A comparative structural study of two related donor–acceptor pyridine-based BF
2 complexes, namely, 3-(dimethylamino)-1,1-difluoro-1
H-pyrido[1,2-
c][1,3,5,2]oxadiazaborinin-9-ium-1-uide, C
8H
10BF
2N
3O (
1), and 3-{(1
E,3
E)-4-[4-(dimethylamino)phenyl]buta-1,3-dien-1-yl}-1,1-difluoro-1
H-pyrido[1,2-
c][1,3,5,2]oxadiazaborinin-9-ium-1-uide, C
18H
18BF
2N
3O (
2), containing a dimethylamino group and either the shortest (in
1) or the longest (in
2) charge-transfer path known until now in this family of compounds, is presented. Single-crystal X-ray diffraction analysis supported by computational investigations shed more light on these systems, indicating, among other aspects, the predominance of C—H
F contacts in
1, the formation of antiparallel dimers held together by π–π interactions in both compounds, and the involvement of fused BF
2-bearing rings in the charge-transfer process.
Supporting information
CCDC references: 1571851; 1571850
For both structures, data collection: CrysAlis PRO (Oxford Diffraction, 2014); cell refinement: CrysAlis PRO (Oxford Diffraction, 2014); data reduction: CrysAlis PRO (Oxford Diffraction, 2014); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2020) and POV-RAY (Persistence of Vision, 2004); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).
3-(Dimethylamino)-1,1-difluoro-1
H-pyrido[1,2-
c][1,3,5,2]-oxadiazaborinin-9-ium-1-uide (1)
top
Crystal data top
C8H10BF2N3O | Z = 2 |
Mr = 213.00 | F(000) = 220 |
Triclinic, P1 | Dx = 1.529 Mg m−3 |
a = 7.7181 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.2139 (6) Å | Cell parameters from 28335 reflections |
c = 8.7684 (6) Å | θ = 2.5–30.5° |
α = 79.847 (6)° | µ = 0.13 mm−1 |
β = 66.782 (7)° | T = 100 K |
γ = 64.907 (7)° | Block, colorless |
V = 462.62 (6) Å3 | 0.37 × 0.35 × 0.24 mm |
Data collection top
Oxford Diffraction SuperNova Dual Source diffractometer with an Eos detector | 2418 reflections with I > 2σ(I) |
Radiation source: SuperNova(Mo) X-ray Source | Rint = 0.044 |
ω scans | θmax = 30.5°, θmin = 2.5° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2014) | h = −11→11 |
Tmin = 0.924, Tmax = 0.982 | k = −11→11 |
28335 measured reflections | l = −12→12 |
2810 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.129 | w = 1/[σ2(Fo2) + (0.074P)2 + 0.111P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2810 reflections | Δρmax = 0.45 e Å−3 |
138 parameters | Δρmin = −0.24 e Å−3 |
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. |
Refinement. Single-crystal X-ray diffraction data were collected on an Oxford
Diffraction SuperNova diffractometer with an Eos CCD detector, Mo <i.Kα
radiation, λ = 0.71073 Å. Data frames were processed (unit-cell
determination, intensity data integration, correction for Lorentz and
polarization effects and empirical absorption correction) using the
corresponding diffractometer's software package (Oxford Diffraction, 2014).
Each structure was solved by direct methods using SHELXS2014/7 (Sheldrick,
2008) and refined by full-matrix least-squares methods based on F2
using SHELXL2014/7 (Sheldrick, 2015). The programs Mercury (Macrae
et al., 2020) and POV-Ray (Persistence of Vision Pty. Ltd,
2004) were used to prepare the molecular graphics images.
