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For five bromomethylated azobenzenes, namely (E)-[4-(bromomethyl)phenyl][4-(dibromomethyl)phenyl]diazene, C14H11Br3N2, (E)-1,2-bis[4-(dibromomethyl)phenyl]diazene, C14H10Br4N2, (E)-[3-(bromomethyl)phenyl][3-(dibromomethyl)phenyl]diazene, C14H11Br3N2, (E)-[3-(dibromomethyl)phenyl][3-(tribromomethyl)phenyl]diazene, C14H10Br4N2, and (E)-1,2-bis[3-(dibromomethyl)phenyl]diazene, C14H9Br5N2, the computationally cheap CLP PIXEL approach and CrystalExplorer were used for calculating lattice energies and performing Hirshfeld surface analysis via the enrichment ratios of atomic contacts. The procedures and caveats are discussed in detail. The findings from these tools are contrasted with the results of geometric analysis of the structures. We conclude that an energy-based discussion of the crystal packing provides substantially more insight than one based purely on geometry, as has so long been the custom in crystallography. In addition, we find a surprising shortage of halogen–halogen interactions in these highly bromomethylated compounds.
Supporting information
CCDC references: 1876016; 1876015; 1876014; 1876013; 1876012
For all structures, data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015) and shelXle(Hübschle et al., 2011); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015).
(
E)-[4-(Bromomethyl)phenyl][4-(dibromomethyl)phenyl]diazene (5)
top
Crystal data top
C14H11Br3N2 | Dx = 2.036 Mg m−3 |
Mr = 446.98 | Melting point: 146–148 C K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.538 (1) Å | Cell parameters from 6003 reflections |
b = 5.283 (1) Å | θ = 2.5–31.0° |
c = 32.801 (4) Å | µ = 8.29 mm−1 |
β = 99.692 (5)° | T = 100 K |
V = 1458.4 (4) Å3 | Plate, orange |
Z = 4 | 0.45 × 0.35 × 0.18 mm |
F(000) = 856 | |
Data collection top
Bruker SMART 1000 diffractometer | 4445 independent reflections |
Radiation source: fine-focus sealed tube | 3947 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ω scans | θmax = 31.4°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −12→12 |
Tmin = 0.316, Tmax = 0.746 | k = −7→7 |
13694 measured reflections | l = −47→46 |
Refinement top
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0221P)2 + 4.4145P] where P = (Fo2 + 2Fc2)/3 |
4445 reflections | (Δ/σ)max = 0.003 |
172 parameters | Δρmax = 1.41 e Å−3 |
0 restraints | Δρmin = −1.06 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.61597 (4) | 1.05498 (6) | 0.95232 (2) | 0.01420 (8) | |
Br2 | 0.92730 (4) | 0.72243 (7) | 0.95898 (2) | 0.01715 (9) | |
Br3 | 0.67770 (4) | 1.00291 (6) | 0.54184 (2) | 0.01277 (8) | |
N1 | 0.6931 (4) | 0.7036 (6) | 0.75752 (9) | 0.0146 (5) | |
N2 | 0.8014 (4) | 0.8208 (6) | 0.74401 (8) | 0.0142 (5) | |
C1 | 0.6963 (4) | 0.7378 (6) | 0.80072 (9) | 0.0123 (6) | |
C2 | 0.7807 (4) | 0.9300 (7) | 0.82415 (10) | 0.0137 (6) | |
H2 | 0.837587 | 1.052512 | 0.811275 | 0.016* | |
C3 | 0.7804 (4) | 0.9398 (6) | 0.86638 (10) | 0.0115 (6) | |
H3 | 0.836770 | 1.070822 | 0.882433 | 0.014* | |
C4 | 0.6985 (4) | 0.7599 (6) | 0.88542 (9) | 0.0106 (6) | |
C5 | 0.6105 (4) | 0.5728 (6) | 0.86189 (10) | 0.0126 (6) | |
H5 | 0.552169 | 0.452275 | 0.874761 | 0.015* | |
C6 | 0.6084 (4) | 0.5639 (7) | 0.81934 (10) | 0.0137 (6) | |
H6 | 0.547020 | 0.438890 | 0.803044 | 0.016* | |
C7 | 0.7088 (4) | 0.7544 (6) | 0.93152 (10) | 0.0109 (6) | |
H7 | 0.648722 | 0.603256 | 0.938825 | 0.013* | |
C11 | 0.8005 (4) | 0.7837 (6) | 0.70107 (10) | 0.0120 (6) | |
C12 | 0.7182 (4) | 0.5901 (7) | 0.67781 (10) | 0.0139 (6) | |
H12 | 0.658565 | 0.471034 | 0.690584 | 0.017* | |
C13 | 0.7239 (4) | 0.5723 (6) | 0.63590 (10) | 0.0129 (6) | |
H13 | 0.668797 | 0.439258 | 0.620078 | 0.015* | |
