1-(Carbamoyl­methyl)­cyclo­hexane­carboxyl­ic acid

Nagaraj, B.; Yathirajan, H.S.; Nagaraja, P.; Lynch, D.E.

doi:10.1107/S1600536805006148

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 4| April 2005| Pages o884-o885

https://doi.org/10.1107/S1600536805006148

1-(Carbamoylmethyl)cyclohexanecarboxylic acid

Basavegowda Nagaraj,^a Hemmige S. Yathirajan,^a Padmarajaiah Nagaraja ^a and Daniel E. Lynch ^b ^*

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^bSchool of Science and the Environment, Coventry University, Coventry CV1 5FB, UK
^*Correspondence e-mail: apx106@coventry.ac.uk

(Received 22 February 2005; accepted 25 February 2005; online 11 March 2005)

Molecules of the title compound, C₉H₁₅NO₃, form a two-dimensional hydrogen-bonded network, via O—H⋯O and N—H⋯O interactions, which runs parallel to the bc plane. In this structure, neither the carboxylic acid groups nor the carbamoyl groups are involved in dimer formations.

Comment

The title compound, (I), is used as an intermediate in the synthesis of biologically active heterocycles (LaRoche & Helmers, 2004 ). A search of the Cambridge Structural Database (Version 5.26; Allen, 2002 ) reveals that there are 11 structures of 1,1-disubstituted cyclohexane with a carboxylic acid group as one of the substituents. Of these, only three contain 1-cyclohexanecarboxylic acid itself. The remaining structures each contain an amino group (as the second substituent), with further attached groups on the amino N atom. There are no structures similar to 1-(carbamoylmethyl)cyclohexane.

Molecules of the title compound (Fig. 1) form a two-dimensional hydrogen-bonded network, via O—H⋯O and N—H⋯O interactions, which runs parallel to the bc plane. Hydrogen-bonding associations are listed in Table 1. The carboxylic OH group hydrogen bonds to the carbamoyl O atom of an adjacent molecule while the amino group of that molecule, in return, hydrogen bonds with the carbamoyl O atom of the first molecule. These two associations form a hydrogen-bonded ring motif [R₂²(11) graph set (Etter, 1990 )] that, when repeated, propagates the hydrogen-bonding network in the b-axis direction. An N—H⋯O association between the second amino H atom and an adjacent carboxyl carbonyl O atom in the c-axis direction generates the two-dimensional network. Interestingly, in this structure, neither the carboxylic acid groups nor the carbamoyl groups are involved in R₂²(8) graph-set dimer formations, with like groups or with each other.

Figure 1
The molecular configuration and atom-numbering scheme for (I

). Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as spheres of arbitrary radius.

Experimental

Cyclohexanone (1.04 g, 10 mmol) was treated with ethyl cyanoacetate (1.06 g, 10 mmol) in the presence of NaOH (5 ml, 10% aqueous solution). The resultant compound was further treated with NaCN (0.49 g, 10 mmol) in ethanol (5 ml), and hydrolysed to obtain the title compound. Crystals were grown from methanol.

Crystal data

C₉H₁₅NO₃
M_r = 185.22
Monoclinic, P2₁/c
a = 13.4973 (5) Å
b = 8.0905 (2) Å
c = 8.8358 (3) Å
β = 102.627 (2)°
V = 941.53 (5) Å³
Z = 4
D_x = 1.307 Mg m⁻³
Mo Kα radiation
Cell parameters from 2268 reflections
θ = 2.9–27.5°
μ = 0.10 mm⁻¹
T = 120 (2) K
Prism, colourless
0.65 × 0.30 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.939, T_max = 0.990
10959 measured reflections
1842 independent reflections
1627 reflections with I > 2σ(I)
R_int = 0.030
θ_max = 26.0°
h = −16 → 16
k = −9 → 9
l = −10 → 10

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.103
S = 1.05
1842 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0503P)² + 0.4339P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.048 (6)

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1ⁱ	0.963 (18)	1.640 (19)	2.5829 (13)	165 (2)
N1—H1⋯O1ⁱⁱ	0.88	2.21	3.0680 (15)	164
N1—H2⋯O2ⁱⁱⁱ	0.88	2.12	2.9635 (15)	162
Symmetry codes: (i) $[-x,y-{\script{1\over 2}},{\script{1\over 2}}-z]$ ; (ii) $[-x,{\script{1\over 2}}+y,{\script{1\over 2}}-z]$ ; (iii) $[x,{\script{1\over 2}}-y,z-{\script{1\over 2}}]$ .

