organic compounds
N,N′,N′′-Tricyclohexylguanidinium iodide
aDepartment of Chemistry, Al al-Bayt University, Mafraq 25113, Jordan, and bDepartment of Chemistry and Biochemistry, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5
*Correspondence e-mail: fjuqqa@aabu.edu.jo, bfali@aabu.edu.jo
In the title compound, C19H36N3+·I−, the orientation of the cyclohexyl rings around the planar (sum of N—C—N angles = 360°) CN3+ unit produces around the N—H groups. As a consequence of this particular orientation of the tricyclohexylguanidinium cation (hereafter denoted CHGH+), hydrogen bonding is restricted to classical N—H⋯I and non-clasical (cyclohexyl)C—H⋯I hydrogen bonds. The propeller CHGH+ cation and the oriented hydrogen-bonding interactions lead to a three-dimensional supramolecular structure.
Related literature
For background to guanidines, see: Ishikawa & Isobe (2002); Moroni et al. (2001); Yoshiizumi et al. (1998). The title salt is isomorphous with the chloride anion-analogue (Cai & Hu, 2006) and N,N′,N′′-triisopropylguanidinium chloride (Said et al., 2005). (Ishikawa & Isobe, 2002). The structural features and hydrogen -bonding array provided by guanidinium cations suggest them to be good building blocks for the formation of supramolecular entities, see: Said, Bazinet et al. (2006); Said, Ong et al. (2006). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
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Data collection: XSCANS (Bruker, 1996); cell XSCANS; data reduction: XSCANS; 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.
Supporting information
https://doi.org/10.1107/S1600536811049683/bq2321sup1.cif
contains datablocks I, global. DOI:Supporting information file. DOI: https://doi.org/10.1107/S1600536811049683/bq2321Isup2.mol
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811049683/bq2321Isup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811049683/bq2321Isup4.cml
General: N,N',N"-tricyclohexylguanidine was prepared according to literature methods. All other reagents were purchased from Aldrich Chemical Company and used without further purification. Elemental analyses were run on a Perkin Elmer PE CHN 4000 elemental analysis system.
Synthesis and crystallization of N,N',N"-tricyclohexylguanidinium iodide, {C(HNcyclohexyl)3}+I-
In a round bottom flask, a combination of 0.200 g (1.34 mmol) ammonium iodide and 0.41 g (1.34 mmol) N,N',N''-tricyclohexylguanidine were dissolved in 10 mL of distilled water. White precipitate of {C(HNcyclohexyl)3}+I- was deposited immediately of the solution (0.46 g, 92.0% yield). The product was crystallized from a mixture of methanol and distilled water to give white cubic crystals. In addition to confirming the
through elemental analysis, the solid obtained was examined by single-crystal X-ray analysis. Anal. Calcd for C19H36IN3 C, 52.65; H, 8.37; N, 9.70. Found C, 52.56; H, 8.63; N, 9.40.Hydrogen atoms were included in calculated positions and refined as riding on their parent atoms with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) and N—H = 0.86 Å and Uiso(H) = 1.2Ueq(N).
Guanidines are of special interest due to their possible application in medicine (Yoshiizumi et al., 1998; Moroni et al., 2001). They are considered super bases as they are easily protonated to generate guanidinium cations (Ishikawa & Isobe, 2002). The structural features and hydrogen bonding array provided by these cations suggest that they are good building blocks for the formation of supramolecular entities (Said, Bazinet et al., 2006, Said, Ong et al., 2006, Said et al., 2005).
