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Halogen bonding (XB) is a highly-directional class of intermolecular interactions that has been used as a powerful tool to drive the design of crystals in the solid phase. To date, the majority of XB donors have been iodine-containing compounds, with many fewer involving brominated analogues. We report the formation of adducts in the vapour phase from a series of dibromoperfluoroalkyl compounds, BrCF
2(CF
2)
nCF
2Br (
n = 2, 4, 6), and 1,4-diazabicyclo[2.2.2]octane (DABCO). Single-crystal X-ray diffraction studies of the colourless crystals identified 1,4-diazabicyclo[2.2.2]octane–1,4-dibromoperfluorobutane (1/1), C
4Br
2F
8·C
6H
12N
2, (I), 1,4-diazabicyclo[2.2.2]octane–1,6-dibromoperfluorohexane (1/1), C
6Br
2F
12·C
6H
12N
2, (II), and 1,4-diazabicyclo[2.2.2]octane–1,8-dibromoperfluorooctane (1/1), C
8Br
2F
16·C
6H
12N
2, (III), each of which displays a one-dimensional halogen-bonded network. All three adducts exhibit N
Br distances less than the sum of the van der Waals radii, with butane analogue (I) showing the shortest N
Br halogen-bond distances yet reported between a bromoperfluorocarbon and a nitrogen base [2.809 (3) and 2.818 (3) Å], which are 0.58 and 0.59 Å shorter than the sum of the van der Waals radii.
Supporting information
CCDC references: 1576136; 1576135; 1576134
Data collection: CrysAlis PRO (Rigaku OD, 2015) for (I); CrysAlis PRO (Agilent, 2014) for (II), (III). Cell refinement: CrysAlis PRO (Rigaku OD, 2015) for (I); CrysAlis PRO (Agilent, 2014) for (II), (III). Data reduction: CrysAlis PRO (Rigaku OD, 2015) for (I); CrysAlis PRO (Agilent, 2014) for (II), (III). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SHELXT (Sheldrick, 2015a) for (II); SUPERFLIP (Palatinus & Chapuis, 2007; Palatinus & van der Lee, 2008; Palatinus et al., 2012) for (III). Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b) for (I), (II); SHELXL97 (Sheldrick, 2008) for (III). For all structures, molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
1,4-Dibromoperfluorobutane–1,4-diazabicyclo[2.2.2]octane (1/1) (I)
top
Crystal data top
C4Br2F8·C6H12N2 | F(000) = 912 |
Mr = 472.04 | Dx = 2.027 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.4659 (6) Å | Cell parameters from 1842 reflections |
b = 11.0854 (6) Å | θ = 3.7–27.3° |
c = 10.7955 (6) Å | µ = 5.32 mm−1 |
β = 106.271 (5)° | T = 150 K |
V = 1546.96 (15) Å3 | Block, colourless |
Z = 4 | 0.2 × 0.2 × 0.15 mm |
Data collection top
SuperNova, Single source at offset, Eos diffractometer | 3034 independent reflections |
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source | 2260 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.046 |
Detector resolution: 8.0714 pixels mm-1 | θmax = 26.0°, θmin = 3.4° |
ω scans | h = −14→16 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | k = −13→12 |
Tmin = 0.025, Tmax = 1.000 | l = −13→13 |
6191 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.064 | w = 1/[σ2(Fo2) + (0.0076P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.93 | (Δ/σ)max = 0.001 |
3034 reflections | Δρmax = 0.43 e Å−3 |
199 parameters | Δρmin = −0.52 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.47057 (3) | 0.36072 (4) | 0.13908 (5) | 0.02488 (13) | |
Br2 | −0.07338 (3) | 0.33779 (4) | −0.18506 (5) | 0.02532 (13) | |
C1 | 0.3492 (3) | 0.3537 (4) | −0.0077 (5) | 0.0282 (12) | |
C2 | 0.2501 (3) | 0.3426 (4) | 0.0330 (4) | 0.0202 (10) | |
C3 | 0.1478 (3) | 0.3489 (4) | −0.0796 (5) | 0.0208 (10) | |
C4 | 0.0488 (3) | 0.3080 (4) | −0.0446 (5) | 0.0240 (11) | |
F1 | 0.35763 (18) | 0.2579 (3) | −0.0792 (3) | 0.0613 (10) | |
F2 | 0.34425 (18) | 0.4521 (3) | −0.0793 (3) | 0.0598 (10) | |
F3 | 0.25256 (16) | 0.2386 (2) | 0.0954 (3) | 0.0434 (8) | |
F4 | 0.24725 (17) | 0.4318 (2) | 0.1146 (3) | 0.0456 (8) | |
F5 | 0.15754 (17) | 0.2775 (2) | −0.1749 (3) | 0.0408 (8) | |
F6 | 0.13500 (16) | 0.4625 (2) | −0.1215 (3) | 0.0398 (8) | |
F7 | 0.05584 (16) | 0.1913 (2) | −0.0158 (3) | 0.0429 (8) | |
F8 | 0.04251 (17) | 0.3683 (2) | 0.0599 (3) | 0.0387 (7) | |
C5 | 0.6632 (3) | 0.2423 (4) | 0.4059 (5) | 0.0264 (11) | |
H5A | 0.6997 | 0.1996 | 0.3510 | 0.032* | |
