Cyclo­hexyl­ammonium nitrate

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.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.040
• wR factor = 0.121
• Data-to-parameter ratio = 21.9

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PUBL024_ALERT_1_A The number of authors is greater than 5.
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Author Response: Dr. Shemsi had formatted the manuscript. Mr. Addurihem and Dr. Al-Othman helped in the preparation of the original submission. Mr. Abdulaziz synthesized the compound and wrote the synthesis and non-crytsallographic section of the previously submitted article. Mr. Mohamed Aboud assisted in the preparation. Dr. Chidan and Prof. Fun rewrote the crystallographic section and reformated the article for the new submission as well as replying to the queries raised by the Co-editor of sj5386.

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S1. Comment

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 (pK_b = 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).

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).

S2. Experimental

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.).

S3. Refinement

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 U_iso(H) = 1.2 U_eq(N). Other H atoms were positioned geometrically (C=H 0.97–0.98 Å) and refined using a riding model with U_iso(H) = 1.2 U_eq(C)

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: 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).

Figures

	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.

Cyclohexylammonium nitrate

Crystal data

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) Å^3	0.39 × 0.15 × 0.14 mm
Z = 4

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0584P)^2 + 0.0786P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.042 (6)

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
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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.97	1.89	2.8553 (14)	172
N1—H2···O3^ii	0.94	1.97	2.9074 (15)	172
N1—H3···O1^iii	0.85	2.24	2.9880 (15)	148
N1—H3···O3^iii	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.