organic compounds
Cyclohexylammonium nitrate
aPetrochemicals Research Institute, King Abdulaziz City for Science and Technology, Riyadh 11442, Saudi Arabia, bSustainable Energy Technologies (SET) Center, College of Engineering, King Saud University, PO Box 800, Riyadh 11421, Saudi Arabia, cCenter for Environment and Water, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia, dChemistry Department, King Saud University, Riyadh 11451, Saudi Arabia, eX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and fDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, PO Box 2457, Riaydh 11451, Saudi Arabia
*Correspondence e-mail: hfun.c@ksu.edu.sa
In the title salt, C6H14N+·NO3−, the cyclohexyl ring adopts a chair conformation. The ammonium group occupies an equatorial position and the crystal struture is stabilized by intermolecular N—H⋯O hydrogen-bonding interactions, resulting in a three-dimensional network.
CCDC reference: 783310
Related literature
For the Brønsted–Lowry basicity behavior of cyclohexylamine, see: Solomons (1996). For the preparation of salts of anions and complex anions with cyclohexyl primary ammonium cations, see: Jones et al. (1998); Kolev et al. (2007); Lock et al. (1981); Muthamizhchelvan et al. (2005); Wang et al. (2005); Yun et al. (2004). For precautions relating to the reaction of cyclohexylamine with strong acids or oxidizing agents, see: Chang (2008); Patnaik (2007). For the structures of other cyclohexyleammonium salts, see: Shimada et al. (1955); Smith et al. (1994); Odendal et al. (2010). For ring conformations and ring puckering analysis, see: Cremer & Pople (1975). For reference bond lengths, see: Allen et al. (1987).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Supporting information
CCDC reference: 783310
10.1107/S1600536814002244/sj5386sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814002244/sj5386Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814002244/sj5386Isup3.cml
The title compound C6H11NH3+NO3- was obtained as a by-product upon combining 60 ml, 0.5 M of metal nitrate (metal = Mg2+, Al3+, Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, or Cd2+) with 20 ml, 3.0 M (for divalent metal) or 4.5 M (for trivalent metal) CHA in aqueous or ethanolic media. Depending on the identity of M, a metal hydroxide or oxide was precipitated. Filtering this precipitate resulted in a clear filtrate, which upon the gradual evaporation of the solvent at room temperature resulted in the deposition of beautiful, colorless crystals of HCHA+NO3-. The chemical composition of these crystals was determined by C, H, N elemental microanalysis: (%C: 44.47 exp; 44.43 cal.), (%H: 8.70 exp.; 8.72 cal.), (%N: 17.26 exp.; 17.28 cal.), and (%O: 29.61 exp.; 29.59 cal.).
The nitrogen-bound H-atoms were located in a difference Fourier map and were fixed at their found positions (N–H = 0.8498, 0.9440 and 0.9724 Å), with Uiso(H) = 1.2 Ueq(N). Other H atoms were positioned geometrically (C=H 0.97–0.98 Å) and refined using a riding model with Uiso(H) = 1.2 Ueq(C)