C14 | 0.8103 (4) | 0.7486 (6) | 0.61663 (10) | 0.0120 (6) | |
C15 | 0.8945 (4) | 0.9373 (7) | 0.64037 (10) | 0.0140 (6) | |
H15 | 0.955100 | 1.055490 | 0.627698 | 0.017* | |
C16 | 0.8909 (4) | 0.9551 (7) | 0.68238 (10) | 0.0140 (6) | |
H16 | 0.949921 | 1.083574 | 0.698432 | 0.017* | |
C17 | 0.8106 (4) | 0.7318 (6) | 0.57118 (10) | 0.0139 (6) | |
H17A | 0.768991 | 0.564811 | 0.560795 | 0.017* | |
H17B | 0.920742 | 0.747939 | 0.565756 | 0.017* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.01541 (16) | 0.01421 (16) | 0.01425 (15) | 0.00470 (12) | 0.00615 (11) | −0.00083 (11) |
Br2 | 0.00833 (15) | 0.0289 (2) | 0.01414 (15) | 0.00497 (13) | 0.00154 (11) | 0.00409 (12) |
Br3 | 0.00854 (15) | 0.01608 (16) | 0.01370 (14) | −0.00059 (12) | 0.00187 (11) | 0.00244 (11) |
N1 | 0.0130 (13) | 0.0186 (14) | 0.0126 (12) | −0.0007 (11) | 0.0031 (10) | 0.0008 (10) |
N2 | 0.0145 (13) | 0.0177 (14) | 0.0111 (12) | −0.0002 (11) | 0.0037 (10) | 0.0001 (10) |
C1 | 0.0090 (14) | 0.0173 (16) | 0.0108 (13) | 0.0018 (12) | 0.0022 (11) | 0.0003 (11) |
C2 | 0.0130 (15) | 0.0151 (15) | 0.0136 (14) | −0.0015 (12) | 0.0045 (12) | 0.0018 (11) |
C3 | 0.0078 (14) | 0.0121 (14) | 0.0151 (14) | −0.0030 (11) | 0.0037 (11) | −0.0005 (11) |
C4 | 0.0076 (13) | 0.0130 (14) | 0.0119 (13) | 0.0028 (11) | 0.0039 (11) | 0.0013 (11) |
C5 | 0.0078 (14) | 0.0143 (15) | 0.0164 (14) | −0.0031 (12) | 0.0038 (11) | 0.0008 (11) |
C6 | 0.0104 (15) | 0.0167 (16) | 0.0142 (14) | −0.0023 (12) | 0.0026 (11) | −0.0008 (12) |
C7 | 0.0075 (13) | 0.0116 (14) | 0.0147 (14) | 0.0013 (11) | 0.0047 (11) | −0.0010 (11) |
C11 | 0.0083 (14) | 0.0157 (15) | 0.0121 (13) | 0.0019 (12) | 0.0015 (11) | 0.0015 (11) |
C12 | 0.0126 (15) | 0.0154 (15) | 0.0138 (14) | −0.0005 (12) | 0.0027 (11) | 0.0019 (11) |
C13 | 0.0100 (14) | 0.0141 (15) | 0.0144 (14) | −0.0011 (12) | 0.0019 (11) | −0.0006 (11) |
C14 | 0.0104 (14) | 0.0134 (15) | 0.0126 (13) | 0.0028 (12) | 0.0031 (11) | −0.0003 (11) |
C15 | 0.0104 (15) | 0.0176 (16) | 0.0148 (14) | −0.0024 (12) | 0.0049 (11) | 0.0005 (12) |
C16 | 0.0100 (15) | 0.0181 (16) | 0.0139 (14) | −0.0021 (12) | 0.0023 (11) | −0.0030 (12) |
C17 | 0.0147 (15) | 0.0141 (15) | 0.0135 (14) | 0.0023 (12) | 0.0044 (12) | 0.0003 (11) |
Geometric parameters (Å, º) top
Br1—C7 | 1.948 (3) | C6—H6 | 0.9500 |
Br2—C7 | 1.938 (3) | C7—H7 | 1.0000 |
Br3—C17 | 1.974 (3) | C11—C12 | 1.393 (5) |
N1—N2 | 1.254 (4) | C11—C16 | 1.397 (5) |
N1—C1 | 1.424 (4) | C12—C13 | 1.387 (4) |
N2—C11 | 1.421 (4) | C12—H12 | 0.9500 |
C1—C6 | 1.391 (5) | C13—C14 | 1.403 (5) |
C1—C2 | 1.398 (5) | C13—H13 | 0.9500 |
C2—C3 | 1.386 (4) | C14—C15 | 1.389 (5) |
C2—H2 | 0.9500 | C14—C17 | 1.494 (4) |
C3—C4 | 1.389 (4) | C15—C16 | 1.387 (4) |
C3—H3 | 0.9500 | C15—H15 | 0.9500 |
C4—C5 | 1.394 (5) | C16—H16 | 0.9500 |
C4—C7 | 1.500 (4) | C17—H17A | 0.9900 |
C5—C6 | 1.394 (4) | C17—H17B | 0.9900 |
C5—H5 | 0.9500 | | |
| | | |
N2—N1—C1 | 113.4 (3) | Br1—C7—H7 | 108.2 |
N1—N2—C11 | 113.6 (3) | C12—C11—C16 | 120.0 (3) |
C6—C1—C2 | 120.3 (3) | C12—C11—N2 | 124.2 (3) |
C6—C1—N1 | 115.6 (3) | C16—C11—N2 | 115.7 (3) |
C2—C1—N1 | 124.1 (3) | C13—C12—C11 | 119.6 (3) |
C3—C2—C1 | 119.3 (3) | C13—C12—H12 | 120.2 |
C3—C2—H2 | 120.4 | C11—C12—H12 | 120.2 |
C1—C2—H2 | 120.4 | C12—C13—C14 | 120.7 (3) |
C2—C3—C4 | 120.6 (3) | C12—C13—H13 | 119.7 |
C2—C3—H3 | 119.7 | C14—C13—H13 | 119.7 |
C4—C3—H3 | 119.7 | C15—C14—C13 | 119.1 (3) |
C3—C4—C5 | 120.1 (3) | C15—C14—C17 | 120.9 (3) |
C3—C4—C7 | 121.2 (3) | C13—C14—C17 | 120.0 (3) |
C5—C4—C7 | 118.6 (3) | C16—C15—C14 | 120.6 (3) |
C6—C5—C4 | 119.6 (3) | C16—C15—H15 | 119.7 |
C6—C5—H5 | 120.2 | C14—C15—H15 | 119.7 |
C4—C5—H5 | 120.2 | C15—C16—C11 | 119.9 (3) |
C1—C6—C5 | 120.0 (3) | C15—C16—H16 | 120.0 |
C1—C6—H6 | 120.0 | C11—C16—H16 | 120.0 |