All non-hydrogen atoms were refined anisotropically. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
B1 | 0.15455 (18) | 0.78905 (15) | 0.23090 (14) | 0.0188 (2) | |
O2 | 0.13709 (12) | 0.70576 (10) | 0.39554 (9) | 0.01995 (18) | |
C3 | 0.22058 (15) | 0.73233 (13) | 0.48953 (12) | 0.0164 (2) | |
N4 | 0.29568 (14) | 0.85773 (12) | 0.46315 (11) | 0.01862 (19) | |
C5 | 0.28404 (15) | 0.97126 (13) | 0.33165 (12) | 0.0164 (2) | |
C6 | 0.34857 (16) | 1.11463 (14) | 0.31052 (13) | 0.0197 (2) | |
H6 | 0.3972 | 1.1305 | 0.3887 | 0.024* | |
C7 | 0.34090 (17) | 1.23032 (14) | 0.17748 (14) | 0.0210 (2) | |
H7 | 0.3832 | 1.3266 | 0.1640 | 0.025* | |
C8 | 0.27020 (17) | 1.20624 (14) | 0.06084 (14) | 0.0208 (2) | |
H8 | 0.2650 | 1.2851 | −0.0321 | 0.025* | |
C9 | 0.20907 (16) | 1.06668 (14) | 0.08436 (13) | 0.0195 (2) | |
H9 | 0.1610 | 1.0494 | 0.0065 | 0.023* | |
N10 | 0.21565 (13) | 0.95164 (11) | 0.21723 (11) | 0.01670 (18) | |
F11 | 0.30603 (12) | 0.66520 (9) | 0.11001 (9) | 0.02947 (19) | |
F12 | −0.03083 (11) | 0.84862 (10) | 0.20964 (9) | 0.02895 (19) | |
N13 | 0.22392 (14) | 0.62404 (12) | 0.62289 (11) | 0.01902 (19) | |
C14 | 0.30258 (17) | 0.64630 (15) | 0.74086 (14) | 0.0224 (2) | |
H14A | 0.4464 | 0.5634 | 0.7136 | 0.034* | |
H14B | 0.2221 | 0.6202 | 0.8534 | 0.034* | |
H14C | 0.2920 | 0.7703 | 0.7349 | 0.034* | |
C15 | 0.17249 (17) | 0.46669 (14) | 0.64885 (14) | 0.0209 (2) | |
H15A | 0.1228 | 0.4640 | 0.5627 | 0.031* | |
H15B | 0.0654 | 0.4734 | 0.7582 | 0.031* | |
H15C | 0.2948 | 0.3572 | 0.6431 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
B1 | 0.0235 (5) | 0.0213 (5) | 0.0191 (5) | −0.0118 (4) | −0.0131 (4) | 0.0033 (4) |
O2 | 0.0243 (4) | 0.0259 (4) | 0.0202 (4) | −0.0156 (3) | −0.0140 (3) | 0.0046 (3) |
C3 | 0.0150 (4) | 0.0196 (4) | 0.0177 (5) | −0.0071 (3) | −0.0085 (4) | −0.0002 (3) |
N4 | 0.0215 (4) | 0.0211 (4) | 0.0200 (4) | −0.0112 (3) | −0.0121 (3) | 0.0028 (3) |
C5 | 0.0150 (4) | 0.0181 (4) | 0.0180 (4) | −0.0063 (3) | −0.0079 (4) | −0.0009 (3) |
C6 | 0.0215 (5) | 0.0210 (4) | 0.0217 (5) | −0.0108 (4) | −0.0104 (4) | 0.0003 (4) |
C7 | 0.0211 (5) | 0.0199 (4) | 0.0244 (5) | −0.0100 (4) | −0.0089 (4) | 0.0016 (4) |
C8 | 0.0213 (5) | 0.0211 (5) | 0.0219 (5) | −0.0088 (4) | −0.0109 (4) | 0.0043 (4) |
C9 | 0.0205 (5) | 0.0218 (5) | 0.0194 (5) | −0.0087 (4) | −0.0114 (4) | 0.0032 (4) |
N10 | 0.0176 (4) | 0.0185 (4) | 0.0175 (4) | −0.0078 (3) | −0.0097 (3) | 0.0018 (3) |
F11 | 0.0409 (4) | 0.0244 (3) | 0.0238 (4) | −0.0160 (3) | −0.0076 (3) | −0.0028 (3) |
F12 | 0.0332 (4) | 0.0329 (4) | 0.0387 (4) | −0.0203 (3) | −0.0277 (3) | 0.0119 (3) |
N13 | 0.0229 (4) | 0.0225 (4) | 0.0195 (4) | −0.0127 (3) | −0.0130 (3) | 0.0039 (3) |
C14 | 0.0258 (5) | 0.0276 (5) | 0.0217 (5) | −0.0123 (4) | −0.0155 (4) | 0.0028 (4) |
C15 | 0.0236 (5) | 0.0211 (4) | 0.0241 (5) | −0.0120 (4) | −0.0133 (4) | 0.0047 (4) |
Geometric parameters (Å, º) top
B1—F12 | 1.3805 (12) | C7—H7 | 0.9500 |
B1—F11 | 1.3855 (14) | C8—C9 | 1.3704 (14) |
B1—O2 | 1.4652 (13) | C8—H8 | 0.9500 |
B1—N10 | 1.5664 (13) | C9—N10 | 1.3677 (13) |
O2—C3 | 1.3204 (11) | C9—H9 | 0.9500 |
C3—N4 | 1.3293 (12) | N13—C14 | 1.4588 (12) |
C3—N13 | 1.3404 (13) | N13—C15 | 1.4629 (13) |
N4—C5 | 1.3560 (13) | C14—H14A | 0.9800 |
C5—N10 | 1.3630 (12) | C14—H14B | 0.9800 |
C5—C6 | 1.4201 (13) | C14—H14C | 0.9800 |
C6—C7 | 1.3723 (14) | C15—H15A | 0.9800 |
C6—H6 | 0.9500 | C15—H15B | 0.9800 |
C7—C8 | 1.4091 (14) | C15—H15C | 0.9800 |
| | | |
F12—B1—F11 | 110.15 (9) | C7—C8—H8 | 120.7 |
