Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045990/ez2101sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045990/ez2101Isup2.hkl |
CCDC reference: 667334
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.034
- wR factor = 0.097
- Data-to-parameter ratio = 25.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 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 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related structural studies of octane-1,8-diammonium salts see: Brisson & Brisse (1984); Baur & Tillmanns (1986). For related literature see: Allen (2002).
Compound (I) was prepared by adding 1,8-diamino-octane (0.50 g, 3.47 mmol) to 32% hydrochloric acid (2 ml, 69.1 mmol) in a sample vial. The mixture was then refluxed at 363 K for 2 h. The solution was cooled at 2 K h-1 to room temperature. Colourless crystals of octane-1,8-diammonium dichloride hydrate were collected and a suitable single-crystal was taken for the X-ray diffraction study.
H atoms were geometrically positioned and refined in the riding-model approximation, with C—H = 0.97 Å, N—H = 0.89 Å, and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(N). For (I), the highest peak in the final difference map is 0.87 Å from Cl1 and the deepest hole is 1.03 Å from H1.
In an ongoing study of the structural characteristics of layered diammonium salts, we are determining the crystal structures of long-chained diammonium salts. Colourless crystals of octane-1,8-diammonium dichloride hydrate formed when we attempted to synthesize the unhydrated chloride salt. A search of the Cambridge Structural Database (Version 5.28, May 2007 release; Allen, 2002) revealed that only the octane-1,8-diammonium dibromide salt has previously been studied (Brisson & Brisse, 1984; Baur & Tillmanns, 1986) and the crystal structure of the title compound (I) had not previously been determined.
The diammonium octane chain straddles a centre of inversion and the single water of crystallization sits on a twofold rotation axis. Therefore the asymmetric unit contains one chloride anion, one half of the diammonium cation and one half of the water molecule (Figure 1).
Figure 2 illustrates the layered packing arrangement of the title compound (I). Single layers of the extended cations pack end on between two layers of chloride ions. Sandwiched in-between the chloride ions is a single layer of water molecules that hydrogen bonds to the chloride anions and the diammonium cations. The hydrocarbon chains pack in parallel layers with every second hydrocarbon chain layer alternating in a staggered, alternating configuration with respect to the previous layer. Since the packing configuration is a complex, staggered, alternating pattern, the hydrogen bonding network that is formed is an intricately complex bridge between the layers through the water molecules and chloride anions.
Figure 3 shows the hydrogen bonding contacts for the title compound (I). The hydrogen atoms around the ammonium group are involved in hydrogen bonds with two chloride anions and the oxygen of the water molecule. The hydrogen atoms of the water molecule hydrogen bond to a further two chloride anions resulting in four tetrahedrally oriented hydrogen bonds around the water molecule. The hydrogen bond distances and angles for (I) can be found in Table 1. Figure 3 also shows that the hydrocarbon chain is slightly twisted out of its fully extended configuration by up to 15° (where the torsion angles for a standard configuration hydrocarbon chain should be 180°). When examining the torsion angles (Table 2) along the hydrocarbon chain of (I) it is evident that the hydrogen bonding interactions to H1 attached to the water and the chloride anion affect the chain configuration.
For related structural studies of octane-1,8-diammonium salts see: Brisson & Brisse (1984); Baur & Tillmanns (1986). For related literature see: Allen (2002).
Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999), PLATON (Spek, 2003) and publCIF (Westrip, 2007).