H5B | 0.5974 | 0.1996 | 0.3992 | 0.032* | |
C6 | 0.5907 (3) | 0.4310 (4) | 0.4455 (4) | 0.0297 (12) | |
H6A | 0.5239 | 0.3917 | 0.4415 | 0.036* | |
H6B | 0.5764 | 0.5153 | 0.4154 | 0.036* | |
C7 | 0.7404 (3) | 0.4287 (4) | 0.3691 (4) | 0.0255 (11) | |
H7A | 0.7268 | 0.5133 | 0.3400 | 0.031* | |
H7B | 0.7763 | 0.3881 | 0.3122 | 0.031* | |
C8 | 0.7308 (3) | 0.2414 (4) | 0.5477 (5) | 0.0291 (12) | |
H8A | 0.6929 | 0.2007 | 0.6023 | 0.035* | |
H8B | 0.7950 | 0.1953 | 0.5541 | 0.035* | |
C9 | 0.6604 (3) | 0.4305 (4) | 0.5864 (5) | 0.0317 (12) | |
H9A | 0.6763 | 0.5145 | 0.6166 | 0.038* | |
H9B | 0.6233 | 0.3912 | 0.6428 | 0.038* | |
C10 | 0.8092 (3) | 0.4258 (4) | 0.5097 (5) | 0.0309 (12) | |
H10A | 0.8745 | 0.3831 | 0.5132 | 0.037* | |
H10B | 0.8266 | 0.5094 | 0.5403 | 0.037* | |
N1 | 0.6416 (2) | 0.3667 (3) | 0.3606 (3) | 0.0222 (9) | |
N2 | 0.7574 (2) | 0.3650 (3) | 0.5949 (4) | 0.0219 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0157 (2) | 0.0345 (3) | 0.0208 (3) | −0.00078 (18) | −0.0007 (2) | 0.0013 (2) |
Br2 | 0.0159 (2) | 0.0321 (3) | 0.0241 (3) | −0.00058 (18) | −0.0007 (2) | −0.0016 (2) |
C1 | 0.018 (2) | 0.043 (3) | 0.020 (3) | 0.001 (2) | 0.000 (2) | 0.000 (3) |
C2 | 0.022 (2) | 0.020 (2) | 0.015 (3) | −0.0026 (18) | −0.001 (2) | −0.004 (2) |
C3 | 0.021 (2) | 0.022 (2) | 0.017 (3) | 0.0005 (19) | 0.001 (2) | 0.002 (2) |
C4 | 0.020 (2) | 0.023 (2) | 0.025 (3) | 0.0026 (19) | 0.001 (2) | 0.002 (2) |
F1 | 0.0250 (15) | 0.104 (3) | 0.049 (2) | 0.0131 (15) | 0.0010 (15) | −0.044 (2) |
F2 | 0.0290 (15) | 0.093 (2) | 0.048 (2) | −0.0155 (15) | −0.0049 (15) | 0.051 (2) |
F3 | 0.0267 (14) | 0.0503 (17) | 0.043 (2) | −0.0060 (12) | −0.0069 (14) | 0.0314 (17) |
F4 | 0.0265 (14) | 0.0638 (19) | 0.040 (2) | 0.0065 (13) | −0.0023 (14) | −0.0322 (18) |
F5 | 0.0251 (14) | 0.075 (2) | 0.0210 (18) | 0.0005 (13) | 0.0039 (13) | −0.0220 (17) |
F6 | 0.0230 (13) | 0.0348 (15) | 0.052 (2) | −0.0015 (11) | −0.0045 (14) | 0.0251 (16) |
F7 | 0.0246 (14) | 0.0327 (15) | 0.066 (3) | −0.0047 (12) | 0.0033 (15) | 0.0202 (16) |
F8 | 0.0263 (14) | 0.070 (2) | 0.0196 (17) | 0.0058 (13) | 0.0058 (13) | −0.0084 (17) |
C5 | 0.027 (2) | 0.028 (3) | 0.022 (3) | −0.001 (2) | 0.003 (2) | −0.003 (2) |
C6 | 0.026 (2) | 0.041 (3) | 0.021 (3) | 0.008 (2) | 0.003 (2) | 0.003 (3) |
C7 | 0.022 (2) | 0.031 (3) | 0.022 (3) | −0.004 (2) | 0.004 (2) | 0.000 (2) |
C8 | 0.031 (2) | 0.027 (3) | 0.025 (3) | 0.002 (2) | −0.001 (2) | −0.003 (2) |
C9 | 0.026 (2) | 0.046 (3) | 0.022 (3) | 0.010 (2) | 0.006 (2) | −0.002 (3) |
C10 | 0.023 (2) | 0.036 (3) | 0.030 (3) | −0.005 (2) | 0.003 (2) | 0.004 (3) |
N1 | 0.0214 (18) | 0.030 (2) | 0.014 (2) | 0.0003 (16) | 0.0032 (17) | −0.0002 (19) |
N2 | 0.0183 (18) | 0.027 (2) | 0.019 (2) | −0.0008 (15) | 0.0032 (17) | −0.0009 (19) |
Geometric parameters (Å, º) top
Br1—C1 | 1.933 (4) | C6—H6A | 0.9900 |
Br2—C4 | 1.928 (4) | C6—H6B | 0.9900 |
C1—C2 | 1.523 (5) | C6—C9 | 1.547 (6) |
C1—F1 | 1.336 (5) | C6—N1 | 1.472 (5) |
C1—F2 | 1.328 (5) | C7—H7A | 0.9900 |
C2—C3 | 1.562 (5) | C7—H7B | 0.9900 |
C2—F3 | 1.331 (4) | C7—C10 | 1.541 (6) |
C2—F4 | 1.333 (4) | C7—N1 | 1.477 (4) |
C3—C4 | 1.551 (5) | C8—H8A | 0.9900 |
C3—F5 | 1.334 (5) | C8—H8B | 0.9900 |
C3—F6 | 1.333 (4) | C8—N2 | 1.471 (5) |
C4—F7 | 1.328 (4) | C9—H9A | 0.9900 |
C4—F8 | 1.334 (5) | C9—H9B | 0.9900 |
C5—H5A | 0.9900 | C9—N2 | 1.475 (4) |
C5—H5B | 0.9900 | C10—H10A | 0.9900 |
C5—C8 | 1.546 (6) | C10—H10B | 0.9900 |
C5—N1 | 1.465 (5) | C10—N2 | 1.465 (5) |
| | | |
C2—C1—Br1 | 112.0 (3) | N1—C6—H6A | 109.5 |
F1—C1—Br1 | 108.5 (3) | N1—C6—H6B | 109.5 |
F1—C1—C2 | 109.0 (3) | N1—C6—C9 | 110.5 (3) |
F2—C1—Br1 | 109.7 (3) | H7A—C7—H7B | 108.2 |
F2—C1—C2 | 109.2 (3) | C10—C7—H7A | 109.8 |
F2—C1—F1 | 108.4 (4) | C10—C7—H7B | 109.8 |
C1—C2—C3 | 115.2 (4) | N1—C7—H7A | 109.8 |
F3—C2—C1 | 108.4 (3) | N1—C7—H7B | 109.8 |
F3—C2—C3 | 108.9 (3) | N1—C7—C10 | 109.5 (3) |
F3—C2—F4 | 108.0 (4) | C5—C8—H8A | 109.5 |
F4—C2—C1 | 108.7 (3) | C5—C8—H8B | 109.5 |
F4—C2—C3 | 107.4 (3) | H8A—C8—H8B | 108.1 |
C4—C3—C2 | 115.4 (4) | N2—C8—C5 | 110.8 (3) |
F5—C3—C2 | 108.5 (3) | N2—C8—H8A | 109.5 |
F5—C3—C4 | 107.0 (3) | N2—C8—H8B | 109.5 |
