Methyl 4-(piperidin-1-ylcarbon­yl)benzoate

In the title compound, C₁₄H₁₇NO₃, the piperidine ring has a chair conformation and an intra­molecular C—H...O inter­action stabilizes the mol­ecular conformation. In the crystal, weak inter­molecular C—H...O inter­actions occur.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.044
• wR factor = 0.122
• Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        504

Alert level G
PLAT153_ALERT_1_G The su's on the Cell Axes   are Equal (x 100000)        500 Ang.
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        500 Deg.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

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

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S1. Comment

There are many methods documented for the synthesis of a wide range of aromatic carboxylic acid derivatives, including benzamides. These compounds can be prepared using palladium(0)-catalyzed carbonylation of aryl halides with various nucleophiles (Zhao et al., 2008; Margerlein et al., 2001; Stille & Wong, 1975). The aminocarbonylation reaction of aryl halides achieved using the commercially available preligand [(^tBu)₃PH]BF₄ as the key component in combination with Herrmann's palladacycle as the Pd source (Jia & Morris, 1991). In other studies procedures employing Mo(CO)₆ as a carbon monoxide releasing reagent, together with the use of controlled microwave irradiation as the energy source have been used to overcome the problems of introducing a gaseous reactant in small-scale high-speed protocols (Lagerlund & Larhed, 2006). In addition to other methods for obtaining derivatives of aromatic carboxylic acids, methyl 4-(piperidine-1-carbonyl)benzoate, C₁₄H₁₇N₁O₃ (I) was prepared from 4-(methoxycarbonyl)benzoic acid in excellent yield, exploring classical methodology, using thionyl chloride as the more electrophilic acid chloride, followed by treatment with piperidine in the presence of chloroform, at room temperature (Lima et al., 2002). The study of this reaction showed that it could be controlled by the stoichimetric and reaction conditions, making the reaction of the piperidine with acyl chloride more favoured than with the ester group, by the use of an easy and convenient method.

In the structure of the title compound (Fig. 1) all bond lengths and angles are in agreement with literature values (Allen et al., 1987). The aromatic ring and the ester are close to planar [C9–C10–C13–O3, -171.21 (12)°; C10–C13–O3–C14, 175.10 (11)°], whereas the carbonyl group is twisted out of the plane of the ring [C12–C7–C6–O1, 122.57 (15)°]. The piperidine ring has the more energetically favored boat conformation, with an intramolecular C5—H···O(carbonyl) interaction [C···O, 2.750 (3) Å] which stabilizes the molecular conformation. As expected, the supramolecular structure has no formal intermolecular hydrogen bonds (Fig. 2).

Related literature

For Pd(0)-catalysed carbonylation of aryl halides, see: Jia & Morris (1991); Stille & Wong (1975); Magerlein, et al. (2001); Zhao et al. (2008). For procedural modifications for carbonylation reactions, see: Lagerlund & Larhed (2006). For the preparation of other piperidine derivatives, see Lima et al. (2002). For bond-length data, see: Allen et al. (1987).

S2. Experimental

A solution of 0.50 g of 4-(methoxycarbonyl)benzoic acid in 15 ml of chloroform, 0.30 ml of freshly distilled thionyl chloride and a catalytic amount of dimethylformamide was stirred under reflux for 1 h. After this time, the solvent was carefully evaporated at reduced pressure and a solution of 2.78 mmol of piperidine and 0.78 ml of triethylamine in 10 ml of chloroform was added. The reaction mixture was stirred for 30 min at room temperature, after which 10 ml of saturated sodium carbonate aqueous solution was added and the mixture extracted with chloroform (3x15 ml). The organic layer was separated, washed with water, rewashed with brine and dried over anhydrous sodium sulfate. The solvent was evaporated at reduced pressure after which the compound was purified by column chromatography using Merck Silica Gel 60 (0.040–0.063 mm) and a mixture of hexane/ethyl acetate (8:2,V/V) as eluent (0.56 g, 82%). Crystals suitable for X-ray diffraction were grown from a mixture of hexane/ethyl acetate (8:2, V/V). IR (KBr, cm^-1): ν 1724, 1680, 1436, 1276, 1114. ¹H NMR (200 MHz, CDCl₃, p.p.m.): δ 1.27 (m, 2H), 1.70 (m, 2H), 3.33 (m, 2H), 3.74 (m, 2H), 3.95 (s, 3H), 7.47 (d, ³ J = 8.27 Hz), 8.09 (d, ³ J = 8.17). ¹³C NMR (200 MHz, CDCl₃, p.p.m.): δ 24.5, 25.6, 26.5, 42.2, 51.2, 52.6, 126.7, 129.8, 130.8, 140.9, 166.4, 169.2.