The carboxyl H atom was located in a difference Fourier synthesis and its positional parameters were refined. Other H atoms were included in the refinement at calculated positions, in the riding-model approximation, with C—H distances of 0.99 Å and N—H distances of 0.88 Å. The isotropic displacement parameters for all H atoms were set equal to 1.25U_eq of the carrier atom.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805006148/is6057sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805006148/is6057Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

1-(Carbamoylmethyl)cyclohexanecarboxylic acid top

Crystal data top

C₉H₁₅NO₃	F(000) = 400
M_r = 185.22	D_x = 1.307 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 437 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.4973 (5) Å	Cell parameters from 2268 reflections
b = 8.0905 (2) Å	θ = 2.9–27.5°
c = 8.8358 (3) Å	µ = 0.10 mm⁻¹
β = 102.627 (2)°	T = 120 K
V = 941.53 (5) Å³	Prism, colourless
Z = 4	0.65 × 0.30 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	1842 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1627 reflections with I > 2σ(I)
10 cm confocal mirrors monochromator	R_int = 0.030
Detector resolution: 9.091 pixels mm^-1	θ_max = 26.0°, θ_min = 3.5°
φ and ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
T_min = 0.939, T_max = 0.990	l = −10→10
10959 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0503P)² + 0.4339P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
1842 reflections	Δρ_max = 0.20 e Å⁻³
122 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.048 (6)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.01177 (7)	0.16623 (11)	0.19598 (11)	0.0192 (3)
O2	0.18173 (7)	−0.03683 (12)	0.38790 (11)	0.0214 (3)
O3	0.11848 (8)	−0.18613 (12)	0.17583 (11)	0.0224 (3)
H3	0.0775 (13)	−0.237 (2)	0.239 (2)	0.028*
N1	0.07782 (9)	0.40190 (14)	0.12383 (13)	0.0202 (3)
H1	0.0420	0.4629	0.1748	0.025*
H2	0.1191	0.4493	0.0724	0.025*
C1	0.22107 (9)	0.04376 (16)	0.14274 (15)	0.0157 (3)
C2	0.27157 (10)	−0.06508 (17)	0.03825 (16)	0.0207 (3)
H21	0.2217	−0.1471	−0.0157	0.026*
H22	0.2921	0.0050	−0.0415	0.026*
C3	0.36471 (11)	−0.1557 (2)	0.1304 (2)	0.0310 (4)
H31	0.3966	−0.2201	0.0585	0.039*
H32	0.3434	−0.2340	0.2033	0.039*
C4	0.44223 (11)	−0.0342 (2)	0.2213 (2)	0.0354 (4)
H41	0.4999	−0.0963	0.2844	0.044*
H42	0.4688	0.0368	0.1480	0.044*
C5	0.39417 (11)	0.0735 (2)	0.32693 (18)	0.0271 (4)
H51	0.4443	0.1561	0.3789	0.034*
H52	0.3751	0.0037	0.4081	0.034*
C6	0.29991 (10)	0.16275 (17)	0.23608 (16)	0.0199 (3)
H61	0.3207	0.2429	0.1642	0.025*
H62	0.2683	0.2255	0.3094	0.025*
C7	0.13317 (10)	0.14047 (17)	0.03674 (15)	0.0169 (3)
H71	0.1622	0.2166	−0.0298	0.021*
H72	0.0889	0.0611	−0.0320	0.021*
C8	0.06951 (9)	0.23871 (17)	0.12452 (14)	0.0159 (3)
C9	0.17348 (10)	−0.06333 (16)	0.25029 (15)	0.0161 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0178 (5)	0.0183 (5)	0.0229 (5)	0.0012 (4)	0.0078 (4)	0.0003 (4)
O2	0.0227 (5)	0.0249 (5)	0.0166 (5)	0.0010 (4)	0.0041 (4)	−0.0012 (4)
O3	0.0279 (6)	0.0187 (5)	0.0218 (5)	−0.0066 (4)	0.0077 (4)	−0.0022 (4)
N1	0.0241 (6)	0.0163 (6)	0.0219 (6)	0.0026 (5)	0.0088 (5)	0.0015 (5)
C1	0.0153 (6)	0.0155 (6)	0.0161 (7)	0.0014 (5)	0.0031 (5)	−0.0009 (5)
C2	0.0200 (7)	0.0217 (7)	0.0216 (7)	0.0030 (5)	0.0069 (6)	−0.0030 (6)
C3	0.0230 (8)	0.0316 (9)	0.0376 (9)	0.0101 (6)	0.0051 (7)	−0.0063 (7)
C4	0.0167 (7)	0.0444 (10)	0.0433 (10)	0.0075 (7)	0.0024 (7)	−0.0053 (8)
C5	0.0166 (7)	0.0317 (8)	0.0302 (8)	−0.0026 (6)	−0.0009 (6)	−0.0044 (6)
C6	0.0174 (7)	0.0201 (7)	0.0224 (7)	−0.0027 (5)	0.0046 (6)	−0.0025 (5)
C7	0.0184 (7)	0.0176 (7)	0.0151 (6)	0.0011 (5)	0.0042 (5)	0.0013 (5)
C8	0.0151 (6)	0.0181 (7)	0.0126 (6)	0.0015 (5)	−0.0009 (5)	0.0010 (5)
C9	0.0145 (6)	0.0145 (6)	0.0187 (7)	0.0038 (5)	0.0022 (5)	0.0003 (5)