C5—C6—H6 | 120.0 | C14—C17—Br3 | 110.3 (2) |
C4—C7—Br2 | 111.0 (2) | C14—C17—H17A | 109.6 |
C4—C7—Br1 | 112.3 (2) | Br3—C17—H17A | 109.6 |
Br2—C7—Br1 | 108.96 (15) | C14—C17—H17B | 109.6 |
C4—C7—H7 | 108.2 | Br3—C17—H17B | 109.6 |
Br2—C7—H7 | 108.2 | H17A—C17—H17B | 108.1 |
| | | |
C1—N1—N2—C11 | 178.9 (3) | C5—C4—C7—Br1 | −117.6 (3) |
N2—N1—C1—C6 | −163.6 (3) | N1—N2—C11—C12 | −16.0 (5) |
N2—N1—C1—C2 | 16.2 (5) | N1—N2—C11—C16 | 164.7 (3) |
C6—C1—C2—C3 | 2.3 (5) | C16—C11—C12—C13 | −1.4 (5) |
N1—C1—C2—C3 | −177.5 (3) | N2—C11—C12—C13 | 179.4 (3) |
C1—C2—C3—C4 | 0.6 (5) | C11—C12—C13—C14 | −0.7 (5) |
C2—C3—C4—C5 | −2.5 (5) | C12—C13—C14—C15 | 2.0 (5) |
C2—C3—C4—C7 | 174.6 (3) | C12—C13—C14—C17 | −177.9 (3) |
C3—C4—C5—C6 | 1.6 (5) | C13—C14—C15—C16 | −1.3 (5) |
C7—C4—C5—C6 | −175.5 (3) | C17—C14—C15—C16 | 178.6 (3) |
C2—C1—C6—C5 | −3.2 (5) | C14—C15—C16—C11 | −0.8 (5) |
N1—C1—C6—C5 | 176.7 (3) | C12—C11—C16—C15 | 2.1 (5) |
C4—C5—C6—C1 | 1.2 (5) | N2—C11—C16—C15 | −178.6 (3) |
C3—C4—C7—Br2 | −57.0 (4) | C15—C14—C17—Br3 | −73.7 (4) |
C5—C4—C7—Br2 | 120.1 (3) | C13—C14—C17—Br3 | 106.1 (3) |
C3—C4—C7—Br1 | 65.3 (4) | | |
(
E)-1,2-Bis[4-(dibromomethyl)phenyl]diazene (6)
top
Crystal data top
C14H10Br4N2 | Dx = 2.220 Mg m−3 |
Mr = 525.88 | Melting point: 151-153 C K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.379 (3) Å | Cell parameters from 2626 reflections |
b = 8.6401 (10) Å | θ = 2.4–30.9° |
c = 9.8451 (10) Å | µ = 10.22 mm−1 |
β = 114.797 (2)° | T = 100 K |
V = 1573.7 (3) Å3 | Block, red |
Z = 4 | 0.51 × 0.48 × 0.38 mm |
F(000) = 992 | |
Data collection top
Bruker SMART 1000 diffractometer | 2322 independent reflections |
Radiation source: fine-focus sealed tube | 2049 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scans | θmax = 31.2°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −24→29 |
Tmin = 0.406, Tmax = 0.746 | k = −12→12 |
5663 measured reflections | l = −14→13 |
Refinement top
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)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.056 | w = 1/[σ2(Fo2) + (0.0249P)2 + 1.3279P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.002 |
2322 reflections | Δρmax = 0.82 e Å−3 |
92 parameters | Δρmin = −0.60 e Å−3 |
0 restraints | Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00183 (16) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.23156 (2) | 0.44833 (3) | 0.27413 (3) | 0.01427 (7) | |
Br2 | 0.36677 (2) | 0.26407 (2) | 0.50812 (3) | 0.01505 (8) | |
N1 | 0.48068 (10) | 0.9973 (2) | 0.5356 (2) | 0.0120 (4) | |
C1 | 0.44107 (11) | 0.8564 (2) | 0.5167 (2) | 0.0096 (4) | |
C2 | 0.44206 (13) | 0.7356 (2) | 0.4222 (3) | 0.0124 (4) | |
H2 | 0.470686 | 0.743489 | 0.367280 | 0.015* | |
C3 | 0.40098 (13) | 0.6056 (2) | 0.4103 (3) | 0.0124 (4) | |
H3 | 0.401720 | 0.522915 | 0.347309 | 0.015* | |
C4 | 0.35791 (12) | 0.5935 (2) | 0.4902 (2) | 0.0102 (4) | |
C5 | 0.35691 (12) | 0.7138 (2) | 0.5828 (3) | 0.0116 (4) | |
H5 | 0.327697 | 0.706657 | 0.636582 | 0.014* | |
C6 | 0.39902 (12) | 0.8452 (2) | 0.5966 (3) | 0.0119 (4) | |
H6 | 0.398937 | 0.927179 | 0.660821 | 0.014* | |
C7 | 0.31141 (13) | 0.4548 (2) | 0.4738 (3) | 0.0118 (4) | |
H7 | 0.290721 | 0.461829 | 0.549495 | 0.014* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.00683 (12) | 0.01807 (11) | 0.01567 (13) | −0.00205 (7) | 0.00252 (9) | −0.00163 (8) |
Br2 | 0.01663 (14) | 0.00894 (10) | 0.01627 (13) | −0.00040 (7) | 0.00363 (10) | 0.00142 (7) |
N1 | 0.0100 (10) | 0.0096 (7) | 0.0146 (10) | −0.0021 (6) | 0.0032 (8) | 0.0006 (6) |
C1 | 0.0058 (10) | 0.0094 (8) | 0.0104 (10) | −0.0015 (7) | 0.0004 (8) | 0.0003 (7) |
C2 | 0.0119 (11) | 0.0125 (9) | 0.0136 (11) | −0.0025 (8) | 0.0060 (9) | −0.0026 (8) |