S3. Refinement

The H atoms were located from the difference electron density synthesis and allowed to ride on their parent atoms, with C—H(aromatic) = 0.95 Å and C—H(aliphatic) = 0.97 Å and U_iso(H)= 1.5U_eq for methyl H atoms or 1.2U_eq for the remaining H atoms.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of (I).

Methyl 4-(piperidin-1-ylcarbonyl)benzoate

Crystal data

C14H17NO3	Z = 2
Mr = 247.29	F(000) = 264
Triclinic, P1	Dx = 1.294 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.879 (5) Å	Cell parameters from 2414 reflections
b = 9.693 (5) Å	θ = 3.3–29.4°
c = 12.190 (5) Å	µ = 0.09 mm^−1
α = 69.684 (5)°	T = 150 K
β = 82.535 (5)°	Prism, colourless
γ = 77.502 (5)°	0.05 × 0.05 × 0.05 mm
V = 634.9 (7) Å^3

Data collection

Oxford Diffraction Xcalibur Atlas Gemini Ultra diffractometer	Rint = 0.033
Detector resolution: 10.4186 pixels mm^-1	θmax = 29.4°, θmin = 3.3°
ω scans	h = −7→7
4958 measured reflections	k = −11→12
2958 independent reflections	l = −13→16
2036 reflections with I > 2σ(I)

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.044	w = 1/[σ^2(Fo^2) + (0.0676P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.122	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.25 e Å^−3
2958 reflections	Δρmin = −0.26 e Å^−3
164 parameters