F6—C3—C2 | 107.9 (3) | C6—C9—H9A | 109.6 |
F6—C3—C4 | 108.7 (3) | C6—C9—H9B | 109.6 |
F6—C3—F5 | 109.3 (4) | H9A—C9—H9B | 108.1 |
C3—C4—Br2 | 111.2 (3) | N2—C9—C6 | 110.2 (4) |
F7—C4—Br2 | 109.9 (3) | N2—C9—H9A | 109.6 |
F7—C4—C3 | 109.4 (3) | N2—C9—H9B | 109.6 |
F7—C4—F8 | 107.9 (4) | C7—C10—H10A | 109.3 |
F8—C4—Br2 | 109.7 (3) | C7—C10—H10B | 109.3 |
F8—C4—C3 | 108.8 (3) | H10A—C10—H10B | 108.0 |
H5A—C5—H5B | 108.2 | N2—C10—C7 | 111.6 (3) |
C8—C5—H5A | 109.6 | N2—C10—H10A | 109.3 |
C8—C5—H5B | 109.6 | N2—C10—H10B | 109.3 |
N1—C5—H5A | 109.6 | C5—N1—C6 | 109.4 (3) |
N1—C5—H5B | 109.6 | C5—N1—C7 | 109.0 (3) |
N1—C5—C8 | 110.1 (3) | C6—N1—C7 | 107.7 (3) |
H6A—C6—H6B | 108.1 | C8—N2—C9 | 108.1 (3) |
C9—C6—H6A | 109.5 | C10—N2—C8 | 108.8 (3) |
C9—C6—H6B | 109.5 | C10—N2—C9 | 107.7 (3) |
| | | |
Br1—C1—C2—C3 | 174.3 (3) | F5—C3—C4—Br2 | −65.9 (4) |
Br1—C1—C2—F3 | −63.4 (4) | F5—C3—C4—F7 | 55.6 (5) |
Br1—C1—C2—F4 | 53.8 (4) | F5—C3—C4—F8 | 173.2 (3) |
C1—C2—C3—C4 | 166.2 (4) | F6—C3—C4—Br2 | 51.9 (4) |
C1—C2—C3—F5 | 46.2 (5) | F6—C3—C4—F7 | 173.4 (4) |
C1—C2—C3—F6 | −72.1 (4) | F6—C3—C4—F8 | −69.0 (5) |
C2—C3—C4—Br2 | 173.3 (3) | C5—C8—N2—C9 | 60.2 (4) |
C2—C3—C4—F7 | −65.2 (5) | C5—C8—N2—C10 | −56.5 (4) |
C2—C3—C4—F8 | 52.4 (5) | C6—C9—N2—C8 | −58.5 (5) |
F1—C1—C2—C3 | −65.6 (5) | C6—C9—N2—C10 | 59.0 (4) |
F1—C1—C2—F3 | 56.7 (5) | C7—C10—N2—C8 | 58.4 (4) |
F1—C1—C2—F4 | 173.9 (4) | C7—C10—N2—C9 | −58.6 (4) |
F2—C1—C2—C3 | 52.6 (5) | C8—C5—N1—C6 | −57.3 (4) |
F2—C1—C2—F3 | 174.9 (4) | C8—C5—N1—C7 | 60.3 (4) |
F2—C1—C2—F4 | −67.9 (5) | C9—C6—N1—C5 | 58.8 (4) |
F3—C2—C3—C4 | 44.2 (5) | C9—C6—N1—C7 | −59.5 (4) |
F3—C2—C3—F5 | −75.8 (4) | C10—C7—N1—C5 | −58.5 (4) |
F3—C2—C3—F6 | 165.9 (3) | C10—C7—N1—C6 | 60.0 (4) |
F4—C2—C3—C4 | −72.6 (4) | N1—C5—C8—N2 | −2.2 (5) |
F4—C2—C3—F5 | 167.4 (3) | N1—C6—C9—N2 | −0.3 (5) |
F4—C2—C3—F6 | 49.1 (4) | N1—C7—C10—N2 | −1.0 (5) |
1,6-Dibromoperfluorohexane–1,4-diazabicyclo[2.2.2]octane (1/1) (II)
top
Crystal data top
C6Br2F12·C6H12N2 | Z = 2 |
Mr = 572.06 | F(000) = 552 |
Triclinic, P1 | Dx = 2.121 Mg m−3 |
a = 6.0096 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.4941 (8) Å | Cell parameters from 4386 reflections |
c = 14.5016 (11) Å | θ = 3.9–27.1° |
α = 92.051 (6)° | µ = 4.64 mm−1 |
β = 101.375 (6)° | T = 100 K |
γ = 90.507 (6)° | Block, colourless |
V = 895.89 (11) Å3 | 0.18 × 0.16 × 0.12 mm |
Data collection top
Xcalibur, Atlas diffractometer | 3504 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2686 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 5.1636 pixels mm-1 | θmax = 26.0°, θmin = 3.4° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −12→12 |
Tmin = 0.769, Tmax = 1.000 | l = −17→17 |
12221 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.021P)2 + 2.803P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max = 0.001 |
3504 reflections | Δρmax = 0.94 e Å−3 |
253 parameters | Δρmin = −0.72 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.69172 (9) | 0.45860 (5) | 0.79186 (4) | 0.01867 (17) | |
Br2 | −0.13706 (9) | 0.04259 (5) | 0.20985 (4) | 0.01959 (17) | |
F1 | 0.7975 (6) | 0.4096 (5) | 0.6225 (3) | 0.0554 (14) | |
F2 | 0.7593 (7) | 0.2410 (4) | 0.6992 (3) | 0.0600 (15) | |
F3 | 0.3387 (6) | 0.4527 (4) | 0.6086 (3) | 0.0399 (10) | |
F4 | 0.3091 (7) | 0.2778 (4) | 0.6799 (2) | 0.0442 (11) | |
F5 | 0.5053 (6) | 0.3254 (4) | 0.4718 (2) | 0.0383 (10) | |
F6 | 0.4927 (6) | 0.1494 (3) | 0.5435 (3) | 0.0388 (10) | |
F7 | 0.0458 (6) | 0.3529 (3) | 0.4598 (3) | 0.0350 (10) | |
F8 | 0.0337 (6) | 0.1758 (4) | 0.5308 (2) | 0.0326 (9) | |
F9 | 0.2375 (7) | 0.2223 (4) | 0.3250 (3) | 0.0463 (12) | |
F10 | 0.2026 (6) | 0.0481 (4) | 0.3960 (3) | 0.0392 (10) | |
F11 | −0.2157 (8) | 0.2589 (4) | 0.3024 (3) | 0.0672 (16) | |
F12 | −0.2544 (6) | 0.0894 (5) | 0.3777 (3) | 0.0560 (14) | |
C1 | 0.6716 (10) | 0.3545 (6) | 0.6780 (4) | 0.0257 (15) | |
C2 | 0.4245 (9) | 0.3390 (5) | 0.6239 (4) | 0.0166 (12) | |
C3 | 0.3941 (10) | 0.2621 (6) | 0.5280 (4) | 0.0197 (13) | |
C4 | 0.1466 (9) | 0.2400 (6) | 0.4751 (4) | 0.0182 (13) | |
C5 | 0.1192 (9) | 0.1627 (6) | 0.3800 (4) | 0.0182 (13) | |
C6 | −0.1253 (10) | 0.1463 (6) | 0.3240 (4) | 0.0263 (15) | |