C3 | 0.0133 (11) | 0.0110 (9) | 0.0138 (11) | −0.0019 (7) | 0.0065 (9) | −0.0031 (7) |
C4 | 0.0079 (10) | 0.0092 (8) | 0.0113 (10) | −0.0019 (7) | 0.0017 (8) | 0.0006 (7) |
C5 | 0.0103 (11) | 0.0122 (9) | 0.0129 (11) | −0.0010 (7) | 0.0055 (9) | 0.0007 (7) |
C6 | 0.0115 (11) | 0.0103 (8) | 0.0133 (11) | −0.0006 (7) | 0.0046 (9) | −0.0009 (7) |
C7 | 0.0111 (11) | 0.0104 (9) | 0.0144 (11) | −0.0023 (7) | 0.0057 (9) | −0.0021 (7) |
Geometric parameters (Å, º) top
Br1—C7 | 1.958 (2) | C3—C4 | 1.407 (3) |
Br2—C7 | 1.945 (2) | C3—H3 | 0.9500 |
N1—N1i | 1.255 (4) | C4—C5 | 1.388 (3) |
N1—C1 | 1.429 (3) | C4—C7 | 1.494 (3) |
C1—C6 | 1.389 (3) | C5—C6 | 1.395 (3) |
C1—C2 | 1.404 (3) | C5—H5 | 0.9500 |
C2—C3 | 1.376 (3) | C6—H6 | 0.9500 |
C2—H2 | 0.9500 | C7—H7 | 1.0000 |
| | | |
N1i—N1—C1 | 114.3 (2) | C4—C5—C6 | 119.7 (2) |
C6—C1—C2 | 120.49 (19) | C4—C5—H5 | 120.2 |
C6—C1—N1 | 115.77 (18) | C6—C5—H5 | 120.2 |
C2—C1—N1 | 123.7 (2) | C1—C6—C5 | 120.2 (2) |
C3—C2—C1 | 119.1 (2) | C1—C6—H6 | 119.9 |
C3—C2—H2 | 120.5 | C5—C6—H6 | 119.9 |
C1—C2—H2 | 120.5 | C4—C7—Br2 | 111.44 (16) |
C2—C3—C4 | 120.8 (2) | C4—C7—Br1 | 110.73 (15) |
C2—C3—H3 | 119.6 | Br2—C7—Br1 | 109.11 (10) |
C4—C3—H3 | 119.6 | C4—C7—H7 | 108.5 |
C5—C4—C3 | 119.76 (19) | Br2—C7—H7 | 108.5 |
C5—C4—C7 | 119.2 (2) | Br1—C7—H7 | 108.5 |
C3—C4—C7 | 120.99 (19) | | |
| | | |
N1i—N1—C1—C6 | 178.6 (2) | C7—C4—C5—C6 | −178.7 (2) |
N1i—N1—C1—C2 | −2.6 (4) | C2—C1—C6—C5 | −0.4 (3) |
C6—C1—C2—C3 | −0.2 (3) | N1—C1—C6—C5 | 178.4 (2) |
N1—C1—C2—C3 | −179.0 (2) | C4—C5—C6—C1 | 0.8 (3) |
C1—C2—C3—C4 | 0.6 (3) | C5—C4—C7—Br2 | −128.80 (19) |
C2—C3—C4—C5 | −0.3 (3) | C3—C4—C7—Br2 | 52.9 (3) |
C2—C3—C4—C7 | 178.0 (2) | C5—C4—C7—Br1 | 109.6 (2) |
C3—C4—C5—C6 | −0.4 (3) | C3—C4—C7—Br1 | −68.7 (2) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
(
E)-[3-(Bromomethyl)phenyl][3-(dibromomethyl)phenyl]diazene (7)
top
Crystal data top
C14H11Br3N2 | Dx = 2.006 Mg m−3 |
Mr = 446.98 | Melting point: 120-121 C K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1219 (12) Å | Cell parameters from 3951 reflections |
b = 16.904 (2) Å | θ = 2.4–30.6° |
c = 10.3633 (14) Å | µ = 8.16 mm−1 |
β = 112.122 (2)° | T = 100 K |
V = 1480.4 (3) Å3 | Plate, orange |
Z = 4 | 0.52 × 0.45 × 0.15 mm |
F(000) = 856 | |
Data collection top
Bruker SMART 1000 diffractometer | 4362 independent reflections |
Radiation source: fine-focus sealed tube | 3587 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 31.2°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −12→9 |
Tmin = 0.349, Tmax = 0.746 | k = −23→23 |
12573 measured reflections | l = −15→14 |
Refinement top
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0501P)2 + 3.0958P] where P = (Fo2 + 2Fc2)/3 |
4362 reflections | (Δ/σ)max = 0.001 |
172 parameters | Δρmax = 2.24 e Å−3 |
0 restraints | Δρmin = −1.56 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 1.09235 (4) | 0.54419 (2) | 0.34234 (3) | 0.01965 (10) | |
Br2 | 0.94505 (5) | 0.41237 (2) | 0.11026 (4) | 0.02092 (10) | |
Br3 | −0.00058 (5) | 0.24139 (2) | 0.40366 (4) | 0.02690 (11) | |
N1 | 0.4960 (4) | 0.43930 (17) | 0.3487 (3) | 0.0157 (6) | |
N2 | 0.5936 (3) | 0.39273 (16) | 0.4327 (3) | 0.0136 (5) | |
C1 | 0.5604 (4) | 0.48745 (18) | 0.2701 (3) | 0.0134 (6) | |
C2 | 0.7098 (4) | 0.47785 (19) | 0.2674 (3) | 0.0139 (6) | |
H2 | 0.779123 | 0.438302 | 0.322746 | 0.017* | |
C3 | 0.7572 (4) | 0.52686 (19) | 0.1825 (3) | 0.0138 (6) | |
C4 | 0.6551 (4) | 0.58540 (19) | 0.1023 (3) | 0.0166 (6) | |
H4 | 0.688248 | 0.618877 | 0.044799 | 0.020* | |
C5 | 0.5056 (4) | 0.5950 (2) | 0.1060 (3) | 0.0177 (7) | |
H5 | 0.437065 | 0.635233 | 0.052167 | 0.021* | |
C6 | 0.4570 (4) | 0.54534 (19) | 0.1888 (3) | 0.0157 (6) | |
H6 | 0.353993 | 0.550622 | 0.190390 | 0.019* | |