F12—B1—O2 | 109.68 (9) | N10—C9—C8 | 121.58 (9) |
F11—B1—O2 | 109.64 (9) | N10—C9—H9 | 119.2 |
F12—B1—N10 | 109.81 (8) | C8—C9—H9 | 119.2 |
F11—B1—N10 | 108.87 (9) | C5—N10—C9 | 121.13 (8) |
O2—B1—N10 | 108.66 (8) | C5—N10—B1 | 120.06 (8) |
C3—O2—B1 | 122.28 (8) | C9—N10—B1 | 118.72 (8) |
O2—C3—N4 | 125.25 (9) | C3—N13—C14 | 120.81 (8) |
O2—C3—N13 | 115.67 (8) | C3—N13—C15 | 122.67 (8) |
N4—C3—N13 | 119.07 (9) | C14—N13—C15 | 116.17 (8) |
C3—N4—C5 | 118.59 (8) | N13—C14—H14A | 109.5 |
N4—C5—N10 | 122.56 (9) | N13—C14—H14B | 109.5 |
N4—C5—C6 | 118.86 (9) | H14A—C14—H14B | 109.5 |
N10—C5—C6 | 118.58 (9) | N13—C14—H14C | 109.5 |
C7—C6—C5 | 120.15 (9) | H14A—C14—H14C | 109.5 |
C7—C6—H6 | 119.9 | H14B—C14—H14C | 109.5 |
C5—C6—H6 | 119.9 | N13—C15—H15A | 109.5 |
C6—C7—C8 | 119.99 (9) | N13—C15—H15B | 109.5 |
C6—C7—H7 | 120.0 | H15A—C15—H15B | 109.5 |
C8—C7—H7 | 120.0 | N13—C15—H15C | 109.5 |
C9—C8—C7 | 118.57 (9) | H15A—C15—H15C | 109.5 |
C9—C8—H8 | 120.7 | H15B—C15—H15C | 109.5 |
| | | |
F12—B1—O2—C3 | −138.58 (9) | C6—C5—N10—C9 | 0.11 (15) |
F11—B1—O2—C3 | 100.35 (11) | N4—C5—N10—B1 | −2.32 (15) |
N10—B1—O2—C3 | −18.53 (13) | C6—C5—N10—B1 | 176.65 (9) |
B1—O2—C3—N4 | 12.67 (16) | C8—C9—N10—C5 | −0.15 (16) |
B1—O2—C3—N13 | −168.64 (9) | C8—C9—N10—B1 | −176.74 (10) |
O2—C3—N4—C5 | 1.28 (16) | F12—B1—N10—C5 | 133.56 (10) |
N13—C3—N4—C5 | −177.37 (9) | F11—B1—N10—C5 | −105.77 (10) |
C3—N4—C5—N10 | −6.12 (16) | O2—B1—N10—C5 | 13.59 (13) |
C3—N4—C5—C6 | 174.90 (9) | F12—B1—N10—C9 | −49.82 (13) |
N4—C5—C6—C7 | 179.20 (10) | F11—B1—N10—C9 | 70.86 (11) |
N10—C5—C6—C7 | 0.19 (16) | O2—B1—N10—C9 | −169.79 (8) |
C5—C6—C7—C8 | −0.44 (16) | O2—C3—N13—C14 | −176.83 (9) |
C6—C7—C8—C9 | 0.39 (16) | N4—C3—N13—C14 | 1.94 (15) |
C7—C8—C9—N10 | −0.10 (16) | O2—C3—N13—C15 | 10.31 (15) |
N4—C5—N10—C9 | −178.87 (9) | N4—C3—N13—C15 | −170.92 (9) |
3-{(1
E,3
E)-4-[4-(Dimethylamino)phenyl]buta-1,3-dien-1-yl}-1,1-difluoro-1
H-pyrido[1,2-
c][1,3,5,2]oxadiazaborinin-9-ium-1-uide (2)
top
Crystal data top
C18H18BF2N3O | Z = 2 |
Mr = 341.16 | F(000) = 356 |
Triclinic, P1 | Dx = 1.379 Mg m−3 |
a = 8.1445 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.2758 (3) Å | Cell parameters from 8425 reflections |
c = 12.7398 (6) Å | θ = 2.5–28.6° |
α = 93.518 (4)° | µ = 0.10 mm−1 |
β = 105.066 (4)° | T = 100 K |
γ = 95.613 (3)° | Block, red |
V = 821.83 (6) Å3 | 0.34 × 0.23 × 0.17 mm |
Data collection top
Oxford Diffraction SuperNova Dual Source diffractometer with an Eos detector | 2965 reflections with I > 2σ(I) |
Radiation source: SuperNova (Mo) X-ray Source | Rint = 0.092 |
ω scans | θmax = 28.9°, θmin = 2.5° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2014) | h = −10→10 |
Tmin = 0.508, Tmax = 0.983 | k = −11→11 |
20647 measured reflections | l = −17→17 |
3953 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.073P)2 + 0.1888P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3953 reflections | Δρmax = 0.31 e Å−3 |
228 parameters | Δρmin = −0.37 e Å−3 |
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. |
Refinement. Single-crystal X-ray diffraction data were collected on an Oxford
Diffraction SuperNova diffractometer with an Eos CCD detector, Mo <i.Kα
radiation, λ = 0.71073 Å. Data frames were processed (unit-cell
determination, intensity data integration, correction for Lorentz and
polarization effects and empirical absorption correction) using the
corresponding diffractometer's software package (Oxford Diffraction, 2014).