N1 | 0.7560 (7) | 0.6409 (4) | 0.9540 (3) | 0.0157 (10) | |
N2 | 0.8071 (7) | 0.8576 (4) | 1.0479 (3) | 0.0135 (10) | |
C7 | 0.9959 (8) | 0.6855 (5) | 0.9717 (4) | 0.0154 (12) | |
H7A | 1.0448 | 0.6926 | 0.9122 | 0.019* | |
H7B | 1.0910 | 0.6238 | 1.0084 | 0.019* | |
C8 | 1.0238 (9) | 0.8163 (6) | 1.0254 (4) | 0.0185 (13) | |
H8A | 1.1358 | 0.8103 | 1.0831 | 0.022* | |
H8B | 1.0779 | 0.8791 | 0.9871 | 0.022* | |
C9 | 0.6153 (9) | 0.7392 (5) | 0.9010 (4) | 0.0175 (13) | |
H9A | 0.4574 | 0.7116 | 0.8877 | 0.021* | |
H9B | 0.6623 | 0.7507 | 0.8415 | 0.021* | |
C10 | 0.6408 (9) | 0.8669 (5) | 0.9587 (4) | 0.0184 (13) | |
H10A | 0.6897 | 0.9332 | 0.9218 | 0.022* | |
H10B | 0.4947 | 0.8906 | 0.9724 | 0.022* | |
C11 | 0.6861 (9) | 0.6296 (5) | 1.0452 (4) | 0.0166 (12) | |
H11A | 0.7724 | 0.5633 | 1.0803 | 0.020* | |
H11B | 0.5265 | 0.6057 | 1.0346 | 0.020* | |
C12 | 0.7259 (9) | 0.7576 (5) | 1.1030 (4) | 0.0190 (13) | |
H12A | 0.5852 | 0.7841 | 1.1206 | 0.023* | |
H12B | 0.8372 | 0.7462 | 1.1602 | 0.023* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0226 (3) | 0.0185 (4) | 0.0139 (3) | −0.0010 (2) | 0.0020 (2) | −0.0039 (2) |
Br2 | 0.0238 (3) | 0.0191 (4) | 0.0138 (3) | 0.0006 (2) | −0.0006 (2) | −0.0040 (2) |
F1 | 0.029 (2) | 0.109 (4) | 0.030 (2) | −0.026 (2) | 0.0163 (19) | −0.030 (2) |
F2 | 0.063 (3) | 0.039 (3) | 0.057 (3) | 0.034 (2) | −0.037 (2) | −0.027 (2) |
F3 | 0.048 (2) | 0.027 (2) | 0.035 (2) | 0.0166 (18) | −0.0128 (19) | −0.0137 (18) |
F4 | 0.047 (2) | 0.068 (3) | 0.018 (2) | −0.033 (2) | 0.0093 (18) | −0.006 (2) |
F5 | 0.033 (2) | 0.067 (3) | 0.0161 (19) | −0.0233 (19) | 0.0109 (16) | −0.0084 (19) |
F6 | 0.042 (2) | 0.023 (2) | 0.041 (2) | 0.0170 (17) | −0.0157 (18) | −0.0147 (18) |
F7 | 0.038 (2) | 0.027 (2) | 0.032 (2) | 0.0178 (16) | −0.0109 (17) | −0.0101 (17) |
F8 | 0.030 (2) | 0.053 (3) | 0.0147 (18) | −0.0173 (17) | 0.0070 (16) | −0.0038 (17) |
F9 | 0.054 (3) | 0.067 (3) | 0.021 (2) | −0.036 (2) | 0.0193 (19) | −0.011 (2) |
F10 | 0.048 (2) | 0.025 (2) | 0.034 (2) | 0.0192 (17) | −0.0139 (18) | −0.0131 (18) |
F11 | 0.078 (3) | 0.043 (3) | 0.056 (3) | 0.043 (2) | −0.043 (3) | −0.032 (2) |
F12 | 0.030 (2) | 0.107 (4) | 0.032 (2) | −0.023 (2) | 0.0144 (19) | −0.033 (2) |
C1 | 0.030 (3) | 0.025 (4) | 0.021 (3) | 0.004 (3) | 0.003 (3) | −0.007 (3) |
C2 | 0.020 (3) | 0.015 (3) | 0.015 (3) | 0.001 (2) | 0.004 (2) | 0.002 (2) |
C3 | 0.024 (3) | 0.015 (3) | 0.022 (3) | 0.001 (2) | 0.010 (3) | −0.002 (3) |
C4 | 0.019 (3) | 0.019 (3) | 0.017 (3) | −0.001 (2) | 0.003 (2) | 0.003 (3) |
C5 | 0.017 (3) | 0.022 (4) | 0.016 (3) | 0.000 (2) | 0.004 (2) | 0.001 (3) |
C6 | 0.024 (3) | 0.028 (4) | 0.025 (4) | 0.007 (3) | 0.001 (3) | −0.006 (3) |
N1 | 0.016 (2) | 0.017 (3) | 0.013 (2) | −0.0002 (19) | 0.001 (2) | −0.004 (2) |
N2 | 0.016 (2) | 0.008 (3) | 0.016 (2) | −0.0036 (18) | 0.0005 (19) | −0.0035 (19) |
C7 | 0.012 (3) | 0.019 (3) | 0.014 (3) | 0.003 (2) | 0.001 (2) | −0.002 (2) |
C8 | 0.017 (3) | 0.023 (4) | 0.014 (3) | −0.001 (2) | −0.001 (2) | 0.001 (2) |
C9 | 0.020 (3) | 0.013 (3) | 0.016 (3) | 0.001 (2) | −0.003 (2) | −0.006 (2) |
C10 | 0.022 (3) | 0.016 (3) | 0.016 (3) | 0.005 (2) | 0.001 (2) | −0.001 (2) |
C11 | 0.019 (3) | 0.012 (3) | 0.019 (3) | −0.006 (2) | 0.006 (2) | −0.002 (2) |
C12 | 0.017 (3) | 0.020 (3) | 0.020 (3) | 0.000 (2) | 0.004 (2) | −0.001 (3) |
Geometric parameters (Å, º) top
Br1—C1 | 1.930 (6) | N1—C9 | 1.479 (7) |
Br2—C6 | 1.937 (6) | N1—C11 | 1.472 (7) |
F1—C1 | 1.349 (7) | N2—C8 | 1.468 (7) |
F2—C1 | 1.328 (7) | N2—C10 | 1.476 (7) |
F3—C2 | 1.313 (6) | N2—C12 | 1.477 (7) |
F4—C2 | 1.343 (6) | C7—H7A | 0.9700 |
F5—C3 | 1.341 (7) | C7—H7B | 0.9700 |
F6—C3 | 1.334 (7) | C7—C8 | 1.545 (7) |
F7—C4 | 1.341 (7) | C8—H8A | 0.9700 |
F8—C4 | 1.346 (6) | C8—H8B | 0.9700 |
F9—C5 | 1.337 (6) | C9—H9A | 0.9700 |
F10—C5 | 1.318 (7) | C9—H9B | 0.9700 |
F11—C6 | 1.327 (7) | C9—C10 | 1.545 (7) |
F12—C6 | 1.351 (8) | C10—H10A | 0.9700 |
C1—C2 | 1.541 (8) | C10—H10B | 0.9700 |
C2—C3 | 1.560 (8) | C11—H11A | 0.9700 |
C3—C4 | 1.545 (8) | C11—H11B | 0.9700 |
C4—C5 | 1.553 (8) | C11—C12 | 1.549 (7) |
C5—C6 | 1.537 (8) | C12—H12A | 0.9700 |