C7 | 0.9147 (4) | 0.51828 (19) | 0.1700 (3) | 0.0157 (6) | |
H7 | 0.917280 | 0.556187 | 0.096781 | 0.019* | |
C11 | 0.5242 (4) | 0.34393 (18) | 0.5071 (3) | 0.0133 (6) | |
C12 | 0.3667 (4) | 0.34994 (19) | 0.4934 (3) | 0.0144 (6) | |
H12 | 0.298856 | 0.387776 | 0.431683 | 0.017* | |
C13 | 0.3095 (4) | 0.3004 (2) | 0.5702 (3) | 0.0153 (6) | |
C14 | 0.4110 (4) | 0.2447 (2) | 0.6609 (3) | 0.0178 (7) | |
H14 | 0.371548 | 0.210409 | 0.712955 | 0.021* | |
C15 | 0.5673 (5) | 0.2392 (2) | 0.6753 (3) | 0.0184 (7) | |
H15 | 0.635204 | 0.201636 | 0.737713 | 0.022* | |
C16 | 0.6254 (4) | 0.2887 (2) | 0.5980 (3) | 0.0160 (6) | |
H16 | 0.732794 | 0.285066 | 0.607032 | 0.019* | |
C17 | 0.1423 (5) | 0.3077 (2) | 0.5578 (4) | 0.0226 (7) | |
H17A | 0.108921 | 0.363708 | 0.540690 | 0.027* | |
H17B | 0.133999 | 0.291236 | 0.646449 | 0.027* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.00936 (17) | 0.02557 (18) | 0.02167 (16) | −0.00070 (13) | 0.00316 (13) | −0.00445 (13) |
Br2 | 0.0205 (2) | 0.01986 (16) | 0.02431 (17) | 0.00050 (13) | 0.01055 (14) | −0.00337 (12) |
Br3 | 0.01277 (19) | 0.0289 (2) | 0.0310 (2) | −0.00430 (15) | −0.00094 (14) | 0.00581 (15) |
N1 | 0.0137 (15) | 0.0168 (12) | 0.0150 (12) | −0.0008 (11) | 0.0036 (11) | 0.0013 (10) |
N2 | 0.0107 (14) | 0.0148 (12) | 0.0141 (11) | 0.0004 (10) | 0.0034 (10) | 0.0010 (10) |
C1 | 0.0125 (16) | 0.0140 (13) | 0.0115 (12) | −0.0020 (12) | 0.0021 (11) | −0.0012 (11) |
C2 | 0.0109 (16) | 0.0150 (14) | 0.0125 (13) | −0.0004 (12) | 0.0006 (11) | 0.0002 (11) |
C3 | 0.0120 (16) | 0.0137 (13) | 0.0122 (12) | 0.0000 (12) | 0.0007 (11) | −0.0013 (11) |
C4 | 0.0169 (18) | 0.0144 (14) | 0.0154 (14) | −0.0015 (13) | 0.0025 (13) | 0.0029 (11) |
C5 | 0.0152 (17) | 0.0167 (14) | 0.0170 (14) | 0.0010 (13) | 0.0012 (12) | 0.0032 (12) |
C6 | 0.0105 (16) | 0.0165 (14) | 0.0172 (14) | −0.0001 (12) | 0.0020 (12) | −0.0003 (12) |
C7 | 0.0159 (17) | 0.0161 (14) | 0.0144 (13) | −0.0018 (13) | 0.0048 (12) | −0.0012 (11) |
C11 | 0.0131 (16) | 0.0131 (13) | 0.0122 (12) | −0.0024 (12) | 0.0029 (11) | −0.0015 (11) |
C12 | 0.0130 (16) | 0.0151 (14) | 0.0133 (13) | 0.0012 (12) | 0.0030 (12) | 0.0000 (11) |
C13 | 0.0128 (16) | 0.0176 (14) | 0.0148 (13) | −0.0018 (12) | 0.0044 (12) | −0.0050 (11) |
C14 | 0.0171 (18) | 0.0198 (15) | 0.0152 (14) | −0.0054 (14) | 0.0045 (13) | 0.0003 (12) |
C15 | 0.0173 (18) | 0.0161 (14) | 0.0163 (14) | −0.0006 (13) | 0.0001 (12) | 0.0032 (12) |
C16 | 0.0105 (16) | 0.0174 (14) | 0.0177 (14) | −0.0027 (13) | 0.0024 (12) | −0.0007 (12) |
C17 | 0.0166 (19) | 0.0266 (18) | 0.0269 (17) | −0.0027 (15) | 0.0108 (15) | −0.0020 (14) |
Geometric parameters (Å, º) top
Br1—C7 | 1.957 (3) | C6—H6 | 0.9500 |
Br2—C7 | 1.948 (3) | C7—H7 | 1.0000 |
Br3—C17 | 1.985 (4) | C11—C12 | 1.393 (5) |
N1—N2 | 1.260 (4) | C11—C16 | 1.398 (5) |
N1—C1 | 1.425 (4) | C12—C13 | 1.385 (5) |
N2—C11 | 1.430 (4) | C12—H12 | 0.9500 |
C1—C2 | 1.383 (5) | C13—C14 | 1.404 (5) |
C1—C6 | 1.400 (5) | C13—C17 | 1.487 (5) |
C2—C3 | 1.390 (4) | C14—C15 | 1.380 (6) |
C2—H2 | 0.9500 | C14—H14 | 0.9500 |
C3—C4 | 1.398 (4) | C15—C16 | 1.395 (5) |
C3—C7 | 1.497 (5) | C15—H15 | 0.9500 |
C4—C5 | 1.388 (5) | C16—H16 | 0.9500 |
C4—H4 | 0.9500 | C17—H17A | 0.9900 |
C5—C6 | 1.387 (5) | C17—H17B | 0.9900 |
C5—H5 | 0.9500 | | |
| | | |
N2—N1—C1 | 114.6 (3) | Br1—C7—H7 | 107.5 |
N1—N2—C11 | 113.1 (3) | C12—C11—C16 | 120.8 (3) |
C2—C1—C6 | 121.0 (3) | C12—C11—N2 | 123.5 (3) |
C2—C1—N1 | 124.5 (3) | C16—C11—N2 | 115.7 (3) |
C6—C1—N1 | 114.4 (3) | C13—C12—C11 | 119.6 (3) |
C1—C2—C3 | 119.1 (3) | C13—C12—H12 | 120.2 |
C1—C2—H2 | 120.4 | C11—C12—H12 | 120.2 |
C3—C2—H2 | 120.4 | C12—C13—C14 | 119.6 (3) |
C2—C3—C4 | 120.1 (3) | C12—C13—C17 | 119.7 (3) |