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. Molecular structure of the compound, with atom labels and 50% probability displacement ellipsoids for the non-H atoms. | |
Fig. 2. Crystal packing of the title compound, showing the hydrogen bonding interactions as dashed lines. |
C6H14N+·NO3− | F(000) = 352 |
Mr = 162.19 | Dx = 1.207 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 11857 reflections |
a = 8.9322 (9) Å | θ = 2.4–28.3° |
b = 9.9010 (9) Å | µ = 0.10 mm−1 |
c = 10.3951 (10) Å | T = 294 K |
β = 103.866 (2)° | Block, colorless |
V = 892.53 (15) Å3 | 0.39 × 0.15 × 0.14 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 2214 independent reflections |
Radiation source: fine-focus sealed tube | 1750 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
φ and ω scans | θmax = 28.3°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.964, Tmax = 0.987 | k = 0→13 |
2214 measured reflections | l = 0→13 |
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)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.0584P)2 + 0.0786P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.005 |
2214 reflections | Δρmax = 0.15 e Å−3 |
101 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.042 (6) |
C6H14N+·NO3− | V = 892.53 (15) Å3 |
Mr = 162.19 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.9322 (9) Å | µ = 0.10 mm−1 |
b = 9.9010 (9) Å | T = 294 K |
c = 10.3951 (10) Å | 0.39 × 0.15 × 0.14 mm |
β = 103.866 (2)° |
Bruker APEXII CCD diffractometer | 2214 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1750 reflections with I > 2σ(I) |
Tmin = 0.964, Tmax = 0.987 | Rint = 0.000 |
2214 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.15 e Å−3 |
2214 reflections | Δρmin = −0.15 e Å−3 |
101 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.94737 (12) | 0.24027 (11) | 0.84734 (10) | 0.0591 (3) | |
H1 | 1.0040 | 0.2396 | 0.9397 | 0.071* | |
H2 | 0.9334 | 0.1504 | 0.8165 | 0.071* | |
H3 | 1.0001 | 0.2818 | 0.8017 | 0.071* | |
C1 | 0.79115 (13) | 0.30167 (11) | 0.83331 (11) | 0.0504 (3) | |
H4 | 0.7312 | 0.2428 | 0.8779 | 0.060* | |
C2 | 0.80481 (15) | 0.43882 (13) | 0.89905 (13) | 0.0619 (3) | |
H5 | 0.8701 | 0.4967 | 0.8605 | 0.074* | |
H6 | 0.8523 | 0.4293 | 0.9928 | 0.074* | |
C3 | 0.64691 (18) | 0.50274 (15) | 0.88097 (18) | 0.0806 (4) | |
H7 | 0.6580 | 0.5927 | 0.9190 | 0.097* | |
H8 | 0.5855 | 0.4495 | 0.9276 | 0.097* | |
C4 | 0.56468 (19) | 0.51139 (15) | 0.7354 (2) | 0.0887 (5) | |
H9 | 0.4622 | 0.5482 | 0.7270 | 0.106* | |
H10 | 0.6208 | 0.5721 | 0.6906 | 0.106* | |
C5 | 0.55222 (17) | 0.37454 (16) | 0.67001 (17) | 0.0833 (5) | |
H11 | 0.5052 | 0.3842 | 0.5762 | 0.100* | |
H12 | 0.4864 | 0.3168 | 0.7081 | 0.100* | |
C6 | 0.70975 (16) | 0.30923 (13) | 0.68820 (12) | 0.0638 (3) | |
H13 | 0.6979 | 0.2189 | 0.6509 | 0.077* | |
H14 | 0.7716 | 0.3614 | 0.6412 | 0.077* | |