Each structure was solved by direct methods using SHELXS2014/7 (Sheldrick,
2008) and refined by full-matrix least-squares methods based on F2
using SHELXL2014/7 (Sheldrick, 2015). The programs Mercury (Macrae
et al., 2020) and POV-Ray (Persistence of Vision Pty. Ltd,
2004) were used to prepare the molecular graphics images.
All non-hydrogen atoms were refined anisotropically. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
B1 | 0.2606 (2) | 0.0227 (2) | 0.29228 (13) | 0.0232 (3) | |
O2 | 0.16721 (12) | 0.10249 (13) | 0.19984 (8) | 0.0242 (3) | |
C3 | 0.22710 (18) | 0.13520 (18) | 0.11526 (11) | 0.0214 (3) | |
N4 | 0.37553 (15) | 0.10459 (15) | 0.10316 (9) | 0.0227 (3) | |
C5 | 0.48359 (18) | 0.03306 (17) | 0.18358 (11) | 0.0210 (3) | |
C6 | 0.64306 (18) | 0.00080 (18) | 0.17044 (12) | 0.0248 (3) | |
H6 | 0.6737 | 0.0263 | 0.1058 | 0.030* | |
C7 | 0.75499 (19) | −0.06748 (19) | 0.25046 (13) | 0.0287 (4) | |
H7 | 0.8638 | −0.0879 | 0.2419 | 0.034* | |
C8 | 0.7083 (2) | −0.1069 (2) | 0.34466 (12) | 0.0292 (4) | |
H8 | 0.7849 | −0.1532 | 0.4013 | 0.035* | |
C9 | 0.55000 (19) | −0.07757 (19) | 0.35357 (12) | 0.0259 (3) | |
H9 | 0.5161 | −0.1070 | 0.4164 | 0.031* | |
N10 | 0.43969 (15) | −0.00762 (15) | 0.27532 (9) | 0.0213 (3) | |
F11 | 0.28629 (11) | 0.12133 (12) | 0.38840 (7) | 0.0320 (3) | |
F12 | 0.17079 (11) | −0.12496 (11) | 0.29893 (7) | 0.0313 (2) | |
C13 | 0.11647 (18) | 0.21145 (18) | 0.02888 (11) | 0.0230 (3) | |
H13 | 0.1608 | 0.2421 | −0.0299 | 0.028* | |
C14 | −0.04312 (18) | 0.24205 (17) | 0.02540 (11) | 0.0218 (3) | |
H14 | −0.0887 | 0.2119 | 0.0838 | 0.026* | |
C15 | −0.14948 (18) | 0.31794 (17) | −0.06164 (11) | 0.0224 (3) | |
H15 | −0.1019 | 0.3540 | −0.1180 | 0.027* | |
C16 | −0.31252 (18) | 0.34050 (17) | −0.06754 (11) | 0.0218 (3) | |
H16 | −0.3568 | 0.3019 | −0.0105 | 0.026* | |
C17 | −0.42918 (18) | 0.41718 (17) | −0.15110 (11) | 0.0217 (3) | |
C18 | −0.38915 (19) | 0.47354 (18) | −0.24392 (11) | 0.0243 (3) | |
H18 | −0.2795 | 0.4614 | −0.2544 | 0.029* | |
C19 | −0.5044 (2) | 0.54619 (19) | −0.32062 (12) | 0.0261 (3) | |
H19 | −0.4729 | 0.5823 | −0.3828 | 0.031* | |
C20 | −0.6686 (2) | 0.56789 (19) | −0.30836 (11) | 0.0278 (4) | |
C21 | −0.70956 (19) | 0.51175 (19) | −0.21539 (12) | 0.0263 (3) | |
H21 | −0.8188 | 0.5241 | −0.2043 | 0.032* | |
C22 | −0.59203 (19) | 0.43864 (18) | −0.13978 (11) | 0.0227 (3) | |
H22 | −0.6233 | 0.4016 | −0.0777 | 0.027* | |
N23 | −0.7829 (2) | 0.6411 (2) | −0.38437 (12) | 0.0455 (4) | |
C24 | −0.7416 (2) | 0.6897 (2) | −0.48204 (13) | 0.0371 (4) | |
H24A | −0.6395 | 0.7701 | −0.4623 | 0.056* | |
H24B | −0.8379 | 0.7380 | −0.5272 | 0.056* | |