C2—C3—C7 | 122.3 (3) | C14—C13—C17 | 120.6 (3) |
C4—C3—C7 | 117.6 (3) | C15—C14—C13 | 120.8 (3) |
C5—C4—C3 | 120.5 (3) | C15—C14—H14 | 119.6 |
C5—C4—H4 | 119.7 | C13—C14—H14 | 119.6 |
C3—C4—H4 | 119.7 | C14—C15—C16 | 119.9 (3) |
C6—C5—C4 | 119.5 (3) | C14—C15—H15 | 120.1 |
C6—C5—H5 | 120.2 | C16—C15—H15 | 120.1 |
C4—C5—H5 | 120.2 | C15—C16—C11 | 119.4 (3) |
C5—C6—C1 | 119.7 (3) | C15—C16—H16 | 120.3 |
C5—C6—H6 | 120.2 | C11—C16—H16 | 120.3 |
C1—C6—H6 | 120.2 | C13—C17—Br3 | 111.4 (2) |
C3—C7—Br2 | 111.9 (2) | C13—C17—H17A | 109.4 |
C3—C7—Br1 | 113.0 (2) | Br3—C17—H17A | 109.4 |
Br2—C7—Br1 | 109.14 (17) | C13—C17—H17B | 109.4 |
C3—C7—H7 | 107.5 | Br3—C17—H17B | 109.4 |
Br2—C7—H7 | 107.5 | H17A—C17—H17B | 108.0 |
| | | |
C1—N1—N2—C11 | −178.5 (3) | C4—C3—C7—Br1 | 114.7 (3) |
N2—N1—C1—C2 | 9.4 (5) | N1—N2—C11—C12 | −3.0 (4) |
N2—N1—C1—C6 | −173.0 (3) | N1—N2—C11—C16 | 177.5 (3) |
C6—C1—C2—C3 | 0.2 (5) | C16—C11—C12—C13 | −0.3 (5) |
N1—C1—C2—C3 | 177.6 (3) | N2—C11—C12—C13 | −179.7 (3) |
C1—C2—C3—C4 | 0.6 (5) | C11—C12—C13—C14 | −0.1 (5) |
C1—C2—C3—C7 | −177.8 (3) | C11—C12—C13—C17 | 178.8 (3) |
C2—C3—C4—C5 | −0.3 (5) | C12—C13—C14—C15 | 0.5 (5) |
C7—C3—C4—C5 | 178.2 (3) | C17—C13—C14—C15 | −178.3 (3) |
C3—C4—C5—C6 | −0.8 (5) | C13—C14—C15—C16 | −0.7 (5) |
C4—C5—C6—C1 | 1.5 (5) | C14—C15—C16—C11 | 0.3 (5) |
C2—C1—C6—C5 | −1.2 (5) | C12—C11—C16—C15 | 0.2 (5) |
N1—C1—C6—C5 | −178.9 (3) | N2—C11—C16—C15 | 179.6 (3) |
C2—C3—C7—Br2 | 56.7 (4) | C12—C13—C17—Br3 | 88.1 (3) |
C4—C3—C7—Br2 | −121.7 (3) | C14—C13—C17—Br3 | −93.0 (3) |
C2—C3—C7—Br1 | −66.9 (4) | | |
(
E)-1,2-Bis[3-(dibromomethyl)phenyl]diazene (8)
top
Crystal data top
C14H10Br4N2 | F(000) = 248 |
Mr = 525.88 | Dx = 2.274 Mg m−3 |
Triclinic, P1 | Melting point: 130-132 C K |
a = 4.899 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.294 (2) Å | Cell parameters from 2578 reflections |
c = 9.942 (3) Å | θ = 2.5–31.2° |
α = 98.103 (4)° | µ = 10.47 mm−1 |
β = 103.640 (3)° | T = 100 K |
γ = 96.650 (3)° | Block, red |
V = 384.0 (2) Å3 | 0.45 × 0.25 × 0.20 mm |
Z = 1 | |
Data collection top
Bruker SMART 1000 diffractometer | 2249 independent reflections |
Radiation source: fine-focus sealed tube | 1993 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans | θmax = 31.2°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −6→7 |
Tmin = 0.308, Tmax = 0.746 | k = −11→11 |
5417 measured reflections | l = −14→14 |
Refinement top
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)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0356P)2 + 0.5445P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2249 reflections | Δρmax = 1.08 e Å−3 |
92 parameters | Δρmin = −1.11 e Å−3 |
0 restraints | Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.022 (2) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.70209 (6) | 0.44619 (3) | 0.34815 (3) | 0.01868 (11) | |
Br2 | 0.20145 (6) | 0.33924 (4) | 0.06638 (3) | 0.01621 (11) | |
N1 | 0.0313 (5) | −0.0658 (3) | 0.4728 (3) | 0.0132 (5) | |
C1 | 0.4352 (5) | 0.1125 (3) | 0.2374 (3) | 0.0112 (5) | |
C2 | 0.5243 (6) | −0.0295 (4) | 0.1812 (3) | 0.0120 (5) | |
H2 | 0.638710 | −0.023851 | 0.116479 | 0.014* | |
C3 | 0.4455 (6) | −0.1808 (4) | 0.2198 (3) | 0.0139 (5) | |
H3 | 0.505053 | −0.277981 | 0.181129 | 0.017* | |
C4 | 0.2802 (6) | −0.1874 (3) | 0.3148 (3) | 0.0134 (5) | |
H4 | 0.225421 | −0.289857 | 0.340843 | 0.016* | |
C5 | 0.1935 (5) | −0.0453 (3) | 0.3726 (3) | 0.0112 (5) | |
C6 | 0.2684 (6) | 0.1049 (3) | 0.3332 (3) | 0.0121 (5) | |
H6 | 0.206496 | 0.201498 | 0.371228 | 0.015* | |
C7 | 0.5238 (6) | 0.2695 (4) | 0.1914 (3) | 0.0128 (5) | |
H7 | 0.667019 | 0.248602 | 0.136699 | 0.015* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.02306 (17) | 0.00910 (16) | 0.01960 (17) | −0.00228 (11) | 0.00056 (11) | 0.00057 (11) |