O1 | 0.90382 (12) | 0.78324 (9) | 0.87802 (9) | 0.0694 (3) | |
O2 | 0.82965 (10) | 0.96820 (10) | 0.95391 (9) | 0.0681 (3) | |
O3 | 0.87733 (12) | 0.96351 (10) | 0.75996 (9) | 0.0729 (3) | |
N2 | 0.86827 (10) | 0.90604 (10) | 0.86507 (9) | 0.0529 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0641 (6) | 0.0561 (5) | 0.0586 (6) | 0.0105 (4) | 0.0177 (4) | 0.0154 (4) |
C1 | 0.0543 (6) | 0.0449 (5) | 0.0521 (6) | 0.0010 (4) | 0.0129 (5) | 0.0065 (4) |
C2 | 0.0651 (7) | 0.0546 (7) | 0.0635 (7) | −0.0030 (5) | 0.0108 (6) | −0.0057 (5) |
C3 | 0.0777 (9) | 0.0615 (8) | 0.1048 (12) | 0.0089 (7) | 0.0265 (9) | −0.0157 (8) |
C4 | 0.0674 (8) | 0.0606 (8) | 0.1274 (15) | 0.0139 (7) | 0.0022 (9) | 0.0051 (8) |
C5 | 0.0720 (8) | 0.0705 (9) | 0.0906 (10) | 0.0057 (7) | −0.0135 (7) | 0.0017 (8) |
C6 | 0.0754 (8) | 0.0569 (7) | 0.0535 (7) | 0.0052 (6) | 0.0041 (6) | 0.0008 (5) |
O1 | 0.0868 (6) | 0.0492 (5) | 0.0696 (6) | 0.0075 (4) | 0.0139 (5) | 0.0001 (4) |
O2 | 0.0688 (5) | 0.0736 (6) | 0.0650 (5) | 0.0105 (4) | 0.0221 (4) | −0.0094 (4) |
O3 | 0.0975 (7) | 0.0663 (6) | 0.0549 (5) | 0.0129 (5) | 0.0181 (5) | 0.0090 (4) |
N2 | 0.0479 (5) | 0.0538 (5) | 0.0536 (5) | 0.0040 (4) | 0.0051 (4) | −0.0018 (4) |
N1—C1 | 1.4968 (15) | C3—H8 | 0.9700 |
N1—H1 | 0.9724 | C4—C5 | 1.508 (2) |
N1—H2 | 0.9440 | C4—H9 | 0.9700 |
N1—H3 | 0.8498 | C4—H10 | 0.9700 |
C1—C6 | 1.5112 (16) | C5—C6 | 1.519 (2) |
C1—C2 | 1.5119 (17) | C5—H11 | 0.9700 |
C1—H4 | 0.9800 | C5—H12 | 0.9700 |
C2—C3 | 1.5159 (19) | C6—H13 | 0.9700 |
C2—H5 | 0.9700 | C6—H14 | 0.9700 |
C2—H6 | 0.9700 | O1—N2 | 1.2556 (13) |
C3—C4 | 1.518 (3) | O2—N2 | 1.2261 (12) |
C3—H7 | 0.9700 | O3—N2 | 1.2516 (13) |
C1—N1—H1 | 110.6 | H7—C3—H8 | 108.0 |
C1—N1—H2 | 107.8 | C5—C4—C3 | 111.37 (13) |
H1—N1—H2 | 108.9 | C5—C4—H9 | 109.4 |
C1—N1—H3 | 112.2 | C3—C4—H9 | 109.4 |
H1—N1—H3 | 109.1 | C5—C4—H10 | 109.4 |
H2—N1—H3 | 108.2 | C3—C4—H10 | 109.4 |
N1—C1—C6 | 109.37 (10) | H9—C4—H10 | 108.0 |
N1—C1—C2 | 110.38 (10) | C4—C5—C6 | 111.12 (12) |
C6—C1—C2 | 111.97 (10) | C4—C5—H11 | 109.4 |
N1—C1—H4 | 108.3 | C6—C5—H11 | 109.4 |
C6—C1—H4 | 108.3 | C4—C5—H12 | 109.4 |
C2—C1—H4 | 108.3 | C6—C5—H12 | 109.4 |
C1—C2—C3 | 110.31 (11) | H11—C5—H12 | 108.0 |
C1—C2—H5 | 109.6 | C1—C6—C5 | 110.81 (12) |
C3—C2—H5 | 109.6 | C1—C6—H13 | 109.5 |
C1—C2—H6 | 109.6 | C5—C6—H13 | 109.5 |
C3—C2—H6 | 109.6 | C1—C6—H14 | 109.5 |
H5—C2—H6 | 108.1 | C5—C6—H14 | 109.5 |
C2—C3—C4 | 111.14 (13) | H13—C6—H14 | 108.1 |
C2—C3—H7 | 109.4 | O2—N2—O3 | 121.20 (10) |
C4—C3—H7 | 109.4 | O2—N2—O1 | 120.99 (10) |
C2—C3—H8 | 109.4 | O3—N2—O1 | 117.79 (10) |
C4—C3—H8 | 109.4 | ||
N1—C1—C2—C3 | 178.21 (11) | C3—C4—C5—C6 | −55.5 (2) |
C6—C1—C2—C3 | 56.11 (15) | N1—C1—C6—C5 | −178.51 (11) |
C1—C2—C3—C4 | −55.73 (16) | C2—C1—C6—C5 | −55.83 (15) |
C2—C3—C4—C5 | 56.08 (19) | C4—C5—C6—C1 | 55.08 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.97 | 1.89 | 2.8553 (14) | 172 |
N1—H2···O3ii | 0.94 | 1.97 | 2.9074 (15) | 172 |