H24C | −0.7193 | 0.5941 | −0.5232 | 0.056* | |
C25 | −0.9488 (2) | 0.6653 (2) | −0.36915 (14) | 0.0385 (4) | |
H25A | −1.0108 | 0.5596 | −0.3642 | 0.058* | |
H25B | −1.0141 | 0.7172 | −0.4312 | 0.058* | |
H25C | −0.9340 | 0.7353 | −0.3017 | 0.058* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
B1 | 0.0198 (8) | 0.0301 (9) | 0.0202 (7) | 0.0021 (6) | 0.0065 (6) | 0.0022 (6) |
O2 | 0.0204 (5) | 0.0333 (6) | 0.0216 (5) | 0.0067 (4) | 0.0082 (4) | 0.0049 (4) |
C3 | 0.0206 (7) | 0.0205 (7) | 0.0229 (7) | −0.0013 (5) | 0.0077 (5) | −0.0016 (5) |
N4 | 0.0208 (6) | 0.0241 (7) | 0.0243 (6) | 0.0026 (5) | 0.0080 (5) | 0.0023 (5) |
C5 | 0.0188 (7) | 0.0204 (7) | 0.0227 (7) | −0.0014 (5) | 0.0062 (5) | −0.0031 (5) |
C6 | 0.0211 (7) | 0.0250 (8) | 0.0294 (7) | −0.0005 (6) | 0.0106 (6) | −0.0002 (6) |
C7 | 0.0178 (7) | 0.0286 (8) | 0.0376 (8) | 0.0014 (6) | 0.0059 (6) | −0.0054 (6) |
C8 | 0.0239 (7) | 0.0307 (9) | 0.0284 (8) | 0.0065 (6) | −0.0009 (6) | −0.0025 (6) |
C9 | 0.0231 (7) | 0.0314 (8) | 0.0221 (7) | 0.0045 (6) | 0.0041 (5) | 0.0010 (6) |
N10 | 0.0189 (6) | 0.0236 (7) | 0.0203 (6) | 0.0015 (5) | 0.0044 (5) | −0.0012 (5) |
F11 | 0.0273 (5) | 0.0476 (6) | 0.0222 (4) | 0.0091 (4) | 0.0081 (3) | −0.0037 (4) |
F12 | 0.0210 (4) | 0.0367 (6) | 0.0375 (5) | 0.0016 (4) | 0.0094 (4) | 0.0107 (4) |
C13 | 0.0244 (7) | 0.0229 (8) | 0.0224 (7) | 0.0024 (6) | 0.0073 (5) | 0.0025 (5) |
C14 | 0.0236 (7) | 0.0186 (7) | 0.0226 (7) | −0.0008 (6) | 0.0065 (5) | 0.0000 (5) |
C15 | 0.0248 (7) | 0.0193 (7) | 0.0224 (7) | 0.0013 (6) | 0.0058 (5) | 0.0008 (5) |
C16 | 0.0243 (7) | 0.0197 (7) | 0.0209 (7) | 0.0017 (6) | 0.0061 (5) | 0.0007 (5) |
C17 | 0.0235 (7) | 0.0192 (7) | 0.0212 (7) | 0.0012 (6) | 0.0051 (5) | −0.0006 (5) |
C18 | 0.0241 (7) | 0.0249 (8) | 0.0254 (7) | 0.0037 (6) | 0.0093 (6) | 0.0005 (6) |
C19 | 0.0335 (8) | 0.0266 (8) | 0.0212 (7) | 0.0068 (6) | 0.0109 (6) | 0.0044 (6) |
C20 | 0.0351 (8) | 0.0286 (8) | 0.0211 (7) | 0.0139 (7) | 0.0066 (6) | 0.0010 (6) |
C21 | 0.0246 (7) | 0.0298 (8) | 0.0255 (7) | 0.0080 (6) | 0.0074 (6) | −0.0003 (6) |
C22 | 0.0255 (7) | 0.0221 (7) | 0.0217 (7) | 0.0018 (6) | 0.0084 (5) | 0.0019 (5) |
N23 | 0.0527 (10) | 0.0674 (11) | 0.0278 (7) | 0.0409 (9) | 0.0156 (6) | 0.0178 (7) |
C24 | 0.0484 (10) | 0.0363 (9) | 0.0234 (8) | 0.0093 (8) | 0.0018 (7) | 0.0045 (6) |
C25 | 0.0339 (9) | 0.0460 (11) | 0.0326 (9) | 0.0143 (8) | 0.0001 (7) | 0.0027 (7) |
Geometric parameters (Å, º) top
B1—F12 | 1.3800 (19) | C15—H15 | 0.9500 |
B1—F11 | 1.3859 (17) | C16—C17 | 1.454 (2) |
B1—O2 | 1.4593 (19) | C16—H16 | 0.9500 |
B1—N10 | 1.5706 (19) | C17—C22 | 1.398 (2) |