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O3	0.73762 (16)	0.78416 (10)	0.51830 (8)	0.0285 (2)
O2	1.10549 (18)	0.65801 (11)	0.54066 (9)	0.0377 (3)
O1	1.41852 (17)	1.30674 (12)	0.11938 (9)	0.0378 (3)
N1	1.14709 (19)	1.30851 (12)	0.00274 (9)	0.0232 (3)
C7	1.1642 (2)	1.13450 (14)	0.20582 (11)	0.0214 (3)
C11	0.8703 (2)	1.03005 (14)	0.34869 (11)	0.0220 (3)
H11	0.7179	1.0388	0.3812	0.026*
C10	1.0327 (2)	0.90031 (14)	0.39573 (11)	0.0211 (3)
C13	0.9679 (2)	0.76837 (15)	0.49291 (11)	0.0240 (3)
C4	1.3404 (3)	1.36011 (16)	−0.19405 (12)	0.0285 (3)
H4A	1.4773	1.2843	−0.167	0.034*
H4B	1.389	1.439	−0.2616	0.034*
C8	1.3275 (2)	1.00679 (15)	0.25594 (12)	0.0256 (3)
H8	1.482	1	0.2262	0.031*
C12	0.9354 (2)	1.14597 (14)	0.25349 (11)	0.0234 (3)
H12	0.8259	1.2316	0.2214	0.028*
C5	1.2352 (3)	1.42408 (15)	−0.09739 (12)	0.0281 (3)
H5A	1.3527	1.4615	−0.0725	0.034*
H5B	1.1085	1.5071	−0.1269	0.034*
C3	1.1643 (3)	1.29141 (15)	−0.22919 (12)	0.0275 (3)
H3A	1.2388	1.2434	−0.2858	0.033*
H3B	1.0372	1.3697	−0.266	0.033*
C2	1.0677 (2)	1.17679 (15)	−0.12294 (11)	0.0260 (3)
H2A	0.9453	1.1417	−0.1463	0.031*
H2B	1.1909	1.0915	−0.093	0.031*
C6	1.2522 (2)	1.25752 (15)	0.10503 (12)	0.0233 (3)
C9	1.2617 (2)	0.89002 (15)	0.34957 (12)	0.0259 (3)
H9	1.3711	0.8044	0.3817	0.031*
C1	0.9701 (2)	1.24338 (16)	−0.02665 (12)	0.0258 (3)
H1A	0.8338	1.3201	−0.0527	0.031*
H1B	0.9226	1.1659	0.0424	0.031*
C14	0.6585 (3)	0.65522 (17)	0.60534 (13)	0.0328 (3)
H14A	0.7227	0.5674	0.5842	0.049*
H14B	0.4912	0.6707	0.6088	0.049*
H14C	0.7094	0.6423	0.6806	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3	0.0247 (5)	0.0288 (5)	0.0255 (5)	−0.0082 (4)	0.0020 (4)	−0.0002 (4)
O2	0.0287 (6)	0.0328 (6)	0.0408 (6)	−0.0048 (5)	−0.0073 (5)	0.0027 (5)
O1	0.0341 (6)	0.0479 (6)	0.0359 (6)	−0.0257 (5)	−0.0023 (5)	−0.0085 (5)
N1	0.0275 (6)	0.0235 (6)	0.0219 (6)	−0.0127 (5)	0.0033 (4)	−0.0085 (5)
C7	0.0230 (7)	0.0256 (6)	0.0204 (7)	−0.0095 (5)	0.0002 (5)	−0.0110 (5)
C11	0.0180 (7)	0.0274 (7)	0.0226 (7)	−0.0067 (5)	0.0020 (5)	−0.0102 (6)
C10	0.0228 (7)	0.0254 (7)	0.0184 (6)	−0.0077 (5)	−0.0025 (5)	−0.0088 (5)
C13	0.0234 (7)	0.0286 (7)	0.0215 (7)	−0.0067 (6)	−0.0033 (5)	−0.0083 (6)
C4	0.0320 (8)	0.0276 (7)	0.0240 (7)	−0.0118 (6)	0.0052 (6)	−0.0050 (6)
C8	0.0175 (7)	0.0344 (7)	0.0260 (7)	−0.0073 (6)	0.0012 (5)	−0.0108 (6)
C12	0.0216 (7)	0.0233 (7)	0.0260 (7)	−0.0030 (5)	−0.0020 (5)	−0.0095 (6)
C5	0.0356 (8)	0.0213 (7)	0.0279 (7)	−0.0126 (6)	0.0033 (6)	−0.0064 (6)
C3	0.0311 (8)	0.0294 (7)	0.0221 (7)	−0.0055 (6)	−0.0010 (5)	−0.0090 (6)
C2	0.0286 (8)	0.0279 (7)	0.0251 (7)	−0.0089 (6)	−0.0044 (6)	−0.0099 (6)
C6	0.0214 (7)	0.0252 (7)	0.0259 (7)	−0.0077 (5)	0.0034 (5)	−0.0113 (6)
C9	0.0221 (7)	0.0291 (7)	0.0257 (7)	−0.0020 (6)	−0.0053 (5)	−0.0083 (6)
C1	0.0235 (7)	0.0308 (7)	0.0250 (7)	−0.0103 (6)	−0.0004 (5)	−0.0087 (6)
C14	0.0298 (8)	0.0348 (8)	0.0278 (8)	−0.0132 (6)	0.0000 (6)	0.0008 (6)

Geometric parameters (Å, º)

