Crystal structure of 4-chloro-N-[2-(piperidin-1-yl)eth­yl]benzamide monohydrate

In the title compound, C₁₄H₁₉ClN₂O₂·H₂O, the piperdine ring adopts a chair conformation. The dihedral angle between the mean plane of the piperidine ring and that of the phenyl ring is 41.64 (1)°. In the crystal, mol­ecules are linked by O—H...N, N—H...O and C—H...O hydrogen bonds involving the water mol­ecule, forming double-stranded chains propagating along [010].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.051
• wR factor = 0.160
• Data-to-parameter ratio = 20.9

checkCIF/PLATON results

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Alert level C
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....        C12 Check
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1 Note
              C14 H19 Cl N2 O
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...    -12.437 Report
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -1.717 Report
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3 Note
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         41 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

The piperidine derivatives were reported to have antimicrobial activity. Piperidine derivatives have been synthesized for pharmaceutical research as they are very efficient against resistance microorganisms. The substituted piperidine derivatives were also reported to have antimicrobial activity (Pandey & Chawla, 2012; Jayalakshmi & Nanjundan, 2008; Parthiban et al., 2005; Aridoss et al., 2008; Ramachandran et al. 2011).

In the title compound, Fig. 1, the piperidine ring is cis to the phenyl ring. The C—N distances [1.335 (2) - 1.464 (2) Å] are in the normal range and are in good agreement with values of from similar structures (Ávila et al., 2010; Prathebha et al., 2014). The bond angle sum around atoms N1 and N2 [333.2 (4)° and 359.97 (1)°, respectively] shows sp³ hybridization. The C═O distance [1.231 (2) Å] is comparable with the value reported previously (Al-abbasi et al., 2010). The piperdine ring adopts a chair conformation with puckering parameters of q2 = 0.6994 (0) Å, φ2 = 88.60 (0)° q3 = -0.0267 (0) Å, QT = 0.6999 Å and θ2 = 92.19 (2)°.

In the crystal, adjacent molecules are linked by O-H···N, O-H···O and C-H···O hydrogen bonds, involving the water molecule, forming double stranded chains propagating along [010]; see Table 1 and Fig. 2

Related literature

For the synthesis of the title compound, see: Prathebha et al. (2013, 2014). For the biological activities of piperdine derivatives, see: Pandey & Chawla (2012); Jayalakshmi & Nanjundan (2008); Parthiban et al. (2005); Aridoss et al. (2008); Ramachandran et al. (2011). For related structures, see: Prathebha et al. (2014); Ávila et al. (2010); Al-abbasi et al. (2010).

S2. Experimental

The title compound was synthesized following a publish procedure (Prathebha et al., 2013, 2014). In a 250 mL round-bottomed flask 120 mL of ethylmethylketone was added to 1,2-aminoethylpiperidine (0.02 mol) and stirred at room temperature. After 5 min triethylamine (0.04 mol) was added and the mixture was stirred for 15 min. Then 4-chlorobenzoylchloride (0.04 mol) was added and the reaction mixture was stirred at room temperature for ca. 2 h. A white precipitate of triethylammoniumchloride was formed. It was filtered and the filtrate was evaporated to give the crude product. It was recrystallized twice from ethylmethylketone (yield: 82%) giving colourless block-like crystals of the title compound.

S3. Refinement

The water H atoms were located in a difference Fourier map and freely refined. The NH and C-bound H atoms were positioned geometrically and treated as riding on their parent atoms: C—H = 0.93 - 0.97 Å, N—H = 0.86 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and = 1.2U_eq(N,C) for other H atoms.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: XPREP in SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view along the b axis of the crystal packing of the title compound. The dashed lines indicate the hydrogen bonds (see Table 1 for details; C-bound H atoms have been omitted for clarity).

