Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025019/hk2253sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025019/hk2253Isup2.hkl |
CCDC reference: 651536
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.006 Å
- R factor = 0.035
- wR factor = 0.082
- Data-to-parameter ratio = 18.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 3000 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.03 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C16 H22 N2
Alert level G PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............ 1 Times
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For the preparation of the title compound, (I), 1,6-dibromohexane (12.2 g, 50 mmol) was added to 2-propanol solution (50 ml) of pyridine (9.5 g, 120 mmol) at 353 K. After stirring for 12 h, two layers were formed. The top layer containing the unreacted starting materials was decanted. The bottom layer, a white solid phase, was recrystallized by the addition of ethanol. Then, the crystals of (I) were obtained by evaporating the solvent slowly at room temperature for about 7 d.
H atoms were positioned geometrically, with C—H = 0.93 and 0.97 Å for aromatic and methylene H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
The title compound, (I), with cucurbit[6,7,8]urils, can be utilized to form host–guest complexes (Cong et al., 2007), which are of wide current interest for application in molecular identification and molecular self-assembly. A relative crystal structure has already been reported (Ji et al., 2006). We report herein the crystal structure of the title compound, (I).
The asymmetric unit of the title compound, (I), contains one half molecule (Fig. 1), in which the bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987).
For general background, see: Cong et al. (2007); Allen et al. (1987). For related literature, see: Ji et al. (2006).
Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry code (A): 2 - x, -y, -z]. |
C16H22N22+·2Br− | Z = 1 |
Mr = 402.16 | F(000) = 202 |
Triclinic, P1 | Dx = 1.596 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.4750 (15) Å | Cell parameters from 25 reflections |
b = 7.9320 (16) Å | θ = 10–13° |
c = 8.3450 (17) Å | µ = 4.84 mm−1 |
α = 94.12 (3)° | T = 298 K |
β = 115.64 (3)° | Block, colourless |
γ = 105.91 (3)° | 0.30 × 0.20 × 0.10 mm |
V = 418.5 (2) Å3 |
Enraf–Nonius CAD-4 diffractometer | 1155 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.054 |
Graphite monochromator | θmax = 26.0°, θmin = 2.7° |
ω/2θ scans | h = −9→7 |
Absorption correction: ψ scan (North et al., 1968) | k = −9→9 |
Tmin = 0.326, Tmax = 0.617 | l = 0→10 |
1774 measured reflections | 3 standard reflections every 120 min |
1639 independent reflections | intensity decay: none |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.04P)2 + 0.3P] where P = (Fo2 + 2Fc2)/3 |
1639 reflections | (Δ/σ)max = 0.001 |
91 parameters | Δρmax = 0.65 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
C16H22N22+·2Br− | γ = 105.91 (3)° |
Mr = 402.16 | V = 418.5 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.4750 (15) Å | Mo Kα radiation |
b = 7.9320 (16) Å | µ = 4.84 mm−1 |
c = 8.3450 (17) Å | T = 298 K |
α = 94.12 (3)° | 0.30 × 0.20 × 0.10 mm |
β = 115.64 (3)° |
Enraf–Nonius CAD-4 diffractometer | 1155 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.054 |
Tmin = 0.326, Tmax = 0.617 | 3 standard reflections every 120 min |
1774 measured reflections | intensity decay: none |
1639 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.65 e Å−3 |
1639 reflections | Δρmin = −0.43 e Å−3 |
91 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 | ||
Br | 0.04735 (6) | 0.78621 (5) | 0.21069 (5) | 0.04621 (16) | |
N | 0.8561 (4) | 1.2391 (4) | 0.2347 (4) | 0.0336 (6) | |
C1 | 0.5568 (6) | 1.0791 (5) | 0.2592 (5) | 0.0491 (10) | |
H1A | 0.4965 | 1.0004 | 0.3138 | 0.059* | |
C2 | 0.4352 (6) | 1.1500 (5) | 0.1262 (6) | 0.0477 (10) | |
H2A | 0.2912 | 1.1182 | 0.0875 | 0.057* | |
C3 | 0.5292 (6) | 1.2688 (5) | 0.0511 (6) | 0.0506 (10) | |
H3A | 0.4494 | 1.3204 | −0.0374 | 0.061* | |
C4 | 0.7412 (6) | 1.3119 (5) | 0.1062 (5) | 0.0427 (9) | |
H4A | 0.8045 | 1.3915 | 0.0542 | 0.051* | |
C5 | 0.7674 (6) | 1.1244 (5) | 0.3114 (5) | 0.0423 (9) | |