O2—C3 | 1.3250 (17) | C17—C18 | 1.400 (2) |
C3—N4 | 1.3043 (19) | C18—C19 | 1.380 (2) |
C3—C13 | 1.450 (2) | C18—H18 | 0.9500 |
N4—C5 | 1.3719 (19) | C19—C20 | 1.413 (2) |
C5—N10 | 1.3599 (19) | C19—H19 | 0.9500 |
C5—C6 | 1.401 (2) | C20—N23 | 1.373 (2) |
C6—C7 | 1.370 (2) | C20—C21 | 1.405 (2) |
C6—H6 | 0.9500 | C21—C22 | 1.384 (2) |
C7—C8 | 1.397 (2) | C21—H21 | 0.9500 |
C7—H7 | 0.9500 | C22—H22 | 0.9500 |
C8—C9 | 1.367 (2) | N23—C24 | 1.441 (2) |
C8—H8 | 0.9500 | N23—C25 | 1.445 (2) |
C9—N10 | 1.3576 (19) | C24—H24A | 0.9800 |
C9—H9 | 0.9500 | C24—H24B | 0.9800 |
C13—C14 | 1.338 (2) | C24—H24C | 0.9800 |
C13—H13 | 0.9500 | C25—H25A | 0.9800 |
C14—C15 | 1.438 (2) | C25—H25B | 0.9800 |
C14—H14 | 0.9500 | C25—H25C | 0.9800 |
C15—C16 | 1.342 (2) | | |
| | | |
F12—B1—F11 | 109.81 (12) | C14—C15—H15 | 118.3 |
F12—B1—O2 | 110.14 (12) | C15—C16—C17 | 127.54 (14) |
F11—B1—O2 | 110.23 (13) | C15—C16—H16 | 116.2 |
F12—B1—N10 | 109.14 (13) | C17—C16—H16 | 116.2 |
F11—B1—N10 | 108.69 (11) | C22—C17—C18 | 116.60 (13) |
O2—B1—N10 | 108.80 (11) | C22—C17—C16 | 119.24 (13) |
C3—O2—B1 | 123.43 (11) | C18—C17—C16 | 124.15 (13) |
N4—C3—O2 | 125.81 (14) | C19—C18—C17 | 121.85 (14) |
N4—C3—C13 | 117.66 (13) | C19—C18—H18 | 119.1 |
O2—C3—C13 | 116.53 (12) | C17—C18—H18 | 119.1 |
C3—N4—C5 | 119.15 (12) | C18—C19—C20 | 121.18 (13) |
N10—C5—N4 | 121.75 (12) | C18—C19—H19 | 119.4 |
N10—C5—C6 | 119.27 (14) | C20—C19—H19 | 119.4 |
N4—C5—C6 | 118.98 (13) | N23—C20—C21 | 121.55 (14) |
C7—C6—C5 | 120.23 (14) | N23—C20—C19 | 121.17 (14) |
C7—C6—H6 | 119.9 | C21—C20—C19 | 117.28 (14) |
C5—C6—H6 | 119.9 | C22—C21—C20 | 120.50 (14) |
C6—C7—C8 | 119.66 (14) | C22—C21—H21 | 119.8 |
C6—C7—H7 | 120.2 | C20—C21—H21 | 119.8 |
C8—C7—H7 | 120.2 | C21—C22—C17 | 122.59 (14) |
C9—C8—C7 | 118.56 (15) | C21—C22—H22 | 118.7 |
C9—C8—H8 | 120.7 | C17—C22—H22 | 118.7 |
C7—C8—H8 | 120.7 | C20—N23—C24 | 120.56 (15) |
N10—C9—C8 | 122.01 (14) | C20—N23—C25 | 120.30 (14) |
N10—C9—H9 | 119.0 | C24—N23—C25 | 119.10 (14) |
C8—C9—H9 | 119.0 | N23—C24—H24A | 109.5 |
C9—N10—C5 | 120.25 (12) | N23—C24—H24B | 109.5 |
C9—N10—B1 | 118.74 (12) | H24A—C24—H24B | 109.5 |
C5—N10—B1 | 121.01 (12) | N23—C24—H24C | 109.5 |
C14—C13—C3 | 125.21 (14) | H24A—C24—H24C | 109.5 |
C14—C13—H13 | 117.4 | H24B—C24—H24C | 109.5 |
C3—C13—H13 | 117.4 | N23—C25—H25A | 109.5 |
C13—C14—C15 | 123.77 (14) | N23—C25—H25B | 109.5 |
C13—C14—H14 | 118.1 | H25A—C25—H25B | 109.5 |
C15—C14—H14 | 118.1 | N23—C25—H25C | 109.5 |
C16—C15—C14 | 123.46 (14) | H25A—C25—H25C | 109.5 |
C16—C15—H15 | 118.3 | H25B—C25—H25C | 109.5 |
| | | |
F12—B1—O2—C3 | −117.06 (14) | F11—B1—N10—C5 | −122.52 (14) |