N1—C7 | 1.482 (6) | C12—H12B | 0.9700 |
| | | |
F1—C1—Br1 | 108.9 (4) | C8—N2—C10 | 108.2 (4) |
F1—C1—C2 | 109.2 (5) | C8—N2—C12 | 107.9 (4) |
F2—C1—Br1 | 109.5 (4) | C10—N2—C12 | 108.0 (4) |
F2—C1—F1 | 107.4 (5) | N1—C7—H7A | 109.5 |
F2—C1—C2 | 110.1 (5) | N1—C7—H7B | 109.5 |
C2—C1—Br1 | 111.6 (4) | N1—C7—C8 | 110.8 (4) |
F3—C2—F4 | 109.0 (5) | H7A—C7—H7B | 108.1 |
F3—C2—C1 | 108.7 (5) | C8—C7—H7A | 109.5 |
F3—C2—C3 | 108.7 (5) | C8—C7—H7B | 109.5 |
F4—C2—C1 | 107.0 (5) | N2—C8—C7 | 110.8 (4) |
F4—C2—C3 | 108.3 (4) | N2—C8—H8A | 109.5 |
C1—C2—C3 | 115.0 (5) | N2—C8—H8B | 109.5 |
F5—C3—C2 | 107.9 (4) | C7—C8—H8A | 109.5 |
F5—C3—C4 | 108.0 (5) | C7—C8—H8B | 109.5 |
F6—C3—F5 | 107.7 (5) | H8A—C8—H8B | 108.1 |
F6—C3—C2 | 108.4 (5) | N1—C9—H9A | 109.6 |
F6—C3—C4 | 108.9 (4) | N1—C9—H9B | 109.6 |
C4—C3—C2 | 115.7 (5) | N1—C9—C10 | 110.1 (4) |
F7—C4—F8 | 107.2 (5) | H9A—C9—H9B | 108.1 |
F7—C4—C3 | 109.3 (4) | C10—C9—H9A | 109.6 |
F7—C4—C5 | 109.0 (5) | C10—C9—H9B | 109.6 |
F8—C4—C3 | 108.4 (4) | N2—C10—C9 | 111.3 (4) |
F8—C4—C5 | 107.5 (4) | N2—C10—H10A | 109.4 |
C3—C4—C5 | 115.1 (5) | N2—C10—H10B | 109.4 |
F9—C5—C4 | 108.4 (5) | C9—C10—H10A | 109.4 |
F9—C5—C6 | 106.9 (5) | C9—C10—H10B | 109.4 |
F10—C5—F9 | 108.8 (5) | H10A—C10—H10B | 108.0 |
F10—C5—C4 | 109.1 (5) | N1—C11—H11A | 109.5 |
F10—C5—C6 | 107.8 (5) | N1—C11—H11B | 109.5 |
C6—C5—C4 | 115.6 (5) | N1—C11—C12 | 110.6 (4) |
F11—C6—Br2 | 109.5 (4) | H11A—C11—H11B | 108.1 |
F11—C6—F12 | 107.1 (5) | C12—C11—H11A | 109.5 |
F11—C6—C5 | 110.6 (5) | C12—C11—H11B | 109.5 |
F12—C6—Br2 | 108.7 (4) | N2—C12—C11 | 110.8 (4) |
F12—C6—C5 | 109.4 (5) | N2—C12—H12A | 109.5 |
C5—C6—Br2 | 111.5 (4) | N2—C12—H12B | 109.5 |
C9—N1—C7 | 108.0 (4) | C11—C12—H12A | 109.5 |
C11—N1—C7 | 108.5 (4) | C11—C12—H12B | 109.5 |
C11—N1—C9 | 108.1 (4) | H12A—C12—H12B | 108.1 |
| | | |
Br1—C1—C2—F3 | 54.7 (6) | F10—C5—C6—Br2 | −55.4 (6) |
Br1—C1—C2—F4 | −62.8 (5) | F10—C5—C6—F11 | −177.4 (5) |
Br1—C1—C2—C3 | 176.8 (4) | F10—C5—C6—F12 | 64.9 (6) |
F1—C1—C2—F3 | −65.8 (6) | C1—C2—C3—F5 | −61.8 (6) |
F1—C1—C2—F4 | 176.7 (5) | C1—C2—C3—F6 | 54.6 (6) |
F1—C1—C2—C3 | 56.3 (7) | C1—C2—C3—C4 | 177.2 (5) |
F2—C1—C2—F3 | 176.6 (5) | C2—C3—C4—F7 | 57.3 (6) |
F2—C1—C2—F4 | 59.1 (6) | C2—C3—C4—F8 | −59.3 (6) |
F2—C1—C2—C3 | −61.3 (7) | C2—C3—C4—C5 | −179.7 (5) |
F3—C2—C3—F5 | 60.3 (6) | C3—C4—C5—F9 | −56.7 (6) |
F3—C2—C3—F6 | 176.6 (4) | C3—C4—C5—F10 | 61.6 (6) |
F3—C2—C3—C4 | −60.8 (6) | C3—C4—C5—C6 | −176.8 (5) |
F4—C2—C3—F5 | 178.6 (5) | C4—C5—C6—Br2 | −177.7 (4) |
F4—C2—C3—F6 | −65.1 (6) | C4—C5—C6—F11 | 60.3 (7) |
F4—C2—C3—C4 | 57.5 (6) | C4—C5—C6—F12 | −57.4 (7) |
F5—C3—C4—F7 | −63.7 (6) | N1—C7—C8—N2 | 2.6 (6) |
F5—C3—C4—F8 | 179.7 (5) | N1—C9—C10—N2 | 3.2 (6) |
F5—C3—C4—C5 | 59.3 (6) | N1—C11—C12—N2 | 4.1 (6) |
F6—C3—C4—F7 | 179.6 (5) | C7—N1—C9—C10 | −60.1 (5) |
F6—C3—C4—F8 | 63.0 (6) | C7—N1—C11—C12 | 55.6 (6) |
F6—C3—C4—C5 | −57.4 (6) | C8—N2—C10—C9 | 56.6 (6) |
F7—C4—C5—F9 | 66.4 (6) | C8—N2—C12—C11 | −61.1 (5) |
F7—C4—C5—F10 | −175.2 (4) | C9—N1—C7—C8 | 57.2 (5) |
F7—C4—C5—C6 | −53.6 (7) | C9—N1—C11—C12 | −61.3 (5) |
F8—C4—C5—F9 | −177.6 (5) | C10—N2—C8—C7 | −59.6 (6) |
F8—C4—C5—F10 | −59.3 (6) | C10—N2—C12—C11 | 55.7 (6) |
F8—C4—C5—C6 | 62.3 (7) | C11—N1—C7—C8 | −59.7 (6) |
F9—C5—C6—Br2 | 61.5 (6) | C11—N1—C9—C10 | 57.1 (5) |
F9—C5—C6—F11 | −60.6 (7) | C12—N2—C8—C7 | 57.0 (6) |
F9—C5—C6—F12 | −178.3 (5) | C12—N2—C10—C9 | −60.0 (6) |
1,8-Dibromoperfluorooctane–1,4-diazabicyclo[2.2.2]octane (1/1) (III)
top
Crystal data top
C8Br2F16·C6H12N2 | Z = 2 |
Mr = 672.08 | F(000) = 648 |
Triclinic, P1 | Dx = 2.157 Mg m−3 |
a = 6.03367 (19) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.4836 (5) Å | Cell parameters from 4902 reflections |
c = 16.4471 (9) Å | θ = 3.7–28.5° |
α = 88.785 (4)° | µ = 4.07 mm−1 |
β = 84.126 (3)° | T = 150 K |
γ = 89.724 (3)° | Plate, colourless |
V = 1034.65 (8) Å3 | 0.14 × 0.08 × 0.04 mm |
Data collection top
SuperNova Single source at offset Eos diffractometer | 4680 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 3723 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.042 |