The title compound (I), Fig. 1, is a typical N,N',N"-trisubstituted guanidinium halide salt with normal geometric parameters (Said et al., 2005). The central guanidinium fragment of the cation of the title salt is planar [sum of NCN angles is 360°] with bond lengths and angles as expected for a central Csp2
accounting for charge delocalization between the three C—N bonds. The bond length C1—N1 [1.330 (5) Å] is comparable with literature averages for substituted and unsubstituted guanidinium cations (1.321 and 1.328 Å, respectively; (Allen et al., 1987)). The cyclohexyl ring has the normal chair conformation with conventional bond lengths and angles. A partial packing diagram is shown in Fig. 2. The CHGH+ ions occur in chains, with the I- anions arranged parallel to the cation chains. The cations and anions occur in a 3-fold array: three anions surround each cation [via its three N—H···I, 2.856 Å; (165°) and C—H···I (3.027 Å; 158°) interactions, Table 1, Fig. 3], and three cations surround each anion resulting in the formation of three-dimensional supramolecular structure.This type of supramolecular synthons has been observed frequently in other related compounds. The stability of this is evidenced by the crystallization of a whole series of isomorphous compounds of this type, such as N,N',N''-tricyclohexylguanidinium chloride (Cai & Hu, 2006), even with different substituents like N,N',N''-triisipropylguanidinium chloride (Said et al., 2005).For background to guanidines, see: Ishikawa & Isobe (2002); Moroni et al. (2001); Yoshiizumi et al. (1998). For the title salt is isomorphous with the chloride anion-analogue (Cai & Hu, 2006) and N,N',N''-triisopropylguanidinium chloride (Said et al., 2005). (Ishikawa & Isobe, 2002). The structural features and hydrogen -bonding array provided by guanidinium cations suggest them to be good building blocks for the formation of supramolecular entities, see: Said, Bazinet et al. (2006); Said, Ong et al. (2006). For bond-length data, see: Allen et al. (1987);
Data collection: XSCANS (Bruker, 1996); cell
XSCANS (Bruker, 1996); data reduction: XSCANS (Bruker, 1996); 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).C19H36N3+·I− | Dx = 1.343 Mg m−3 |
Mr = 433.41 | Mo Kα radiation, λ = 0.71073 Å |
Cubic, P213 | Cell parameters from 30 reflections |
Hall symbol: P 2ac 2ab 3 | θ = 3.9–6.9° |
a = 12.893 (4) Å | µ = 1.50 mm−1 |
V = 2143 (2) Å3 | T = 188 K |
Z = 4 | Block, colorless |
F(000) = 896 | 0.5 × 0.3 × 0.3 mm |
Bruker P4 diffractometer | 628 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.055 |
Graphite monochromator | θmax = 25.9°, θmin = 2.2° |
ω scans | h = 0→15 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = 0→15 |
Tmin = 0.271, Tmax = 0.320 | l = 0→15 |
2387 measured reflections | 3 standard reflections every 97 reflections |
802 independent reflections | intensity decay: none |
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-atom parameters constrained |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0269P)2 + 0.7683P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
802 reflections | Δρmax = 0.33 e Å−3 |
70 parameters | Δρmin = −0.27 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 802 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.08 (8) |
C19H36N3+·I− | Z = 4 |
Mr = 433.41 | Mo Kα radiation |
Cubic, P213 | µ = 1.50 mm−1 |
a = 12.893 (4) Å | T = 188 K |
V = 2143 (2) Å3 | 0.5 × 0.3 × 0.3 mm |
Bruker P4 diffractometer | 628 reflections with I > 2σ(I) |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | Rint = 0.055 |