4-Chloro-N-[2-(piperidin-1-yl)ethyl]benzamide monohydrate

Crystal data

C14H19ClN2O·H2O	F(000) = 608
Mr = 284.78	Dx = 1.245 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3780 reflections
a = 14.9115 (6) Å	θ = 1.7–28.4°
b = 6.6899 (3) Å	µ = 0.25 mm^−1
c = 15.6215 (7) Å	T = 293 K
β = 102.956 (2)°	Block, colourless
V = 1518.67 (11) Å^3	0.25 × 0.23 × 0.20 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer	3780 independent reflections
Radiation source: fine-focus sealed tube	1953 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω and φ scan	θmax = 28.4°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −19→19
Tmin = 0.939, Tmax = 0.951	k = −8→7
12566 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0714P)^2 + 0.2535P] where P = (Fo^2 + 2Fc^2)/3
3780 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.28 e Å^−3
2 restraints	Δρmin = −0.21 e Å^−3

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
O1W	0.36430 (12)	−0.0064 (2)	0.33083 (13)	0.0544 (4)
H1WA	0.3601 (17)	−0.005 (4)	0.2772 (11)	0.062 (8)*
H1WB	0.3987 (15)	0.082 (3)	0.3533 (15)	0.064 (8)*
C1	0.13069 (15)	−0.6539 (4)	0.39904 (16)	0.0561 (6)
H1A	0.1347	−0.6240	0.4605	0.067*
H1B	0.1773	−0.7528	0.3957	0.067*
C2	0.03637 (15)	−0.7388 (4)	0.35887 (18)	0.0671 (7)
H2A	0.0342	−0.7795	0.2988	0.081*
H2B	0.0257	−0.8563	0.3916	0.081*
C3	−0.03859 (16)	−0.5866 (4)	0.35964 (18)	0.0682 (7)
H3A	−0.0428	−0.5605	0.4197	0.082*
H3B	−0.0973	−0.6390	0.3279	0.082*
C4	−0.01743 (15)	−0.3941 (4)	0.31710 (18)	0.0665 (7)
H4A	−0.0223	−0.4163	0.2549	0.080*
H4B	−0.0621	−0.2930	0.3234	0.080*
C5	0.07842 (15)	−0.3203 (4)	0.35883 (17)	0.0610 (7)
H5A	0.0910	−0.1994	0.3293	0.073*
H5B	0.0817	−0.2878	0.4200	0.073*
C6	0.24037 (14)	−0.3914 (3)	0.38842 (15)	0.0508 (6)
H6A	0.2500	−0.3780	0.4517	0.061*
H6B	0.2448	−0.2593	0.3641	0.061*
C7	0.31449 (13)	−0.5225 (3)	0.36732 (16)	0.0511 (6)
H7A	0.3226	−0.6393	0.4051	0.061*
H7B	0.2961	−0.5678	0.3069	0.061*
C8	0.48147 (13)	−0.5074 (3)	0.38619 (13)	0.0411 (5)
C9	0.56372 (13)	−0.3766 (3)	0.39205 (13)	0.0405 (5)
C10	0.63653 (15)	−0.4479 (4)	0.35953 (15)	0.0530 (6)