Geometric parameters (Å, º) top

O1—C8	1.2510 (16)	C3—C4	1.529 (2)
O2—C9	1.2156 (16)	C3—H31	0.99
O3—C9	1.3257 (16)	C3—H32	0.99
O3—H3	0.963 (18)	C4—C5	1.522 (2)
N1—C8	1.3252 (18)	C4—H41	0.99
N1—H1	0.88	C4—H42	0.99
N1—H2	0.88	C5—C6	1.529 (2)
C1—C9	1.5274 (18)	C5—H51	0.99
C1—C6	1.5348 (18)	C5—H52	0.99
C1—C2	1.5387 (18)	C6—H61	0.99
C1—C7	1.5528 (17)	C6—H62	0.99
C2—C3	1.528 (2)	C7—C8	1.5043 (18)
C2—H21	0.99	C7—H71	0.99
C2—H22	0.99	C7—H72	0.99

C9—O3—H3	111.3 (10)	C3—C4—H42	109.5
C8—N1—H1	120.0	H41—C4—H42	108.1
C8—N1—H2	120.0	C4—C5—C6	111.46 (12)
H1—N1—H2	120.0	C4—C5—H51	109.3
C9—C1—C6	110.97 (11)	C6—C5—H51	109.3
C9—C1—C2	110.51 (10)	C4—C5—H52	109.3
C6—C1—C2	109.59 (10)	C6—C5—H52	109.3
C9—C1—C7	106.94 (10)	H51—C5—H52	108.0
C6—C1—C7	110.90 (10)	C5—C6—C1	112.67 (11)
C2—C1—C7	107.86 (10)	C5—C6—H61	109.1
C3—C2—C1	112.06 (11)	C1—C6—H61	109.1
C3—C2—H21	109.2	C5—C6—H62	109.1
C1—C2—H21	109.2	C1—C6—H62	109.1
C3—C2—H22	109.2	H61—C6—H62	107.8
C1—C2—H22	109.2	C8—C7—C1	113.73 (10)
H21—C2—H22	107.9	C8—C7—H71	108.8
C2—C3—C4	111.14 (13)	C1—C7—H71	108.8
C2—C3—H31	109.4	C8—C7—H72	108.8
C4—C3—H31	109.4	C1—C7—H72	108.8
C2—C3—H32	109.4	H71—C7—H72	107.7
C4—C3—H32	109.4	O1—C8—N1	122.14 (12)
H31—C3—H32	108.0	O1—C8—C7	120.10 (12)
C5—C4—C3	110.83 (12)	N1—C8—C7	117.75 (12)
C5—C4—H41	109.5	O2—C9—O3	123.19 (12)
C3—C4—H41	109.5	O2—C9—C1	124.28 (12)
C5—C4—H42	109.5	O3—C9—C1	112.48 (11)

C9—C1—C2—C3	−67.91 (14)	C6—C1—C7—C8	−66.21 (14)
C6—C1—C2—C3	54.69 (15)	C2—C1—C7—C8	173.78 (11)
C7—C1—C2—C3	175.52 (12)	C1—C7—C8—O1	−70.50 (15)
C1—C2—C3—C4	−56.56 (17)	C1—C7—C8—N1	108.96 (13)
C2—C3—C4—C5	56.00 (18)	C6—C1—C9—O2	13.30 (17)
C3—C4—C5—C6	−55.11 (18)	C2—C1—C9—O2	135.09 (13)
C4—C5—C6—C1	55.11 (16)	C7—C1—C9—O2	−107.76 (14)
C9—C1—C6—C5	68.36 (14)	C6—C1—C9—O3	−169.07 (11)
C2—C1—C6—C5	−53.96 (15)	C2—C1—C9—O3	−47.28 (14)
C7—C1—C6—C5	−172.93 (11)	C7—C1—C9—O3	69.87 (13)
C9—C1—C7—C8	54.90 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1ⁱ	0.963 (18)	1.640 (19)	2.5829 (13)	165 (2)
N1—H1···O1ⁱⁱ	0.88	2.21	3.0680 (15)	164
N1—H2···O2ⁱⁱⁱ	0.88	2.12	2.9635 (15)	162

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) x, −y+1/2, z−1/2.

Acknowledgements

The authors thank the EPSRC National Crystallography Service (Southampton, England) and acknowledge the use of the EPSRC's Chemical Database Service at Daresbury (Fletcher et al., 1996 ).

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