Tmin = 0.271, Tmax = 0.320 | 3 standard reflections every 97 reflections |
2387 measured reflections | intensity decay: none |
802 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.076 | Δρmax = 0.33 e Å−3 |
S = 1.04 | Δρmin = −0.27 e Å−3 |
802 reflections | Absolute structure: Flack (1983), 802 Friedel pairs |
70 parameters | Absolute structure parameter: 0.08 (8) |
0 restraints |
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 | ||
I1 | 0.89107 (4) | 0.89107 (4) | 0.89107 (4) | 0.0589 (2) | |
N1 | 0.8894 (5) | 0.1398 (4) | 0.7489 (4) | 0.0715 (16) | |
H1A | 0.8803 | 0.0781 | 0.7728 | 0.086* | |
C1 | 0.8343 (6) | 0.1657 (6) | 0.6657 (6) | 0.064 (3) | |
C2 | 0.9631 (6) | 0.2045 (6) | 0.8033 (6) | 0.071 (2) | |
H2A | 0.9812 | 0.2636 | 0.7591 | 0.086* | |
C3 | 0.9164 (6) | 0.2440 (8) | 0.9017 (8) | 0.114 (4) | |
H3A | 0.8951 | 0.1861 | 0.9448 | 0.137* | |
H3B | 0.8556 | 0.2855 | 0.8862 | 0.137* | |
C4 | 0.9957 (9) | 0.3091 (9) | 0.9588 (11) | 0.149 (5) | |
H4A | 1.0115 | 0.3701 | 0.9177 | 0.179* | |
H4B | 0.9660 | 0.3323 | 1.0239 | 0.179* | |
C5 | 1.0919 (7) | 0.2525 (9) | 0.9799 (7) | 0.100 (3) | |
H5A | 1.0780 | 0.1967 | 1.0285 | 0.120* | |
H5B | 1.1419 | 0.2990 | 1.0116 | 0.120* | |
C6 | 1.1359 (5) | 0.2091 (7) | 0.8838 (7) | 0.084 (2) | |
H6A | 1.1957 | 0.1668 | 0.9009 | 0.101* | |
H6C | 1.1593 | 0.2654 | 0.8397 | 0.101* | |
C7 | 1.0581 (6) | 0.1441 (7) | 0.8255 (7) | 0.086 (3) | |
H7C | 1.0885 | 0.1206 | 0.7608 | 0.103* | |
H7A | 1.0404 | 0.0835 | 0.8663 | 0.103* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0589 (2) | 0.0589 (2) | 0.0589 (2) | −0.0007 (3) | −0.0007 (3) | −0.0007 (3) |
N1 | 0.084 (4) | 0.060 (3) | 0.070 (4) | −0.014 (4) | −0.026 (4) | 0.014 (3) |
C1 | 0.064 (3) | 0.064 (3) | 0.064 (3) | −0.012 (4) | −0.012 (4) | 0.012 (4) |
C2 | 0.082 (6) | 0.071 (5) | 0.061 (5) | −0.020 (5) | −0.024 (4) | 0.010 (4) |
C3 | 0.082 (7) | 0.132 (8) | 0.129 (9) | 0.040 (6) | −0.022 (7) | −0.045 (8) |
C4 | 0.129 (9) | 0.147 (10) | 0.172 (12) | 0.014 (9) | −0.035 (9) | −0.102 (10) |
C5 | 0.097 (7) | 0.138 (8) | 0.065 (5) | −0.021 (8) | −0.028 (6) | 0.008 (6) |
C6 | 0.064 (5) | 0.090 (6) | 0.098 (6) | −0.014 (4) | −0.005 (5) | 0.007 (6) |
C7 | 0.049 (4) | 0.104 (7) | 0.105 (6) | −0.010 (4) | −0.001 (5) | −0.026 (6) |
N1—C1 | 1.330 (5) | C4—C5 | 1.465 (13) |
N1—C2 | 1.446 (9) | C4—H4A | 0.9700 |
N1—H1A | 0.8600 | C4—H4B | 0.9700 |
C1—N1i | 1.330 (5) | C5—C6 | 1.473 (13) |
C1—N1ii | 1.330 (5) | C5—H5A | 0.9700 |
C2—C7 | 1.479 (10) | C5—H5B | 0.9700 |
C2—C3 | 1.493 (11) | C6—C7 | 1.508 (10) |
C2—H2A | 0.9800 | C6—H6A | 0.9700 |
C3—C4 | 1.514 (13) | C6—H6C | 0.9700 |
C3—H3A | 0.9700 | C7—H7C | 0.9700 |
C3—H3B | 0.9700 | C7—H7A | 0.9700 |
C1—N1—C2 | 126.7 (5) | C5—C4—H4B | 109.1 |
C1—N1—H1A | 116.7 | C3—C4—H4B | 109.1 |
C2—N1—H1A | 116.7 | H4A—C4—H4B | 107.8 |
N1i—C1—N1 | 119.99 (3) | C4—C5—C6 | 111.1 (8) |
N1i—C1—N1ii | 119.99 (3) | C4—C5—H5A | 109.4 |
N1—C1—N1ii | 119.99 (3) | C6—C5—H5A | 109.4 |
N1—C2—C7 | 109.5 (6) | C4—C5—H5B | 109.4 |
N1—C2—C3 | 110.1 (7) | C6—C5—H5B | 109.4 |
C7—C2—C3 | 110.4 (7) | H5A—C5—H5B | 108.0 |
N1—C2—H2A | 108.9 | C5—C6—C7 | 112.0 (7) |
C7—C2—H2A | 108.9 | C5—C6—H6A | 109.2 |
C3—C2—H2A | 108.9 | C7—C6—H6A | 109.2 |
C2—C3—C4 | 109.3 (8) | C5—C6—H6C | 109.2 |
C2—C3—H3A | 109.8 | C7—C6—H6C | 109.2 |
C4—C3—H3A | 109.8 | H6A—C6—H6C | 107.9 |
C2—C3—H3B | 109.8 | C2—C7—C6 | 110.8 (7) |
C4—C3—H3B | 109.8 | C2—C7—H7C | 109.5 |
H3A—C3—H3B | 108.3 | C6—C7—H7C | 109.5 |