H10	0.6343	−0.5769	0.3370	0.064*
C11	0.71251 (15)	−0.3293 (4)	0.36017 (16)	0.0633 (7)
H11	0.7610	−0.3773	0.3377	0.076*
C12	0.71562 (14)	−0.1406 (4)	0.39423 (16)	0.0552 (6)
C13	0.64543 (15)	−0.0669 (4)	0.42879 (15)	0.0541 (6)
H13	0.6491	0.0607	0.4529	0.065*
C14	0.56919 (14)	−0.1860 (3)	0.42700 (14)	0.0479 (5)
H14	0.5209	−0.1371	0.4497	0.058*
N1	0.14836 (11)	−0.4716 (2)	0.35340 (11)	0.0435 (4)
N2	0.40087 (11)	−0.4147 (3)	0.37969 (11)	0.0480 (5)
H2	0.4002	−0.2864	0.3830	0.058*
O1	0.48880 (10)	−0.6908 (2)	0.38625 (10)	0.0573 (4)
Cl1	0.81091 (5)	0.01012 (12)	0.39483 (6)	0.0952 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1W	0.0567 (10)	0.0380 (10)	0.0677 (12)	−0.0102 (8)	0.0123 (9)	0.0000 (9)
C1	0.0484 (13)	0.0450 (14)	0.0746 (15)	−0.0061 (11)	0.0129 (11)	0.0122 (12)
C2	0.0503 (14)	0.0549 (16)	0.0971 (19)	−0.0147 (12)	0.0184 (13)	0.0019 (14)
C3	0.0445 (13)	0.0754 (19)	0.0887 (18)	−0.0116 (13)	0.0234 (12)	−0.0014 (15)
C4	0.0427 (13)	0.0672 (18)	0.0939 (18)	0.0093 (12)	0.0244 (12)	0.0050 (15)
C5	0.0478 (13)	0.0479 (15)	0.0937 (18)	0.0037 (11)	0.0297 (12)	−0.0020 (13)
C6	0.0437 (12)	0.0424 (13)	0.0682 (14)	−0.0064 (10)	0.0164 (10)	−0.0050 (11)
C7	0.0364 (11)	0.0373 (13)	0.0779 (15)	−0.0021 (9)	0.0091 (10)	−0.0042 (11)
C8	0.0383 (11)	0.0353 (12)	0.0482 (12)	−0.0031 (9)	0.0067 (8)	−0.0020 (9)
C9	0.0365 (10)	0.0375 (12)	0.0456 (11)	−0.0029 (9)	0.0049 (8)	0.0003 (9)
C10	0.0440 (12)	0.0439 (13)	0.0720 (15)	−0.0020 (10)	0.0150 (11)	−0.0097 (11)
C11	0.0442 (13)	0.0648 (18)	0.0857 (18)	−0.0042 (12)	0.0247 (12)	−0.0076 (14)
C12	0.0413 (12)	0.0530 (16)	0.0710 (15)	−0.0140 (10)	0.0121 (11)	0.0048 (12)
C13	0.0495 (13)	0.0394 (13)	0.0718 (15)	−0.0083 (10)	0.0102 (11)	−0.0057 (11)
C14	0.0397 (11)	0.0420 (13)	0.0628 (14)	−0.0029 (9)	0.0129 (10)	−0.0057 (11)
N1	0.0361 (9)	0.0344 (10)	0.0610 (11)	−0.0010 (7)	0.0132 (8)	0.0014 (8)
N2	0.0360 (9)	0.0314 (10)	0.0751 (12)	−0.0035 (7)	0.0094 (8)	−0.0013 (9)
O1	0.0493 (9)	0.0342 (10)	0.0869 (11)	−0.0040 (7)	0.0124 (8)	−0.0050 (8)
Cl1	0.0650 (5)	0.0851 (6)	0.1438 (8)	−0.0346 (4)	0.0410 (5)	−0.0043 (5)