C8H22N22+·2Cl−·H2O | F(000) = 512 |
Mr = 235.19 | Dx = 1.178 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1647 reflections |
a = 24.719 (3) Å | θ = 1.7–28.3° |
b = 5.0827 (6) Å | µ = 0.46 mm−1 |
c = 10.8593 (14) Å | T = 293 K |
β = 103.590 (3)° | Block, colourless |
V = 1326.2 (3) Å3 | 0.40 × 0.22 × 0.12 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1647 independent reflections |
Radiation source: fine-focus sealed tube | 1209 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
φ and ω scans | θmax = 28.3°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −32→29 |
Tmin = 0.837, Tmax = 0.947 | k = −6→5 |
3965 measured reflections | l = −14→10 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | All H-atom parameters refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0507P)2 + 0.1994P] where P = (Fo2 + 2Fc2)/3 |
1647 reflections | (Δ/σ)max = 0.001 |
65 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.12 e Å−3 |
C8H22N22+·2Cl−·H2O | V = 1326.2 (3) Å3 |
Mr = 235.19 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.719 (3) Å | µ = 0.46 mm−1 |
b = 5.0827 (6) Å | T = 293 K |
c = 10.8593 (14) Å | 0.40 × 0.22 × 0.12 mm |
β = 103.590 (3)° |
Bruker SMART CCD area-detector diffractometer | 1647 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1209 reflections with I > 2σ(I) |
Tmin = 0.837, Tmax = 0.947 | Rint = 0.021 |
3965 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.097 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.18 e Å−3 |
1647 reflections | Δρmin = −0.12 e Å−3 |
65 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 | ||
C1 | 0.62661 (7) | 0.6672 (3) | 0.20031 (15) | 0.0486 (4) | |
H1A | 0.6280 | 0.8093 | 0.2606 | 0.058* | |
H1B | 0.6498 | 0.7160 | 0.1433 | 0.058* | |
C2 | 0.64942 (7) | 0.4197 (3) | 0.27064 (15) | 0.0493 (4) | |
H2A | 0.6574 | 0.2924 | 0.2108 | 0.059* | |
H2B | 0.6214 | 0.3445 | 0.3094 | 0.059* | |
C3 | 0.70194 (6) | 0.4707 (3) | 0.37245 (14) | 0.0497 (4) | |
H3A | 0.6938 | 0.5977 | 0.4322 | 0.060* | |
H3B | 0.7298 | 0.5474 | 0.3335 | 0.060* | |
C4 | 0.72584 (6) | 0.2236 (3) | 0.44406 (14) | 0.0461 (4) | |
H4A | 0.6966 | 0.1353 | 0.4740 | 0.055* | |
H4B | 0.7382 | 0.1054 | 0.3860 | 0.055* | |
N1 | 0.56868 (5) | 0.6322 (3) | 0.12689 (13) | 0.0519 (3) | |
H1C | 0.5672 | 0.5002 | 0.0724 | 0.078* | |
H1D | 0.5570 | 0.7795 | 0.0846 | 0.078* | |
H1E | 0.5470 | 0.5960 | 0.1794 | 0.078* | |
Cl1 | 0.566023 (17) | 0.86236 (8) | 0.44656 (4) | 0.05515 (17) | |
O1 | 0.5000 | 0.2880 (4) | 0.2500 | 0.0574 (4) | |
H1 | 0.4814 (10) | 0.184 (5) | 0.192 (2) | 0.098 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0510 (8) | 0.0405 (8) | 0.0498 (8) | −0.0002 (7) | 0.0030 (6) | 0.0041 (7) |
C2 | 0.0507 (9) | 0.0385 (8) | 0.0519 (9) | 0.0024 (6) | −0.0013 (7) | 0.0033 (7) |
C3 | 0.0501 (8) | 0.0419 (8) | 0.0517 (8) | 0.0004 (7) | 0.0010 (7) | 0.0043 (7) |
C4 | 0.0471 (8) | 0.0414 (8) | 0.0458 (8) | 0.0024 (7) | 0.0032 (6) | 0.0019 (7) |
N1 | 0.0520 (7) | 0.0473 (8) | 0.0524 (8) | 0.0094 (6) | 0.0042 (6) | 0.0102 (6) |
Cl1 | 0.0640 (3) | 0.0467 (3) | 0.0507 (2) | 0.00232 (18) | 0.00525 (17) | −0.00322 (17) |
O1 | 0.0654 (11) | 0.0490 (10) | 0.0520 (10) | 0.000 | 0.0021 (8) | 0.000 |
C1—N1 | 1.477 (2) | C3—H3B | 0.9700 |
C1—C2 | 1.510 (2) | C4—C4i | 1.514 (3) |
C1—H1A | 0.9700 | C4—H4A | 0.9700 |
C1—H1B | 0.9700 | C4—H4B | 0.9700 |
C2—C3 | 1.517 (2) | N1—H1C | 0.8900 |
C2—H2A | 0.9700 | N1—H1D | 0.8900 |
C2—H2B | 0.9700 | N1—H1E | 0.8900 |
C3—C4 | 1.522 (2) | O1—H1 | 0.87 (2) |
C3—H3A | 0.9700 | ||
N1—C1—C2 | 111.86 (12) | C2—C3—H3B | 108.9 |
N1—C1—H1A | 109.2 | C4—C3—H3B | 108.9 |
C2—C1—H1A | 109.2 | H3A—C3—H3B | 107.7 |
N1—C1—H1B | 109.2 | C4i—C4—C3 | 113.70 (16) |
C2—C1—H1B | 109.2 | C4i—C4—H4A | 108.8 |
H1A—C1—H1B | 107.9 | C3—C4—H4A | 108.8 |
C1—C2—C3 | 112.36 (13) | C4i—C4—H4B | 108.8 |
C1—C2—H2A | 109.1 | C3—C4—H4B | 108.8 |
C3—C2—H2A | 109.1 | H4A—C4—H4B | 107.7 |
C1—C2—H2B | 109.1 | C1—N1—H1C | 109.5 |
C3—C2—H2B | 109.1 | C1—N1—H1D | 109.5 |
H2A—C2—H2B | 107.9 | H1C—N1—H1D | 109.5 |
C2—C3—C4 | 113.25 (13) | C1—N1—H1E | 109.5 |
C2—C3—H3A | 108.9 | H1C—N1—H1E | 109.5 |
C4—C3—H3A | 108.9 | H1D—N1—H1E | 109.5 |
