*
H16B	0.5519	0.4485	0.1727	0.038*
H16C	0.5263	0.5889	0.2237	0.038*
O2	0.51008 (4)	0.9736 (2)	0.35246 (11)	0.0331 (3)	0.5
H2B	0.5278	0.8954	0.3562	0.040*	0.5
H2C	0.5038	1.0005	0.2970	0.040*	0.5
O3	0.51664 (4)	0.2904 (3)	0.49776 (11)	0.0399 (4)	0.5
H3A	0.5127	0.2158	0.5427	0.048*	0.5
H3B	0.5124	0.2081	0.4519	0.048*	0.5
O2A	0.51008 (4)	0.9736 (2)	0.35246 (11)	0.0331 (3)	0.5
H2BA	0.5278	0.8954	0.3562	0.040*	0.5
H2D	0.5105	1.0762	0.3907	0.040*	0.5
O3A	0.51664 (4)	0.2904 (3)	0.49776 (11)	0.0399 (4)	0.5
H3AA	0.5127	0.2158	0.5427	0.048*	0.5
H3C	0.5069	0.4131	0.5000	0.048*	0.5

	U11	U22	U33	U12	U13	U23
Br1	0.01904 (12)	0.06914 (19)	0.03582 (14)	−0.00163 (10)	0.00390 (9)	−0.01717 (11)
O1	0.0346 (8)	0.0241 (7)	0.0318 (7)	0.0020 (6)	0.0068 (6)	0.0023 (6)
N1	0.0216 (8)	0.0231 (8)	0.0259 (8)	0.0039 (6)	0.0034 (6)	0.0019 (6)
N2	0.0191 (7)	0.0207 (7)	0.0184 (7)	−0.0018 (6)	0.0054 (5)	−0.0001 (6)
C1	0.0228 (9)	0.0258 (9)	0.0183 (8)	0.0036 (7)	0.0017 (6)	−0.0033 (7)
C2	0.0311 (10)	0.0250 (9)	0.0186 (8)	0.0045 (8)	0.0015 (7)	−0.0035 (7)
C3	0.0393 (11)	0.0286 (10)	0.0215 (9)	0.0126 (9)	0.0013 (8)	−0.0015 (8)
C4	0.0306 (10)	0.0446 (12)	0.0234 (10)	0.0181 (9)	−0.0020 (8)	−0.0067 (9)
C5	0.0206 (9)	0.0421 (12)	0.0227 (9)	0.0039 (8)	0.0003 (7)	−0.0109 (8)
C6	0.0228 (9)	0.0308 (10)	0.0207 (9)	0.0024 (8)	0.0023 (7)	−0.0047 (7)
C7	0.0227 (9)	0.0216 (9)	0.0202 (8)	0.0033 (7)	0.0028 (7)	0.0020 (7)
C8	0.0188 (8)	0.0189 (8)	0.0257 (9)	0.0025 (7)	0.0044 (7)	0.0041 (7)
C9	0.0226 (9)	0.0200 (8)	0.0211 (9)	0.0010 (7)	0.0014 (7)	0.0017 (7)
C10	0.0213 (8)	0.0206 (9)	0.0181 (8)	−0.0001 (7)	0.0034 (6)	0.0003 (7)
C11	0.0188 (8)	0.0224 (9)	0.0182 (8)	−0.0002 (7)	0.0046 (6)	−0.0001 (7)
C12	0.0227 (9)	0.0211 (9)	0.0206 (8)	0.0023 (7)	0.0051 (7)	0.0007 (7)
C13	0.0262 (10)	0.0188 (9)	0.0288 (10)	−0.0001 (7)	0.0018 (7)	−0.0007 (7)
C14	0.0313 (10)	0.0302 (10)	0.0201 (9)	−0.0013 (8)	0.0070 (7)	−0.0011 (8)
C15	0.0235 (9)	0.0289 (10)	0.0226 (9)	0.0030 (7)	0.0066 (7)	0.0055 (8)
C16	0.0220 (9)	0.0305 (10)	0.0232 (9)	−0.0017 (7)	0.0041 (7)	−0.0048 (7)
O2	0.0281 (7)	0.0337 (8)	0.0376 (8)	0.0058 (6)	0.0050 (6)	−0.0057 (6)