Geometric parameters (Å, º)

O1W—H1WA	0.826 (16)	C6—H6A	0.9700
O1W—H1WB	0.808 (16)	C6—H6B	0.9700
C1—N1	1.466 (3)	C7—N2	1.451 (2)
C1—C2	1.516 (3)	C7—H7A	0.9700
C1—H1A	0.9700	C7—H7B	0.9700
C1—H1B	0.9700	C8—O1	1.231 (2)
C2—C3	1.514 (3)	C8—N2	1.336 (2)
C2—H2A	0.9700	C8—C9	1.493 (3)
C2—H2B	0.9700	C9—C10	1.383 (3)
C3—C4	1.515 (4)	C9—C14	1.382 (3)
C3—H3A	0.9700	C10—C11	1.381 (3)
C3—H3B	0.9700	C10—H10	0.9300
C4—C5	1.514 (3)	C11—C12	1.366 (3)
C4—H4A	0.9700	C11—H11	0.9300
C4—H4B	0.9700	C12—C13	1.372 (3)
C5—N1	1.469 (3)	C12—Cl1	1.741 (2)
C5—H5A	0.9700	C13—C14	1.383 (3)
C5—H5B	0.9700	C13—H13	0.9300
C6—N1	1.460 (3)	C14—H14	0.9300
C6—C7	1.504 (3)	N2—H2	0.8600
H1WA—O1W—H1WB	109 (2)	C7—C6—H6B	109.2
N1—C1—C2	111.19 (19)	H6A—C6—H6B	107.9
N1—C1—H1A	109.4	N2—C7—C6	110.77 (17)
C2—C1—H1A	109.4	N2—C7—H7A	109.5
N1—C1—H1B	109.4	C6—C7—H7A	109.5
C2—C1—H1B	109.4	N2—C7—H7B	109.5
H1A—C1—H1B	108.0	C6—C7—H7B	109.5
C3—C2—C1	111.3 (2)	H7A—C7—H7B	108.1
C3—C2—H2A	109.4	O1—C8—N2	122.74 (18)
C1—C2—H2A	109.4	O1—C8—C9	120.83 (18)
C3—C2—H2B	109.4	N2—C8—C9	116.42 (18)
C1—C2—H2B	109.4	C10—C9—C14	118.80 (18)
H2A—C2—H2B	108.0	C10—C9—C8	118.50 (18)
C2—C3—C4	109.98 (18)	C14—C9—C8	122.69 (18)
C2—C3—H3A	109.7	C11—C10—C9	120.6 (2)
C4—C3—H3A	109.7	C11—C10—H10	119.7
C2—C3—H3B	109.7	C9—C10—H10	119.7
C4—C3—H3B	109.7	C12—C11—C10	119.3 (2)
H3A—C3—H3B	108.2	C12—C11—H11	120.3
C5—C4—C3	110.9 (2)	C10—C11—H11	120.3
C5—C4—H4A	109.4	C11—C12—C13	121.5 (2)
C3—C4—H4A	109.4	C11—C12—Cl1	119.58 (18)
C5—C4—H4B	109.4	C13—C12—Cl1	118.89 (19)
C3—C4—H4B	109.4	C12—C13—C14	118.7 (2)
H4A—C4—H4B	108.0	C12—C13—H13	120.6
N1—C5—C4	111.4 (2)	C14—C13—H13	120.6
N1—C5—H5A	109.4	C9—C14—C13	120.98 (19)
C4—C5—H5A	109.4	C9—C14—H14	119.5
N1—C5—H5B	109.4	C13—C14—H14	119.5
C4—C5—H5B	109.4	C6—N1—C1	112.30 (17)
H5A—C5—H5B	108.0	C6—N1—C5	110.17 (17)
N1—C6—C7	112.24 (17)	C1—N1—C5	109.74 (16)
N1—C6—H6A	109.2	C8—N2—C7	122.38 (17)
C7—C6—H6A	109.2	C8—N2—H2	118.8
N1—C6—H6B	109.2	C7—N2—H2	118.8
N1—C1—C2—C3	−57.0 (3)	C11—C12—C13—C14	−1.4 (4)
C1—C2—C3—C4	53.1 (3)	Cl1—C12—C13—C14	179.04 (17)
C2—C3—C4—C5	−53.1 (3)	C10—C9—C14—C13	0.7 (3)
C3—C4—C5—N1	57.3 (3)	C8—C9—C14—C13	−178.0 (2)
N1—C6—C7—N2	163.46 (18)	C12—C13—C14—C9	0.7 (3)
O1—C8—C9—C10	28.2 (3)	C7—C6—N1—C1	69.4 (2)
N2—C8—C9—C10	−150.8 (2)	C7—C6—N1—C5	−167.94 (19)
O1—C8—C9—C14	−153.1 (2)	C2—C1—N1—C6	−177.55 (19)
N2—C8—C9—C14	27.9 (3)	C2—C1—N1—C5	59.6 (2)
C14—C9—C10—C11	−1.4 (3)	C4—C5—N1—C6	175.98 (19)
C8—C9—C10—C11	177.3 (2)	C4—C5—N1—C1	−59.9 (2)
C9—C10—C11—C12	0.7 (4)	O1—C8—N2—C7	−3.5 (3)
C10—C11—C12—C13	0.8 (4)	C9—C8—N2—C7	175.58 (18)
C10—C11—C12—Cl1	−179.72 (18)	C6—C7—N2—C8	163.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···N1^i	0.83 (2)	2.03 (2)	2.851 (3)	174 (2)
N2—H2···O1W	0.86	2.06	2.855 (2)	153
C6—H6B···O1W	0.97	2.59	3.406 (3)	142

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.