Detector resolution: 8.0714 pixels mm-1 | θmax = 27.5°, θmin = 3.4° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −13→13 |
Tmin = 0.622, Tmax = 1.000 | l = −20→21 |
14918 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: iterative |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.0543P)2 + 1.8052P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
4680 reflections | Δρmax = 1.01 e Å−3 |
307 parameters | Δρmin = −0.69 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 1.23740 (7) | 0.52567 (4) | 0.18081 (3) | 0.02372 (14) | |
Br2 | 0.31570 (7) | 0.97270 (4) | 0.81774 (3) | 0.02532 (14) | |
F1 | 1.3167 (7) | 0.7383 (4) | 0.2593 (3) | 0.0833 (16) | |
F2 | 1.3831 (5) | 0.5669 (5) | 0.3265 (2) | 0.0725 (13) | |
F3 | 0.8768 (5) | 0.6934 (4) | 0.28024 (19) | 0.0543 (10) | |
F4 | 0.9322 (5) | 0.5136 (3) | 0.34060 (19) | 0.0451 (8) | |
F5 | 1.0979 (5) | 0.8127 (3) | 0.3973 (2) | 0.0527 (10) | |
F6 | 1.1252 (5) | 0.6296 (3) | 0.45864 (18) | 0.0488 (9) | |
F7 | 0.6478 (5) | 0.7905 (3) | 0.40831 (18) | 0.0478 (9) | |
F8 | 0.6682 (5) | 0.6037 (3) | 0.4658 (2) | 0.0432 (8) | |
F9 | 0.8583 (5) | 0.8949 (3) | 0.5291 (2) | 0.0516 (10) | |
F10 | 0.8853 (5) | 0.7085 (3) | 0.58647 (18) | 0.0528 (10) | |
F11 | 0.4022 (5) | 0.8649 (4) | 0.53924 (19) | 0.0505 (9) | |
F12 | 0.4369 (5) | 0.6839 (3) | 0.6011 (2) | 0.0546 (10) | |
F13 | 0.5997 (6) | 0.9860 (3) | 0.6536 (2) | 0.0494 (9) | |
F14 | 0.6676 (6) | 0.8086 (4) | 0.71488 (19) | 0.0603 (11) | |
F15 | 0.1540 (5) | 0.9307 (5) | 0.6751 (2) | 0.0803 (15) | |
F16 | 0.2275 (8) | 0.7598 (4) | 0.7402 (3) | 0.098 (2) | |
C7 | 1.2412 (8) | 0.6223 (5) | 0.2782 (3) | 0.0330 (11) | |
C8 | 1.0085 (6) | 0.6313 (4) | 0.3270 (3) | 0.0208 (9) | |
C9 | 1.0034 (7) | 0.6992 (4) | 0.4097 (3) | 0.0228 (9) | |
C10 | 0.7661 (7) | 0.7177 (4) | 0.4556 (3) | 0.0206 (9) | |
C11 | 0.7649 (7) | 0.7810 (4) | 0.5399 (3) | 0.0225 (9) | |
C12 | 0.5298 (7) | 0.7974 (4) | 0.5869 (3) | 0.0242 (9) | |
C13 | 0.5292 (7) | 0.8682 (4) | 0.6694 (3) | 0.0219 (9) | |
C14 | 0.3021 (8) | 0.8752 (5) | 0.7208 (3) | 0.0378 (13) | |
N1 | 0.7315 (5) | 0.6447 (3) | −0.0400 (2) | 0.0189 (7) | |
N2 | 0.7042 (5) | 0.8534 (3) | 0.0414 (2) | 0.0189 (7) | |
C1 | 0.8227 (7) | 0.6268 (4) | 0.0389 (3) | 0.0238 (9) | |
H1A | 0.9790 | 0.6037 | 0.0296 | 0.029* | |
H1B | 0.7448 | 0.5575 | 0.0696 | 0.029* | |
C2 | 0.4988 (6) | 0.6868 (4) | −0.0243 (3) | 0.0217 (9) | |
H2A | 0.4133 | 0.6216 | 0.0075 | 0.026* | |
H2B | 0.4356 | 0.6983 | −0.0759 | 0.026* | |
C3 | 0.8580 (7) | 0.7475 (4) | −0.0859 (3) | 0.0238 (9) | |
H3A | 0.7961 | 0.7640 | −0.1372 | 0.029* | |
H3B | 1.0119 | 0.7211 | −0.0981 | 0.029* | |
C4 | 0.8483 (7) | 0.8712 (4) | −0.0353 (3) | 0.0243 (9) | |
H4A | 0.9972 | 0.8935 | −0.0233 | 0.029* | |
H4B | 0.7914 | 0.9409 | −0.0670 | 0.029* | |
C5 | 0.4823 (6) | 0.8127 (4) | 0.0220 (3) | 0.0217 (9) | |
H5A | 0.4188 | 0.8783 | −0.0111 | 0.026* | |
H5B | 0.3845 | 0.8016 | 0.0723 | 0.026* | |
C6 | 0.7980 (7) | 0.7497 (4) | 0.0891 (3) | 0.0242 (9) | |
H6A | 0.7012 | 0.7336 | 0.1390 | 0.029* | |
H6B | 0.9427 | 0.7750 | 0.1040 | 0.029* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0275 (2) | 0.0276 (3) | 0.0159 (2) | 0.00098 (16) | −0.00033 (16) | −0.00486 (18) |
Br2 | 0.0299 (2) | 0.0282 (3) | 0.0170 (3) | −0.00127 (17) | 0.00269 (17) | −0.00512 (18) |
F1 | 0.106 (3) | 0.060 (2) | 0.071 (3) | −0.059 (2) | 0.064 (2) | −0.044 (2) |
F2 | 0.0323 (17) | 0.149 (4) | 0.040 (2) | 0.029 (2) | −0.0150 (15) | −0.043 (2) |
F3 | 0.059 (2) | 0.087 (3) | 0.0182 (17) | 0.0405 (18) | −0.0105 (14) | −0.0067 (16) |
F4 | 0.064 (2) | 0.0318 (16) | 0.0356 (19) | −0.0178 (14) | 0.0164 (15) | −0.0122 (14) |
F5 | 0.0584 (19) | 0.0421 (18) | 0.052 (2) | −0.0298 (15) | 0.0295 (16) | −0.0262 (16) |
F6 | 0.0370 (16) | 0.093 (3) | 0.0180 (16) | 0.0294 (16) | −0.0096 (12) | −0.0065 (16) |
F7 | 0.0454 (17) | 0.080 (2) | 0.0193 (16) | 0.0333 (16) | −0.0079 (13) | −0.0037 (15) |
F8 | 0.0454 (17) | 0.0393 (17) | 0.0413 (19) | −0.0196 (13) | 0.0169 (14) | −0.0185 (14) |
F9 | 0.0539 (18) | 0.0433 (18) | 0.052 (2) | −0.0283 (14) | 0.0289 (16) | −0.0260 (16) |
F10 | 0.0505 (18) | 0.092 (3) | 0.0169 (16) | 0.0429 (18) | −0.0122 (13) | −0.0055 (16) |