F11—B1—O2—C3 | 121.62 (13) | O2—B1—N10—C5 | −2.47 (18) |
N10—B1—O2—C3 | 2.52 (18) | N4—C3—C13—C14 | 175.79 (13) |
B1—O2—C3—N4 | −1.3 (2) | O2—C3—C13—C14 | −4.1 (2) |
B1—O2—C3—C13 | 178.54 (12) | C3—C13—C14—C15 | −179.99 (12) |
O2—C3—N4—C5 | −0.4 (2) | C13—C14—C15—C16 | 176.36 (13) |
C13—C3—N4—C5 | 179.76 (11) | C14—C15—C16—C17 | 179.24 (12) |
C3—N4—C5—N10 | 0.4 (2) | C15—C16—C17—C22 | −176.11 (13) |
C3—N4—C5—C6 | −179.82 (12) | C15—C16—C17—C18 | 3.4 (2) |
N10—C5—C6—C7 | −1.5 (2) | C22—C17—C18—C19 | −0.2 (2) |
N4—C5—C6—C7 | 178.66 (12) | C16—C17—C18—C19 | −179.71 (13) |
C5—C6—C7—C8 | 0.9 (2) | C17—C18—C19—C20 | 0.4 (2) |
C6—C7—C8—C9 | 0.7 (2) | C18—C19—C20—N23 | 179.58 (15) |
C7—C8—C9—N10 | −1.8 (2) | C18—C19—C20—C21 | −0.3 (2) |
C8—C9—N10—C5 | 1.2 (2) | N23—C20—C21—C22 | −179.85 (15) |
C8—C9—N10—B1 | −179.69 (13) | C19—C20—C21—C22 | 0.1 (2) |
N4—C5—N10—C9 | −179.69 (12) | C20—C21—C22—C17 | 0.1 (2) |
C6—C5—N10—C9 | 0.5 (2) | C18—C17—C22—C21 | −0.1 (2) |
N4—C5—N10—B1 | 1.2 (2) | C16—C17—C22—C21 | 179.46 (12) |
C6—C5—N10—B1 | −178.60 (12) | C21—C20—N23—C24 | −176.59 (15) |
F12—B1—N10—C9 | −61.37 (16) | C19—C20—N23—C24 | 3.5 (3) |
F11—B1—N10—C9 | 58.37 (18) | C21—C20—N23—C25 | 1.2 (3) |
O2—B1—N10—C9 | 178.42 (11) | C19—C20—N23—C25 | −178.69 (15) |
F12—B1—N10—C5 | 117.74 (14) | | |
Hydrogen-bonding parameters (Å, °) for 1 and 2 topThe cut-offs for hydrogen bonding were based on IUPAC recommendations and the
book by Desiraju & Steiner (Arunan et al.,
2011a,b;
Desiraju & Steiner, 2006). |
Compound | D—H···A | H···A | D···A | D—H···A |
1 | C9—H9···F12i | 2.35 | 3.2209 (15) | 152 |
| C14—H14C···F12ii | 2.92 | 3.7863 (14) | 148 |
| C7—H7···F11iii | 2.58 | 3.4274 (13) | 148 |
| C7—H7···F11iv | 2.66 | 3.2127 (16) | 118 |
| C14—H14A···F11v | 2.80 | 3.5723 (16) | 136 |
| C14—H14B···F11vi | 2.70 | 3.2788 (15) | 119 |
| C14—H14A···O2v | 2.90 | 3.8768 (16) | 172 |
| C15—H15A···O2vii | 2.78 | 3.4155 (18) | 123 |
| C15—H15C···N4v | 2.74 | 3.6580 (17) | 156 |
| C7—H7···F12i | 2.47 | 3.3675 (19) | 157 |
| C15—H15···F12ii | 2.80 | 3.2863 (16) | 113 |
| C24—H24B···F12iii | 2.56 | 3.2175 (18) | 124 |
2 | C8—H8···F11iv | 2.89 | 3.3992 (17) | 115 |
| C9—H9···F11iv | 2.60 | 3.2676 (17) | 127 |
| C19—H19···F11v | 2.77 | 3.4066 (19) | 125 |
| C24—H24A···F11v | 2.82 | 3.7389 (19) | 156 |
| C25—H25B···F11vi | 2.85 | 3.3743 (19) | 114 |
| C7—H7···O2i | 2.99 | 3.7359 (19) | 137 |
| C25—H25C···O2vi | 2.94 | 3.697 (2) | 135 |
| C6—H6···N4vii | 2.73 | 3.5014 (19) | 139 |
Symmetry codes for 1:
(i) -x, -y+2, -z;
(ii) -x, -y+2, -z+1;
(iii) x, y+1, z;
(iv) -x+1, -y+2, -z;
(v) -x+1, -y+1, -z+1;
(vi) x, y, z+1;
(vii) -x, -y+1, -z+1.