O3	0.0444 (9)	0.0318 (8)	0.0450 (9)	−0.0004 (7)	0.0113 (7)	−0.0064 (7)
O2A	0.0281 (7)	0.0337 (8)	0.0376 (8)	0.0058 (6)	0.0050 (6)	−0.0057 (6)
O3A	0.0444 (9)	0.0318 (8)	0.0450 (9)	−0.0004 (7)	0.0113 (7)	−0.0064 (7)

Br1—C5	1.902 (2)	C10—C13	1.530 (2)
O1—C2	1.348 (2)	C11—C16	1.532 (2)
O1—H1A	0.8400	C11—C15	1.534 (2)
N1—C7	1.275 (2)	C11—C12	1.538 (2)
N1—C8	1.468 (2)	C12—H12A	0.9900
N2—C10	1.491 (2)	C12—H12B	0.9900
N2—C11	1.491 (2)	C13—H13A	0.9800
N2—H2A	0.9099	C13—H13B	0.9800
C1—C6	1.398 (3)	C13—H13C	0.9800
C1—C2	1.409 (3)	C14—H14A	0.9800
C1—C7	1.463 (2)	C14—H14B	0.9800
C2—C3	1.399 (3)	C14—H14C	0.9800
C3—C4	1.379 (3)	C15—H15A	0.9800
C3—H3	0.9500	C15—H15B	0.9800
C4—C5	1.388 (3)	C15—H15C	0.9800
C4—H4	0.9500	C16—H16A	0.9800
C5—C6	1.379 (3)	C16—H16B	0.9800
C6—H6	0.9500	C16—H16C	0.9800
C7—H7	0.9500	O2—H2B	0.8400
C8—C12	1.525 (3)	O2—H2C	0.8400
C8—C9	1.529 (2)	O3—H3A	0.8399
C8—H8	1.0000	O3—H3B	0.8400
C9—C10	1.537 (2)	O2A—H2BA	0.8400
C9—H9A	0.9900	O2A—H2D	0.8400
C9—H9B	0.9900	O3A—H3AA	0.8399
C10—C14	1.525 (2)	O3A—H3C	0.8401
C2—O1—H1A	107.4	C14—C10—C9	109.03 (15)
C7—N1—C8	117.69 (15)	C13—C10—C9	110.57 (15)
C10—N2—C11	119.17 (13)	N2—C11—C16	105.38 (14)
C10—N2—H2A	106.8	N2—C11—C15	111.20 (14)
C11—N2—H2A	106.4	C16—C11—C15	108.43 (15)
C6—C1—C2	119.71 (17)	N2—C11—C12	111.77 (14)
C6—C1—C7	118.73 (17)	C16—C11—C12	109.21 (15)
C2—C1—C7	121.42 (17)	C15—C11—C12	110.66 (14)
O1—C2—C3	119.07 (18)	C8—C12—C11	113.38 (14)
O1—C2—C1	121.87 (17)	C8—C12—H12A	108.9
C3—C2—C1	119.06 (19)	C11—C12—H12A	108.9
C4—C3—C2	120.81 (19)	C8—C12—H12B	108.9
C4—C3—H3	119.6	C11—C12—H12B	108.9
C2—C3—H3	119.6	H12A—C12—H12B	107.7
C3—C4—C5	119.57 (18)	C10—C13—H13A	109.5
C3—C4—H4	120.2	C10—C13—H13B	109.5
C5—C4—H4	120.2	H13A—C13—H13B	109.5
C6—C5—C4	121.09 (19)	C10—C13—H13C	109.5
C6—C5—Br1	118.76 (17)	H13A—C13—H13C	109.5
C4—C5—Br1	120.12 (15)	H13B—C13—H13C	109.5
C5—C6—C1	119.75 (19)	C10—C14—H14A	109.5
C5—C6—H6	120.1	C10—C14—H14B	109.5
C1—C6—H6	120.1	H14A—C14—H14B	109.5
N1—C7—C1	122.01 (17)	C10—C14—H14C	109.5
N1—C7—H7	119.0	H14A—C14—H14C	109.5
C1—C7—H7	119.0	H14B—C14—H14C	109.5