N1—H3···O1iii | 0.85 | 2.24 | 2.9880 (15) | 148 |
N1—H3···O3iii | 0.85 | 2.28 | 3.0689 (15) | 155 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) x, y−1, z; (iii) −x+2, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.9700 | 1.8900 | 2.8553 (14) | 172.00 |
N1—H2···O3ii | 0.9400 | 1.9700 | 2.9074 (15) | 172.00 |
N1—H3···O1iii | 0.8500 | 2.2400 | 2.9880 (15) | 148.00 |
N1—H3···O3iii | 0.8500 | 2.2800 | 3.0689 (15) | 155.00 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) x, y−1, z; (iii) −x+2, y−1/2, −z+3/2. |
Acknowledgements
The authors are grateful to Dr Mohammed Fettouhi for the data collection and useful discussions and King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia, for the use of the X-ray facility. Funding for this work was provided by King Abdulaziz City for Science and Technology (KACST), Riyadh, Saudi Arabia, through project No. 29–280. CSCK thanks Universiti Sains Malaysia for a postdoctoral research fellowship.
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The title compound C6H11NH3+NO3- was obtained as the unexpected by-product of the reaction of metal (M) nitrate salts (metal = Mg2+, Al3+, Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, or Cd2+) with cyclohexylamine (CHA) in either aqueous or ethanolic media. It was expected that CHA would coordinate to the M cations due to its Lewis basicity. However, metal oxides or hydroxides were formed along with C6H11NH3+NO3-, which reflects the Brønsted-Lowry basicity of CHA (pKb = 3.36, Solomons, 1996). This base strength makes CHA suitable for the preparation of several salts of anions and complex anions through the formation of the primary ammonium cation (C6H11NH3+) (Jones et al., 1998; Kolev et al., 2007; Lock et al., 1981; Muthamizhchelvan et al., 2005; Shimada et al., 1955; Smith et al., 1994; Wang et al., 2005; Yun et al., 2004). This Brønsted-Lowry behavior was responsible for the formation of the present compound, (I) (Fig. 1), which is dangerous to prepare from a direct reaction between CHA and nitric acid (HNO3) because CHA reacts violently with strong acids or oxidizing agents and may cause fire and explosion (Chang, 2008; Patnaik, 2007).
The asymmetric unit of the title compound contains one cyclohexylammonium cation (C1—C6/N1) and one nitrate anion (N2/O1—O3). The cyclohexane ring adopts a chair conformation, with puckering parameters: Q = 0.5668 (17) Å, θ = 179.29 (17)°, and φ = 276 (21)° (Cremer & Pople, 1975). The ammonium functional group is at an equatorial position to minimize 1,3 and 1,5 di-axial interactions. The bond lengths (Allen et al., 1987) and bond angles are in the normal ranges and are comparable with those reported earlier for similar compounds (Shimada et al., 1955; Smith et al., 1994; Odendal et al., 2010). Each proton of the ammonium group is hydrogen-bonded to two oxygen atoms of the nitrate ion. These intermolecular N–H···O hydrogen bonds (Table 2) generate a three-dimensional network (Fig. 2).