F11 | 0.0364 (16) | 0.093 (3) | 0.0236 (17) | 0.0310 (16) | −0.0106 (13) | −0.0121 (17) |
F12 | 0.063 (2) | 0.0417 (18) | 0.052 (2) | −0.0320 (15) | 0.0318 (17) | −0.0249 (16) |
F13 | 0.072 (2) | 0.0342 (17) | 0.0369 (19) | −0.0213 (15) | 0.0241 (16) | −0.0136 (14) |
F14 | 0.062 (2) | 0.101 (3) | 0.0196 (17) | 0.049 (2) | −0.0153 (15) | −0.0143 (18) |
F15 | 0.0312 (17) | 0.165 (4) | 0.049 (2) | 0.033 (2) | −0.0147 (16) | −0.055 (3) |
F16 | 0.133 (4) | 0.071 (3) | 0.075 (3) | −0.073 (3) | 0.077 (3) | −0.050 (2) |
C7 | 0.032 (2) | 0.046 (3) | 0.021 (3) | −0.009 (2) | 0.0049 (19) | −0.012 (2) |
C8 | 0.021 (2) | 0.023 (2) | 0.018 (2) | −0.0001 (16) | −0.0047 (16) | −0.0028 (18) |
C9 | 0.021 (2) | 0.029 (2) | 0.018 (2) | −0.0047 (17) | −0.0010 (16) | −0.0028 (18) |
C10 | 0.023 (2) | 0.026 (2) | 0.013 (2) | −0.0003 (16) | −0.0043 (16) | −0.0019 (17) |
C11 | 0.022 (2) | 0.027 (2) | 0.019 (2) | −0.0018 (16) | −0.0033 (17) | −0.0048 (19) |
C12 | 0.025 (2) | 0.028 (2) | 0.019 (2) | −0.0044 (17) | 0.0010 (17) | −0.0046 (19) |
C13 | 0.023 (2) | 0.024 (2) | 0.019 (2) | −0.0018 (16) | −0.0033 (16) | 0.0005 (18) |
C14 | 0.035 (3) | 0.047 (3) | 0.029 (3) | −0.012 (2) | 0.012 (2) | −0.017 (2) |
N1 | 0.0191 (16) | 0.0215 (18) | 0.0164 (19) | −0.0004 (13) | −0.0025 (13) | −0.0072 (15) |
N2 | 0.0208 (17) | 0.0172 (17) | 0.018 (2) | 0.0011 (13) | −0.0004 (13) | −0.0043 (14) |
C1 | 0.030 (2) | 0.021 (2) | 0.022 (2) | 0.0070 (17) | −0.0097 (18) | −0.0025 (18) |
C2 | 0.0173 (19) | 0.025 (2) | 0.023 (2) | −0.0029 (15) | −0.0036 (16) | −0.0046 (18) |
C3 | 0.026 (2) | 0.025 (2) | 0.019 (2) | −0.0050 (17) | 0.0036 (17) | −0.0069 (18) |
C4 | 0.025 (2) | 0.022 (2) | 0.024 (3) | −0.0053 (16) | 0.0036 (17) | −0.0060 (18) |
C5 | 0.0177 (19) | 0.027 (2) | 0.021 (2) | 0.0033 (16) | −0.0028 (16) | −0.0040 (18) |
C6 | 0.031 (2) | 0.023 (2) | 0.020 (2) | 0.0058 (17) | −0.0081 (18) | −0.0033 (18) |
Geometric parameters (Å, º) top
Br1—C7 | 1.915 (5) | C12—C13 | 1.560 (6) |
Br2—C14 | 1.921 (5) | C13—C14 | 1.537 (6) |
F1—C7 | 1.321 (6) | N1—C1 | 1.469 (5) |
F2—C7 | 1.347 (6) | N1—C2 | 1.469 (5) |
F3—C8 | 1.321 (5) | N1—C3 | 1.472 (5) |
F4—C8 | 1.326 (5) | N2—C4 | 1.466 (5) |
F5—C9 | 1.325 (5) | N2—C5 | 1.474 (5) |
F6—C9 | 1.346 (5) | N2—C6 | 1.471 (5) |
F7—C10 | 1.334 (5) | C1—H1A | 0.9700 |
F8—C10 | 1.336 (5) | C1—H1B | 0.9700 |
F9—C11 | 1.323 (5) | C1—C6 | 1.543 (6) |
F10—C11 | 1.333 (5) | C2—H2A | 0.9700 |
F11—C12 | 1.343 (5) | C2—H2B | 0.9700 |
F12—C12 | 1.323 (5) | C2—C5 | 1.536 (5) |
F13—C13 | 1.320 (5) | C3—H3A | 0.9700 |
F14—C13 | 1.323 (5) | C3—H3B | 0.9700 |
F15—C14 | 1.348 (7) | C3—C4 | 1.554 (6) |
F16—C14 | 1.314 (6) | C4—H4A | 0.9700 |
C7—C8 | 1.547 (6) | C4—H4B | 0.9700 |
C8—C9 | 1.547 (6) | C5—H5A | 0.9700 |
C9—C10 | 1.562 (6) | C5—H5B | 0.9700 |
C10—C11 | 1.549 (6) | C6—H6A | 0.9700 |
C11—C12 | 1.555 (6) | C6—H6B | 0.9700 |
| | | |
F1—C7—Br1 | 109.7 (3) | F16—C14—F15 | 106.7 (5) |
F1—C7—F2 | 107.2 (5) | F16—C14—C13 | 110.3 (4) |
F1—C7—C8 | 109.4 (4) | C13—C14—Br2 | 112.0 (3) |
F2—C7—Br1 | 109.2 (3) | C1—N1—C3 | 108.0 (3) |
F2—C7—C8 | 108.7 (4) | C2—N1—C1 | 108.3 (3) |
C8—C7—Br1 | 112.5 (3) | C2—N1—C3 | 108.0 (3) |
F3—C8—F4 | 108.8 (4) | C4—N2—C5 | 108.6 (3) |
F3—C8—C7 | 107.4 (4) | C4—N2—C6 | 108.2 (3) |
F3—C8—C9 | 108.9 (3) | C6—N2—C5 | 107.8 (3) |
F4—C8—C7 | 107.8 (3) | N1—C1—H1A | 109.5 |
F4—C8—C9 | 108.7 (4) | N1—C1—H1B | 109.5 |
C9—C8—C7 | 115.1 (3) | N1—C1—C6 | 110.9 (3) |
F5—C9—F6 | 108.2 (4) | H1A—C1—H1B | 108.0 |
F5—C9—C8 | 108.9 (4) | C6—C1—H1A | 109.5 |
F5—C9—C10 | 108.4 (3) | C6—C1—H1B | 109.5 |
F6—C9—C8 | 108.1 (3) | N1—C2—H2A | 109.4 |
F6—C9—C10 | 108.0 (4) | N1—C2—H2B | 109.4 |
C8—C9—C10 | 115.0 (3) | N1—C2—C5 | 111.1 (3) |
F7—C10—F8 | 108.4 (4) | H2A—C2—H2B | 108.0 |
F7—C10—C9 | 108.0 (4) | C5—C2—H2A | 109.4 |
F7—C10—C11 | 108.6 (3) | C5—C2—H2B | 109.4 |
F8—C10—C9 | 108.4 (3) | N1—C3—H3A | 109.6 |
F8—C10—C11 | 109.1 (4) | N1—C3—H3B | 109.6 |
C11—C10—C9 | 114.2 (3) | N1—C3—C4 | 110.4 (3) |
F9—C11—F10 | 109.2 (4) | H3A—C3—H3B | 108.1 |
F9—C11—C10 | 108.7 (4) | C4—C3—H3A | 109.6 |
F9—C11—C12 | 108.4 (3) | C4—C3—H3B | 109.6 |
F10—C11—C10 | 108.2 (3) | N2—C4—C3 | 110.6 (3) |
F10—C11—C12 | 107.6 (4) | N2—C4—H4A | 109.5 |