N1—C1—C2—C3 | −164.65 (14) | C2—C3—C4—C4i | −173.09 (17) |
C1—C2—C3—C4 | −179.66 (14) |
Symmetry code: (i) −x+3/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···Cl1ii | 0.89 | 2.29 | 3.1777 (15) | 175 |
N1—H1D···Cl1iii | 0.89 | 2.40 | 3.2215 (14) | 153 |
N1—H1E···O1 | 0.89 | 2.19 | 2.9660 (17) | 145 |
O1—H1···Cl1iv | 0.87 (2) | 2.34 (2) | 3.2036 (13) | 173 (2) |
Symmetry codes: (ii) x, −y+1, z−1/2; (iii) x, −y+2, z−1/2; (iv) −x+1, y−1, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H22N22+·2Cl−·H2O |
Mr | 235.19 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 24.719 (3), 5.0827 (6), 10.8593 (14) |
β (°) | 103.590 (3) |
V (Å3) | 1326.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.46 |
Crystal size (mm) | 0.40 × 0.22 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.837, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3965, 1647, 1209 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.097, 1.04 |
No. of reflections | 1647 |
No. of parameters | 65 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.18, −0.12 |
Computer programs: SMART-NT (Bruker, 1998), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999), PLATON (Spek, 2003) and publCIF (Westrip, 2007).
N1—C1—C2—C3 | −164.65 (14) | C2—C3—C4—C4i | −173.09 (17) |
C1—C2—C3—C4 | −179.66 (14) |
Symmetry code: (i) −x+3/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···Cl1ii | 0.89 | 2.29 | 3.1777 (15) | 175 |
N1—H1D···Cl1iii | 0.89 | 2.40 | 3.2215 (14) | 153 |
N1—H1E···O1 | 0.89 | 2.19 | 2.9660 (17) | 145 |
O1—H1···Cl1iv | 0.87 (2) | 2.34 (2) | 3.2036 (13) | 173 (2) |
Symmetry codes: (ii) x, −y+1, z−1/2; (iii) x, −y+2, z−1/2; (iv) −x+1, y−1, −z+1/2. |
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In an ongoing study of the structural characteristics of layered diammonium salts, we are determining the crystal structures of long-chained diammonium salts. Colourless crystals of octane-1,8-diammonium dichloride hydrate formed when we attempted to synthesize the unhydrated chloride salt. A search of the Cambridge Structural Database (Version 5.28, May 2007 release; Allen, 2002) revealed that only the octane-1,8-diammonium dibromide salt has previously been studied (Brisson & Brisse, 1984; Baur & Tillmanns, 1986) and the crystal structure of the title compound (I) had not previously been determined.
The diammonium octane chain straddles a centre of inversion and the single water of crystallization sits on a twofold rotation axis. Therefore the asymmetric unit contains one chloride anion, one half of the diammonium cation and one half of the water molecule (Figure 1).
Figure 2 illustrates the layered packing arrangement of the title compound (I). Single layers of the extended cations pack end on between two layers of chloride ions. Sandwiched in-between the chloride ions is a single layer of water molecules that hydrogen bonds to the chloride anions and the diammonium cations. The hydrocarbon chains pack in parallel layers with every second hydrocarbon chain layer alternating in a staggered, alternating configuration with respect to the previous layer. Since the packing configuration is a complex, staggered, alternating pattern, the hydrogen bonding network that is formed is an intricately complex bridge between the layers through the water molecules and chloride anions.
Figure 3 shows the hydrogen bonding contacts for the title compound (I). The hydrogen atoms around the ammonium group are involved in hydrogen bonds with two chloride anions and the oxygen of the water molecule. The hydrogen atoms of the water molecule hydrogen bond to a further two chloride anions resulting in four tetrahedrally oriented hydrogen bonds around the water molecule. The hydrogen bond distances and angles for (I) can be found in Table 1. Figure 3 also shows that the hydrocarbon chain is slightly twisted out of its fully extended configuration by up to 15° (where the torsion angles for a standard configuration hydrocarbon chain should be 180°). When examining the torsion angles (Table 2) along the hydrocarbon chain of (I) it is evident that the hydrogen bonding interactions to H1 attached to the water and the chloride anion affect the chain configuration.