C5—C4—C3 | 112.7 (8) | C2—C7—H7A | 109.5 |
C5—C4—H4A | 109.1 | C6—C7—H7A | 109.5 |
C3—C4—H4A | 109.1 | H7C—C7—H7A | 108.1 |
Symmetry codes: (i) −z+3/2, −x+1, y+1/2; (ii) −y+1, z−1/2, −x+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I1iii | 0.86 | 2.86 | 3.693 (5) | 165 |
C2—H2A···I1iv | 0.98 | 3.03 | 3.950 (5) | 158 |
Symmetry codes: (iii) x, y−1, z; (iv) −x+2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C19H36N3+·I− |
Mr | 433.41 |
Crystal system, space group | Cubic, P213 |
Temperature (K) | 188 |
a (Å) | 12.893 (4) |
V (Å3) | 2143 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.50 |
Crystal size (mm) | 0.5 × 0.3 × 0.3 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.271, 0.320 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2387, 802, 628 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.614 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.076, 1.04 |
No. of reflections | 802 |
No. of parameters | 70 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.27 |
Absolute structure | Flack (1983), 802 Friedel pairs |
Absolute structure parameter | 0.08 (8) |
Computer programs: XSCANS (Bruker, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I1i | 0.86 | 2.86 | 3.693 (5) | 165 |
C2—H2A···I1ii | 0.98 | 3.03 | 3.950 (5) | 158 |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, y−1/2, −z+3/2. |
Acknowledgements
We would like to thank Dr Thomas Haas for his help in the analysis of the structure.
References
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Guanidines are of special interest due to their possible application in medicine (Yoshiizumi et al., 1998; Moroni et al., 2001). They are considered super bases as they are easily protonated to generate guanidinium cations (Ishikawa & Isobe, 2002). The structural features and hydrogen bonding array provided by these cations suggest that they are good building blocks for the formation of supramolecular entities (Said, Bazinet et al., 2006, Said, Ong et al., 2006, Said et al., 2005).
The title compound (I), Fig. 1, is a typical N,N',N"-trisubstituted guanidinium halide salt with normal geometric parameters (Said et al., 2005). The central guanidinium fragment of the cation of the title salt is planar [sum of NCN angles is 360°] with bond lengths and angles as expected for a central Csp2 hybridization, accounting for charge delocalization between the three C—N bonds. The bond length C1—N1 [1.330 (5) Å] is comparable with literature averages for substituted and unsubstituted guanidinium cations (1.321 and 1.328 Å, respectively; (Allen et al., 1987)). The cyclohexyl ring has the normal chair conformation with conventional bond lengths and angles. A partial packing diagram is shown in Fig. 2. The CHGH+ ions occur in chains, with the I- anions arranged parallel to the cation chains. The cations and anions occur in a 3-fold array: three anions surround each cation [via its three N—H···I, 2.856 Å; (165°) and C—H···I (3.027 Å; 158°) interactions, Table 1, Fig. 3], and three cations surround each anion resulting in the formation of three-dimensional supramolecular structure.This type of supramolecular synthons has been observed frequently in other related compounds. The stability of this crystal lattice is evidenced by the crystallization of a whole series of isomorphous compounds of this type, such as N,N',N''-tricyclohexylguanidinium chloride (Cai & Hu, 2006), even with different substituents like N,N',N''-triisipropylguanidinium chloride (Said et al., 2005).