C10—C11—C12 | 114.7 (4) | N2—C4—H4B | 109.5 |
F11—C12—C11 | 108.5 (4) | C3—C4—H4A | 109.5 |
F11—C12—C13 | 107.7 (3) | C3—C4—H4B | 109.5 |
F12—C12—F11 | 107.7 (4) | H4A—C4—H4B | 108.1 |
F12—C12—C11 | 109.4 (3) | N2—C5—C2 | 110.6 (3) |
F12—C12—C13 | 109.1 (4) | N2—C5—H5A | 109.5 |
C11—C12—C13 | 114.2 (4) | N2—C5—H5B | 109.5 |
F13—C13—F14 | 109.1 (4) | C2—C5—H5A | 109.5 |
F13—C13—C12 | 108.6 (4) | C2—C5—H5B | 109.5 |
F13—C13—C14 | 108.0 (4) | H5A—C5—H5B | 108.1 |
F14—C13—C12 | 108.7 (4) | N2—C6—C1 | 110.5 (4) |
F14—C13—C14 | 107.0 (4) | N2—C6—H6A | 109.5 |
C14—C13—C12 | 115.4 (4) | N2—C6—H6B | 109.5 |
F15—C14—Br2 | 108.7 (3) | C1—C6—H6A | 109.5 |
F15—C14—C13 | 108.7 (4) | C1—C6—H6B | 109.5 |
F16—C14—Br2 | 110.2 (4) | H6A—C6—H6B | 108.1 |
| | | |
Br1—C7—C8—F3 | −63.1 (4) | F13—C13—C14—Br2 | −55.0 (5) |
Br1—C7—C8—F4 | 54.0 (5) | F13—C13—C14—F15 | 65.2 (5) |
Br1—C7—C8—C9 | 175.5 (3) | F13—C13—C14—F16 | −178.2 (5) |
F1—C7—C8—F3 | 59.2 (5) | F14—C13—C14—Br2 | 62.4 (5) |
F1—C7—C8—F4 | 176.2 (4) | F14—C13—C14—F15 | −177.5 (4) |
F1—C7—C8—C9 | −62.3 (6) | F14—C13—C14—F16 | −60.8 (6) |
F2—C7—C8—F3 | 175.9 (4) | C7—C8—C9—F5 | 53.5 (5) |
F2—C7—C8—F4 | −67.0 (5) | C7—C8—C9—F6 | −63.8 (5) |
F2—C7—C8—C9 | 54.5 (5) | C7—C8—C9—C10 | 175.4 (4) |
F3—C8—C9—F5 | −67.1 (5) | C8—C9—C10—F7 | −61.4 (5) |
F3—C8—C9—F6 | 175.6 (4) | C8—C9—C10—F8 | 55.9 (5) |
F3—C8—C9—C10 | 54.8 (5) | C8—C9—C10—C11 | 177.7 (4) |
F4—C8—C9—F5 | 174.5 (3) | C9—C10—C11—F9 | 59.7 (5) |
F4—C8—C9—F6 | 57.1 (4) | C9—C10—C11—F10 | −58.8 (5) |
F4—C8—C9—C10 | −63.6 (5) | C9—C10—C11—C12 | −178.8 (3) |
F5—C9—C10—F7 | 60.8 (5) | C10—C11—C12—F11 | −56.5 (5) |
F5—C9—C10—F8 | 178.0 (4) | C10—C11—C12—F12 | 60.7 (5) |
F5—C9—C10—C11 | −60.1 (5) | C10—C11—C12—C13 | −176.7 (4) |
F6—C9—C10—F7 | 177.8 (4) | C11—C12—C13—F13 | 64.0 (5) |
F6—C9—C10—F8 | −64.9 (4) | C11—C12—C13—F14 | −54.6 (5) |
F6—C9—C10—C11 | 56.9 (5) | C11—C12—C13—C14 | −174.8 (4) |
F7—C10—C11—F9 | −60.9 (5) | C12—C13—C14—Br2 | −176.6 (3) |
F7—C10—C11—F10 | −179.4 (3) | C12—C13—C14—F15 | −56.4 (5) |
F7—C10—C11—C12 | 60.6 (5) | C12—C13—C14—F16 | 60.2 (6) |
F8—C10—C11—F9 | −178.8 (3) | N1—C1—C6—N2 | −3.9 (5) |
F8—C10—C11—F10 | 62.7 (4) | N1—C2—C5—N2 | −2.6 (5) |
F8—C10—C11—C12 | −57.3 (5) | N1—C3—C4—N2 | −3.7 (5) |
F9—C11—C12—F11 | 65.1 (5) | C1—N1—C2—C5 | 59.6 (4) |
F9—C11—C12—F12 | −177.6 (4) | C1—N1—C3—C4 | −56.4 (4) |
F9—C11—C12—C13 | −55.0 (5) | C2—N1—C1—C6 | −55.8 (4) |
F10—C11—C12—F11 | −176.9 (4) | C2—N1—C3—C4 | 60.5 (4) |
F10—C11—C12—F12 | −59.6 (5) | C3—N1—C1—C6 | 60.9 (4) |
F10—C11—C12—C13 | 62.9 (5) | C3—N1—C2—C5 | −57.1 (4) |
F11—C12—C13—F13 | −56.6 (4) | C4—N2—C5—C2 | 59.9 (4) |
F11—C12—C13—F14 | −175.2 (4) | C4—N2—C6—C1 | −56.5 (4) |
F11—C12—C13—C14 | 64.6 (5) | C5—N2—C4—C3 | −56.1 (4) |
F12—C12—C13—F13 | −173.3 (4) | C5—N2—C6—C1 | 60.8 (4) |
F12—C12—C13—F14 | 68.1 (5) | C6—N2—C4—C3 | 60.7 (4) |
F12—C12—C13—C14 | −52.0 (5) | C6—N2—C5—C2 | −57.2 (4) |
N···Br halogen bond distances (Å) in the current work and previously reported
structures topEntry | Donor | Acceptor | N···Br | Refcode | Reference |
1 | Br(CF2)8Br | Me2N-C6H4-NMe2 | 2.922 (3) | VAQROV | Liantonio et al. (2003) |
2 | Br(CF2)2Br | Me2NCH2CH2NMe2 | 2.862 (5) | REMBOB | Huang et al. (2006) |
3 | Br(CF2)2Br | DABCO | 2.829 (3) | KURMAN | Brisdon et al. (2015) |
4 | Br(CF2)4Br | DABCO | 2.814 (3)av | - | This work |
5 | Br(CF2)6Br | DABCO | 2.949 (4)av | - | This work |
6 | Br(CF2)8Br | DABCO | 2.958 (3)av | - | This work |
Intermolecular F···H and F···F contact distances (Å) less than the sum of
the van der Waals radii and their difference. topAdduct | X | Y | X···Y | Difference |
KURMAN | F1 | H2A | 2.66 | -0.01 |
(I) | F3 | H7Ai | 2.60 | -0.08 |
| F7 | H10Bi | 2.62 | -0.05 |
(II) | F9 | H9Bii | 2.63 | -0.04 |
| F3 | F5ii | 2.872 (6) | -0.068 |
| F6 | F10iii | 2.825 (5) | -0.115 |
(III) | F14 | H3Aiv | 2.66 | -0.01 |
| F5 | F13v | 2.852 (5) | -0.090 |
| F9 | F9v | 2.882 (4) | -0.058 |
| F4 | F10vi | 2.864 (4) | -0.080 |
Symmetry codes:
(i) -x+1, y-1/2, -z+1/2;
(ii) -x+1, -y+1, -z+1;
(iii) -x+1, -y, -z+1;
(iv) x, y, z+1;
(v) -x+2, -y+2, -z+1;
(vi) -x+2, -y+1, -z+1. |
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