Br2 | 0.01474 (16) | 0.01765 (18) | 0.01783 (17) | 0.00473 (11) | 0.00286 (10) | 0.00875 (11) |
N1 | 0.0128 (10) | 0.0114 (11) | 0.0144 (11) | 0.0008 (9) | 0.0016 (8) | 0.0026 (9) |
C1 | 0.0096 (11) | 0.0097 (12) | 0.0123 (12) | 0.0010 (9) | −0.0007 (8) | 0.0021 (9) |
C2 | 0.0128 (11) | 0.0116 (13) | 0.0098 (11) | 0.0021 (10) | 0.0000 (9) | 0.0009 (10) |
C3 | 0.0187 (13) | 0.0075 (12) | 0.0140 (12) | 0.0035 (10) | 0.0019 (10) | −0.0004 (10) |
C4 | 0.0165 (12) | 0.0070 (12) | 0.0146 (12) | 0.0006 (10) | 0.0010 (9) | 0.0011 (10) |
C5 | 0.0099 (11) | 0.0106 (13) | 0.0117 (11) | 0.0002 (9) | 0.0005 (8) | 0.0024 (9) |
C6 | 0.0126 (11) | 0.0093 (12) | 0.0136 (12) | 0.0019 (9) | 0.0016 (9) | 0.0024 (10) |
C7 | 0.0114 (11) | 0.0102 (12) | 0.0150 (12) | 0.0005 (9) | 0.0007 (9) | 0.0018 (10) |
Geometric parameters (Å, º) top
Br1—C7 | 1.938 (3) | C2—H2 | 0.9500 |
Br2—C7 | 1.965 (3) | C3—C4 | 1.384 (4) |
N1—N1i | 1.253 (5) | C3—H3 | 0.9500 |
N1—C5 | 1.429 (4) | C4—C5 | 1.393 (4) |
C1—C2 | 1.393 (4) | C4—H4 | 0.9500 |
C1—C6 | 1.397 (4) | C5—C6 | 1.393 (4) |
C1—C7 | 1.491 (4) | C6—H6 | 0.9500 |
C2—C3 | 1.402 (4) | C7—H7 | 1.0000 |
| | | |
N1i—N1—C5 | 113.9 (3) | C4—C5—C6 | 120.1 (3) |
C2—C1—C6 | 120.1 (3) | C4—C5—N1 | 115.8 (2) |
C2—C1—C7 | 117.7 (2) | C6—C5—N1 | 124.1 (3) |
C6—C1—C7 | 122.2 (2) | C5—C6—C1 | 119.6 (3) |
C1—C2—C3 | 120.1 (3) | C5—C6—H6 | 120.2 |
C1—C2—H2 | 119.9 | C1—C6—H6 | 120.2 |
C3—C2—H2 | 119.9 | C1—C7—Br1 | 112.63 (19) |
C4—C3—C2 | 119.4 (3) | C1—C7—Br2 | 111.38 (18) |
C4—C3—H3 | 120.3 | Br1—C7—Br2 | 109.85 (14) |
C2—C3—H3 | 120.3 | C1—C7—H7 | 107.6 |
C3—C4—C5 | 120.6 (3) | Br1—C7—H7 | 107.6 |
C3—C4—H4 | 119.7 | Br2—C7—H7 | 107.6 |
C5—C4—H4 | 119.7 | | |
| | | |
C6—C1—C2—C3 | 0.4 (4) | C4—C5—C6—C1 | −1.2 (4) |
C7—C1—C2—C3 | −179.5 (2) | N1—C5—C6—C1 | 178.0 (2) |
C1—C2—C3—C4 | −0.4 (4) | C2—C1—C6—C5 | 0.4 (4) |
C2—C3—C4—C5 | −0.4 (4) | C7—C1—C6—C5 | −179.7 (2) |
C3—C4—C5—C6 | 1.2 (4) | C2—C1—C7—Br1 | −128.1 (2) |
C3—C4—C5—N1 | −178.1 (3) | C6—C1—C7—Br1 | 52.1 (3) |
N1i—N1—C5—C4 | 176.8 (3) | C2—C1—C7—Br2 | 108.0 (2) |
N1i—N1—C5—C6 | −2.4 (4) | C6—C1—C7—Br2 | −71.9 (3) |
Symmetry code: (i) −x, −y, −z+1. |
(
E)-[3-(Dibromomethyl)phenyl][3-(tribromomethyl)phenyl]diazene (9)
top
Crystal data top
C14H9Br5N2 | F(000) = 564 |
Mr = 604.78 | Dx = 2.375 Mg m−3 |
Triclinic, P1 | Melting point: 142-143 C K |
a = 7.0161 (11) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.5634 (13) Å | Cell parameters from 1139 reflections |
c = 14.897 (2) Å | θ = 2.5–31.1° |
α = 103.257 (2)° | µ = 11.87 mm−1 |
β = 102.974 (2)° | T = 100 K |
γ = 91.703 (2)° | Block, orange |
V = 845.8 (2) Å3 | 0.45 × 0.43 × 0.21 mm |
Z = 2 | |
Data collection top
Bruker SMART 1000 diffractometer | 6827 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.066 |
ω scans | θmax = 31.3°, θmin = 1.5° |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2012) | h = −10→9 |
Tmin = 0.014, Tmax = 0.052 | k = −12→12 |
15148 measured reflections | l = 0→21 |
8987 independent reflections | |
Refinement top
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0797P)2] where P = (Fo2 + 2Fc2)/3 |
8987 reflections | (Δ/σ)max = 0.001 |
213 parameters | Δρmax = 1.81 e Å−3 |
58 restraints | Δρmin = −1.56 e Å−3 |
Special details top
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. Refined as a 2-component twin. The structure was solved using direct methods
with only the non-overlapping reflections of component 1. The structure was
refined using the hklf 5 routine with all reflections of both components
(including the overlapping ones), resulting in a BASF value of 0.481 (1). Minor but clearly resolved disorder was observed for the dibromomethyl group.