N1—C8—C12	109.52 (15)	C11—C15—H15A	109.5
N1—C8—C9	108.38 (14)	C11—C15—H15B	109.5
C12—C8—C9	109.97 (14)	H15A—C15—H15B	109.5
N1—C8—H8	109.6	C11—C15—H15C	109.5
C12—C8—H8	109.6	H15A—C15—H15C	109.5
C9—C8—H8	109.6	H15B—C15—H15C	109.5
C8—C9—C10	112.81 (14)	C11—C16—H16A	109.5
C8—C9—H9A	109.0	C11—C16—H16B	109.5
C10—C9—H9A	109.0	H16A—C16—H16B	109.5
C8—C9—H9B	109.0	C11—C16—H16C	109.5
C10—C9—H9B	109.0	H16A—C16—H16C	109.5
H9A—C9—H9B	107.8	H16B—C16—H16C	109.5
N2—C10—C14	106.03 (14)	H2B—O2—H2C	106.9
N2—C10—C13	110.90 (14)	H3A—O3—H3B	106.7
C14—C10—C13	108.29 (15)	H2BA—O2A—H2D	116.2
N2—C10—C9	111.84 (14)	H3AA—O3A—H3C	107.5
C6—C1—C2—O1	179.19 (17)	C7—N1—C8—C9	−119.20 (18)
C7—C1—C2—O1	3.7 (3)	N1—C8—C9—C10	−175.48 (14)
C6—C1—C2—C3	0.2 (3)	C12—C8—C9—C10	−55.78 (19)
C7—C1—C2—C3	−175.29 (17)	C11—N2—C10—C14	−162.17 (15)
O1—C2—C3—C4	−178.91 (17)	C11—N2—C10—C13	80.49 (19)
C1—C2—C3—C4	0.1 (3)	C11—N2—C10—C9	−43.4 (2)
C2—C3—C4—C5	0.2 (3)	C8—C9—C10—N2	49.0 (2)
C3—C4—C5—C6	−0.8 (3)	C8—C9—C10—C14	165.96 (15)
C3—C4—C5—Br1	177.42 (15)	C8—C9—C10—C13	−75.08 (19)
C4—C5—C6—C1	1.1 (3)	C10—N2—C11—C16	161.25 (15)
Br1—C5—C6—C1	−177.13 (13)	C10—N2—C11—C15	−81.47 (18)
C2—C1—C6—C5	−0.8 (3)	C10—N2—C11—C12	42.7 (2)
C7—C1—C6—C5	174.83 (16)	N1—C8—C12—C11	174.37 (14)
C8—N1—C7—C1	176.84 (16)	C9—C8—C12—C11	55.37 (19)
C6—C1—C7—N1	−178.48 (17)	N2—C11—C12—C8	−48.0 (2)
C2—C1—C7—N1	−2.9 (3)	C16—C11—C12—C8	−164.17 (15)
C7—N1—C8—C12	120.82 (18)	C15—C11—C12—C8	76.55 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.84	1.87	2.628 (2)	149
O2—H2B···N2	0.84	2.02	2.861 (2)	175
O3—H3A···O2i	0.84	2.24	3.059 (2)	167
O3—H3B···O2ii	0.84	2.04	2.869 (2)	168
O2A—H2BA···N2	0.84	2.02	2.861 (2)	175
O2A—H2D···O3Aiii	0.84	2.04	2.869 (2)	170
O3A—H3AA···O2Ai	0.84	2.24	3.059 (2)	167

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1H1AN1	0.84	1.87	2.628(2)	149
O2H2BN2	0.84	2.02	2.861(2)	175
O3H3AO2i	0.84	2.24	3.059(2)	167
O3H3BO2ii	0.84	2.04	2.869(2)	168
O2AH2BAN2	0.84	2.02	2.861(2)	175
O2AH2DO3A iii	0.84	2.04	2.869(2)	170
O3AH3AAO2A i	0.84	2.24	3.059(2)	167

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