Symmetry codes for 2:
(i) x+1, y, z;
(ii) -x, -y, -z;
(iii) x-1, y+1, z-1;
(iv) -x+1, -y, -z+1;
(v) -x, -y+1, -z;
(vi) -x-1, -y+1, -z;
(vii) -x+1, -y, -z. |
Geometricala, bond topologicalb and integratedc properties for the
NBF2O moiety and the amine group after isolated molecule geometry
optimizations of structures 1 and 2 top | dXRD | d | ρbcp | \Nabla2ρbcp | ε | G/ρbcp | H/ρbcp | δ |
1 | | | | | | | | |
N10—B1 | 1.5664 (13) | 1.585 | 0.99 | 3.3 | 0.02 | 1.16 | -0.93 | 0.27 |
O2—B1 | 1.4652 (13) | 1.478 | 1.05 | 10.9 | 0.02 | 1.56 | -0.84 | 0.27 |
F11—B1 | 1.3855 (12) | 1.382 | 1.20 | 19.6 | 0.01 | 1.92 | -0.78 | 0.31 |
F12—B1 | 1.3805 (12) | 1.374 | 1.23 | 20.4 | 0.01 | 1.94 | -0.78 | 0.31 |
O2—C3 | 1.3204 (11) | 1.312 | 2.26 | -19.5 | 0.08 | 1.00 | -1.61 | 0.94 |
N10—C5 | 1.3630 (12) | 1.365 | 2.18 | -24.5 | 0.15 | 0.54 | -1.33 | 1.14 |
N4—C3 | 1.3293 (12) | 1.324 | 2.45 | -28.2 | 0.18 | 0.48 | -1.29 | 1.23 |
N4—C5 | 1.3560 (13) | 1.347 | 2.30 | -25.6 | 0.13 | 0.46 | -1.24 | 1.21 |
N13—C3 | 1.3404 (13) | 1.348 | 2.29 | -27.0 | 0.28 | 0.51 | -1.33 | 1.09 |
| | | | | | | | |
2 | | | | | | | | |
N10—B1 | 1.5706 (19) | 1.593 | 0.96 | 3.4 | 0.02 | 1.16 | -0.92 | 0.27 |
O2—B1 | 1.4593 (19) | 1.469 | 1.09 | 11.1 | 0.02 | 1.56 | -0.85 | 0.28 |
F11—B1 | 1.3889 (17) | 1.377 | 1.22 | 20.1 | 0.01 | 1.93 | -0.78 | 0.31 |
F12—B1 | 1.3800 (19) | 1.382 | 1.20 | 19.6 | 0.00 | 1.92 | -0.78 | 0.31 |
O2—C3 | 1.3250 (17) | 1.315 | 2.21 | -16.6 | 0.03 | 1.07 | -1.60 | 0.98 |
N10—C5 | 1.3599 (19) | 1.362 | 2.19 | -24.7 | 0.15 | 0.55 | -1.34 | 1.14 |
N4—C3 | 1.3043 (19) | 1.317 | 2.46 | -29.6 | 0.18 | 0.54 | -1.38 | 1.30 |
N4—C5 | 1.3719 (19) | 1.355 | 2.28 | -24.9 | 0.11 | 0.44 | -1.21 | 1.20 |
N23—C20 | 1.373 (2) | 1.377 | 2.10 | -22.9 | 0.16 | 0.51 | -1.28 | 1.11 |
Notes: (a) bond length (d in Å);
(b) electron density (ρbcp in e Å-3),
Laplacian of the electron density (\Nabla2ρbcp in e Å-5), the bond
ellipticity (ε), and kinetic and total energy density over ρbcp ratios
(G/ρbcp and H/ρbcp in he-);
(c) δ is the delocalization index. |