H5A | 0.8498 | 1.0752 | 0.4009 | 0.051* | |
C6 | 1.0866 (5) | 1.2841 (5) | 0.2952 (5) | 0.0400 (8) | |
H6A | 1.1207 | 1.3419 | 0.2086 | 0.048* | |
H6B | 1.1203 | 1.1743 | 0.2976 | 0.048* | |
C7 | 1.2187 (5) | 1.4073 (5) | 0.4823 (5) | 0.0395 (8) | |
H7A | 1.1776 | 1.3533 | 0.5673 | 0.047* | |
H7B | 1.1927 | 1.5206 | 0.4779 | 0.047* | |
C8 | 1.4535 (5) | 1.4423 (5) | 0.5498 (5) | 0.0383 (8) | |
H8A | 1.5296 | 1.5000 | 0.6782 | 0.046* | |
H8B | 1.4750 | 1.3278 | 0.5382 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br | 0.0391 (2) | 0.0478 (2) | 0.0494 (2) | 0.00794 (16) | 0.02235 (17) | 0.01417 (17) |
N | 0.0231 (14) | 0.0321 (15) | 0.0387 (16) | 0.0015 (11) | 0.0143 (12) | 0.0007 (12) |
C1 | 0.036 (2) | 0.053 (2) | 0.054 (2) | −0.0008 (18) | 0.0275 (19) | 0.006 (2) |
C2 | 0.0256 (18) | 0.049 (2) | 0.059 (2) | 0.0040 (17) | 0.0202 (18) | −0.0100 (19) |
C3 | 0.038 (2) | 0.048 (2) | 0.055 (2) | 0.0176 (18) | 0.0123 (18) | 0.0030 (19) |
C4 | 0.041 (2) | 0.0343 (19) | 0.050 (2) | 0.0070 (16) | 0.0219 (18) | 0.0098 (17) |
C5 | 0.0335 (19) | 0.046 (2) | 0.042 (2) | 0.0064 (16) | 0.0184 (16) | 0.0095 (17) |
C6 | 0.0251 (17) | 0.043 (2) | 0.048 (2) | 0.0026 (15) | 0.0204 (15) | −0.0018 (17) |
C7 | 0.0226 (16) | 0.042 (2) | 0.048 (2) | 0.0016 (15) | 0.0189 (15) | 0.0013 (17) |
C8 | 0.0271 (17) | 0.041 (2) | 0.044 (2) | 0.0064 (15) | 0.0175 (15) | 0.0052 (16) |
N—C4 | 1.335 (5) | C5—H5A | 0.9300 |
N—C5 | 1.341 (4) | C6—C7 | 1.512 (5) |
N—C6 | 1.495 (4) | C6—H6A | 0.9700 |
C1—C2 | 1.368 (6) | C6—H6B | 0.9700 |
C1—C5 | 1.368 (5) | C7—C8 | 1.526 (4) |
C1—H1A | 0.9300 | C7—H7A | 0.9700 |
C2—C3 | 1.370 (6) | C7—H7B | 0.9700 |
C2—H2A | 0.9300 | C8—C8i | 1.507 (7) |
C3—C4 | 1.375 (5) | C8—H8A | 0.9700 |
C3—H3A | 0.9300 | C8—H8B | 0.9700 |
C4—H4A | 0.9300 | ||
C4—N—C5 | 120.8 (3) | N—C6—C7 | 111.4 (3) |
C4—N—C6 | 120.4 (3) | N—C6—H6A | 109.3 |
C5—N—C6 | 118.8 (3) | C7—C6—H6A | 109.3 |
C2—C1—C5 | 119.7 (4) | N—C6—H6B | 109.3 |
C2—C1—H1A | 120.1 | C7—C6—H6B | 109.3 |
C5—C1—H1A | 120.1 | H6A—C6—H6B | 108.0 |
C1—C2—C3 | 118.8 (3) | C6—C7—C8 | 111.4 (3) |
C1—C2—H2A | 120.6 | C6—C7—H7A | 109.4 |
C3—C2—H2A | 120.6 | C8—C7—H7A | 109.4 |
C2—C3—C4 | 120.2 (4) | C6—C7—H7B | 109.4 |
C2—C3—H3A | 119.9 | C8—C7—H7B | 109.4 |
C4—C3—H3A | 119.9 | H7A—C7—H7B | 108.0 |
N—C4—C3 | 119.8 (4) | C8i—C8—C7 | 114.5 (4) |
N—C4—H4A | 120.1 | C8i—C8—H8A | 108.6 |
C3—C4—H4A | 120.1 | C7—C8—H8A | 108.6 |
N—C5—C1 | 120.6 (4) | C8i—C8—H8B | 108.6 |
N—C5—H5A | 119.7 | C7—C8—H8B | 108.6 |
C1—C5—H5A | 119.7 | H8A—C8—H8B | 107.6 |
C5—C1—C2—C3 | −1.5 (6) | C6—N—C5—C1 | −179.7 (3) |
C1—C2—C3—C4 | 1.5 (6) | C2—C1—C5—N | 0.7 (6) |
C5—N—C4—C3 | −0.2 (5) | C4—N—C6—C7 | 106.6 (4) |
C6—N—C4—C3 | 179.7 (3) | C5—N—C6—C7 | −73.6 (4) |
C2—C3—C4—N | −0.7 (6) | N—C6—C7—C8 | 175.9 (3) |
C4—N—C5—C1 | 0.2 (5) | C6—C7—C8—C8i | 70.2 (5) |
Symmetry code: (i) −x+3, −y+3, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H22N22+·2Br− |
Mr | 402.16 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.4750 (15), 7.9320 (16), 8.3450 (17) |
α, β, γ (°) | 94.12 (3), 115.64 (3), 105.91 (3) |
V (Å3) | 418.5 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 4.84 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.326, 0.617 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1774, 1639, 1155 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.082, 1.04 |
No. of reflections | 1639 |
No. of parameters | 91 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.43 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1985), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
N—C4 | 1.335 (5) | N—C6 | 1.495 (4) |
N—C5 | 1.341 (4) | ||
C4—N—C5 | 120.8 (3) | N—C4—C3 | 119.8 (4) |
C4—N—C6 | 120.4 (3) | N—C5—C1 | 120.6 (4) |
C5—N—C6 | 118.8 (3) | N—C6—C7 | 111.4 (3) |
The title compound, (I), with cucurbit[6,7,8]urils, can be utilized to form host–guest complexes (Cong et al., 2007), which are of wide current interest for application in molecular identification and molecular self-assembly. A relative crystal structure has already been reported (Ji et al., 2006). We report herein the crystal structure of the title compound, (I).
The asymmetric unit of the title compound, (I), contains one half molecule (Fig. 1), in which the bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987).