O3—C13	1.337 (2)	C4—H4B	0.97
O3—C14	1.4514 (17)	C8—C9	1.3826 (19)
O2—C13	1.2054 (17)	C8—H8	0.93
O1—C6	1.2320 (18)	C12—H12	0.93
N1—C6	1.3496 (18)	C5—H5A	0.97
N1—C1	1.4655 (19)	C5—H5B	0.97
N1—C5	1.4664 (17)	C3—C2	1.5223 (19)
C7—C12	1.391 (2)	C3—H3A	0.97
C7—C8	1.393 (2)	C3—H3B	0.97
C7—C6	1.5113 (18)	C2—C1	1.5213 (19)
C11—C12	1.3861 (18)	C2—H2A	0.97
C11—C10	1.3942 (19)	C2—H2B	0.97
C11—H11	0.93	C9—H9	0.93
C10—C9	1.387 (2)	C1—H1A	0.97
C10—C13	1.4918 (19)	C1—H1B	0.97
C4—C5	1.5191 (19)	C14—H14A	0.96
C4—C3	1.520 (2)	C14—H14B	0.96
C4—H4A	0.97	C14—H14C	0.96
C13—O3—C14	115.47 (10)	C4—C5—H5B	109.6
C6—N1—C1	125.92 (11)	H5A—C5—H5B	108.1
C6—N1—C5	119.70 (12)	C4—C3—C2	110.94 (12)
C1—N1—C5	113.67 (11)	C4—C3—H3A	109.5
C12—C7—C8	119.40 (12)	C2—C3—H3A	109.5
C12—C7—C6	123.66 (11)	C4—C3—H3B	109.5
C8—C7—C6	116.86 (12)	C2—C3—H3B	109.5
C12—C11—C10	120.13 (12)	H3A—C3—H3B	108
C12—C11—H11	119.9	C1—C2—C3	111.32 (11)
C10—C11—H11	119.9	C1—C2—H2A	109.4
C9—C10—C11	119.69 (12)	C3—C2—H2A	109.4
C9—C10—C13	118.03 (11)	C1—C2—H2B	109.4
C11—C10—C13	122.26 (12)	C3—C2—H2B	109.4
O2—C13—O3	123.63 (13)	H2A—C2—H2B	108
O2—C13—C10	124.22 (13)	O1—C6—N1	122.56 (12)
O3—C13—C10	112.10 (11)	O1—C6—C7	118.58 (12)
C5—C4—C3	110.68 (12)	N1—C6—C7	118.86 (12)
C5—C4—H4A	109.5	C8—C9—C10	120.14 (12)
C3—C4—H4A	109.5	C8—C9—H9	119.9
C5—C4—H4B	109.5	C10—C9—H9	119.9
C3—C4—H4B	109.5	N1—C1—C2	110.13 (12)
H4A—C4—H4B	108.1	N1—C1—H1A	109.6
C9—C8—C7	120.44 (13)	C2—C1—H1A	109.6
C9—C8—H8	119.8	N1—C1—H1B	109.6
C7—C8—H8	119.8	C2—C1—H1B	109.6
C11—C12—C7	120.15 (12)	H1A—C1—H1B	108.1
C11—C12—H12	119.9	O3—C14—H14A	109.5
C7—C12—H12	119.9	O3—C14—H14B	109.5
N1—C5—C4	110.27 (11)	H14A—C14—H14B	109.5
N1—C5—H5A	109.6	O3—C14—H14C	109.5
C4—C5—H5A	109.6	H14A—C14—H14C	109.5
N1—C5—H5B	109.6	H14B—C14—H14C	109.5
C12—C11—C10—C9	2.35 (19)	C5—C4—C3—C2	−54.04 (15)
C12—C11—C10—C13	−175.86 (12)	C4—C3—C2—C1	53.59 (15)
C14—O3—C13—O2	−2.60 (19)	C1—N1—C6—O1	171.43 (13)
C14—O3—C13—C10	175.10 (11)	C5—N1—C6—O1	1.71 (19)
C9—C10—C13—O2	6.5 (2)	C1—N1—C6—C7	−8.12 (19)
C11—C10—C13—O2	−175.28 (13)	C5—N1—C6—C7	−177.84 (11)
C9—C10—C13—O3	−171.20 (11)	C12—C7—C6—O1	122.57 (15)
C11—C10—C13—O3	7.03 (18)	C8—C7—C6—O1	−54.07 (17)
C12—C7—C8—C9	2.31 (19)	C12—C7—C6—N1	−57.86 (18)
C6—C7—C8—C9	179.10 (12)	C8—C7—C6—N1	125.50 (14)
C10—C11—C12—C7	−1.17 (19)	C7—C8—C9—C10	−1.1 (2)
C8—C7—C12—C11	−1.15 (19)	C11—C10—C9—C8	−1.19 (19)
C6—C7—C12—C11	−177.71 (12)	C13—C10—C9—C8	177.09 (12)
C6—N1—C5—C4	112.46 (14)	C6—N1—C1—C2	−112.70 (14)
C1—N1—C5—C4	−58.47 (15)	C5—N1—C1—C2	57.56 (15)
C3—C4—C5—N1	55.55 (15)	C3—C2—C1—N1	−54.21 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1	0.97	2.33	2.750 (3)	105
C14—H14B···O2^i	0.96	2.56	3.436 (4)	153

Symmetry code: (i) x−1, y, z.