The major and minor moieties were restrained to have similar geometries (SAME
restraint of SHELXL, e.s.d. 0.02 Angstrom). The carbon atom C10 was
included in the disorder modeling and 1,2 and 1,3 C—C distances involving
the major and minor components of C10 were restrained to be similar (SADI
restraint of SHELXL, e.s.d. 0.02 Angstrom). Uij components of
ADPs for disordered atoms closer to each other than 2.0 Angstrom were
restrained to be similar. Subject to these conditions the occupancy ratio
refined to 0.9601 (19) to 0.0399 (19). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Br1 | 0.90836 (8) | 1.08792 (7) | 0.36771 (5) | 0.02429 (15) | |
Br2 | 0.46223 (8) | 1.07967 (7) | 0.37101 (5) | 0.02458 (15) | |
N1 | 0.7664 (6) | 0.6292 (6) | 0.5351 (3) | 0.0191 (9) | |
N2 | 0.7756 (6) | 0.4901 (6) | 0.5496 (3) | 0.0206 (9) | |
C1 | 0.7187 (7) | 0.6301 (7) | 0.4368 (4) | 0.0181 (10) | |
C3 | 0.6536 (7) | 0.9644 (6) | 0.3090 (4) | 0.0177 (10) | |
C4 | 0.6279 (8) | 0.6584 (7) | 0.2506 (4) | 0.0203 (10) | |
H4 | 0.595699 | 0.667201 | 0.186613 | 0.024* | |
C5 | 0.7064 (7) | 0.7811 (7) | 0.4171 (4) | 0.0179 (10) | |
H5 | 0.729007 | 0.874865 | 0.467909 | 0.021* | |
C6 | 0.6409 (8) | 0.5070 (7) | 0.2697 (4) | 0.0238 (11) | |
H6 | 0.619070 | 0.413565 | 0.218693 | 0.029* | |
C7 | 0.8868 (8) | 0.3130 (8) | 0.7556 (4) | 0.0258 (12) | |
H7 | 0.901178 | 0.208546 | 0.766690 | 0.031* | |
C8 | 0.9118 (8) | 0.4452 (7) | 0.8309 (4) | 0.0251 (12) | |
H8 | 0.944967 | 0.431907 | 0.893937 | 0.030* | |
C9 | 0.6853 (8) | 0.4911 (7) | 0.3621 (4) | 0.0212 (10) | |
H9 | 0.693124 | 0.387486 | 0.374978 | 0.025* | |
C11 | 0.8212 (7) | 0.4838 (7) | 0.6464 (4) | 0.0191 (10) | |
C12 | 0.8889 (8) | 0.5986 (7) | 0.8152 (4) | 0.0228 (11) | |
C14 | 0.8450 (7) | 0.6200 (7) | 0.7228 (4) | 0.0205 (10) | |
H14 | 0.831452 | 0.724552 | 0.711806 | 0.025* | |
C15 | 0.8403 (8) | 0.3321 (7) | 0.6629 (4) | 0.0217 (11) | |
H15 | 0.821753 | 0.240510 | 0.610947 | 0.026* | |
C16 | 0.6612 (7) | 0.7963 (7) | 0.3236 (4) | 0.0186 (10) | |
Br3 | 0.58568 (11) | 0.97768 (9) | 0.17782 (4) | 0.03647 (18) | |
C10 | 0.9060 (9) | 0.7456 (8) | 0.8944 (4) | 0.0281 (13) | 0.9601 (19) |
H10 | 0.878219 | 0.840293 | 0.866313 | 0.034* | 0.9601 (19) |
Br4 | 0.71615 (10) | 0.72607 (10) | 0.97006 (5) | 0.0349 (2) | 0.9601 (19) |
Br5 | 1.16852 (11) | 0.78735 (12) | 0.98005 (6) | 0.0371 (2) | 0.9601 (19) |
C10B | 0.942 (6) | 0.735 (2) | 0.9006 (16) | 0.034 (7) | 0.0399 (19) |
H10B | 0.851659 | 0.724703 | 0.942383 | 0.041* | 0.0399 (19) |
Br4B | 0.910 (3) | 0.930 (2) | 0.8670 (14) | 0.049 (5) | 0.0399 (19) |
Br5B | 1.209 (3) | 0.711 (3) | 0.9683 (15) | 0.0371 (2) | 0.0399 (19) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0214 (3) | 0.0195 (3) | 0.0315 (3) | 0.00001 (18) | 0.0047 (2) | 0.0070 (2) |
Br2 | 0.0248 (3) | 0.0212 (3) | 0.0314 (3) | 0.0066 (2) | 0.0109 (2) | 0.0091 (2) |
N1 | 0.020 (2) | 0.020 (2) | 0.017 (2) | 0.0008 (16) | 0.0021 (16) | 0.0049 (18) |
N2 | 0.024 (2) | 0.020 (2) | 0.019 (2) | 0.0013 (17) | 0.0053 (17) | 0.0067 (19) |
C1 | 0.018 (2) | 0.017 (3) | 0.018 (2) | −0.0003 (17) | 0.0016 (18) | 0.004 (2) |
C3 | 0.025 (2) | 0.017 (3) | 0.009 (2) | 0.0005 (18) | 0.0024 (18) | −0.0006 (19) |
C4 | 0.024 (2) | 0.021 (3) | 0.014 (2) | 0.0005 (19) | 0.0027 (19) | 0.000 (2) |
C5 | 0.023 (2) | 0.016 (3) | 0.012 (2) | 0.0020 (18) | 0.0036 (18) | −0.0009 (19) |
C6 | 0.025 (3) | 0.021 (3) | 0.021 (3) | 0.000 (2) | 0.002 (2) | −0.001 (2) |
C7 | 0.028 (3) | 0.024 (3) | 0.031 (3) | 0.005 (2) | 0.009 (2) | 0.015 (2) |
C8 | 0.027 (3) | 0.025 (3) | 0.026 (3) | 0.004 (2) | 0.005 (2) | 0.012 (2) |
C9 | 0.024 (2) | 0.014 (3) | 0.023 (3) | −0.0007 (19) | 0.004 (2) | 0.003 (2) |
C11 | 0.019 (2) | 0.021 (3) | 0.018 (3) | 0.0020 (18) | 0.0026 (19) | 0.007 (2) |
C12 | 0.023 (3) | 0.025 (3) | 0.021 (3) | 0.001 (2) | 0.005 (2) | 0.007 (2) |
C14 | 0.022 (2) | 0.018 (3) | 0.023 (3) | 0.0022 (19) | 0.005 (2) | 0.008 (2) |
C15 | 0.025 (2) | 0.017 (3) | 0.025 (3) | 0.0035 (19) | 0.006 (2) | 0.006 (2) |
C16 | 0.019 (2) | 0.021 (3) | 0.017 (3) | 0.0016 (18) | 0.0063 (19) | 0.006 (2) |
Br3 | 0.0642 (4) | 0.0289 (4) | 0.0136 (3) | 0.0024 (3) | 0.0029 (3) | 0.0060 (2) |
C10 | 0.035 (3) | 0.030 (3) | 0.017 (3) | 0.001 (2) | 0.000 (2) | 0.007 (3) |
Br4 | 0.0415 (4) | 0.0424 (4) | 0.0201 (3) | 0.0067 (3) | 0.0107 (3) | 0.0022 (3) |
Br5 | 0.0384 (4) | 0.0395 (5) | 0.0274 (4) | −0.0099 (3) | −0.0045 (3) | 0.0095 (3) |
C10B | 0.040 (11) | 0.035 (11) | 0.022 (10) | −0.002 (10) | −0.001 (10) | 0.007 (10) |
Br4B | 0.063 (10) | 0.045 (10) | 0.027 (9) | 0.009 (8) | −0.004 (7) | 0.000 (8) |
Br5B | 0.0384 (4) | 0.0395 (5) | 0.0274 (4) | −0.0099 (3) | −0.0045 (3) | 0.0095 (3) |
Geometric parameters (Å, º) top
Br1—C3 | 1.960 (5) | C7—H7 | 0.9500 |
Br2—C3 | 1.962 (5) | C8—C12 | 1.394 (8) |
N1—N2 | 1.259 (7) | C8—H8 | 0.9500 |
N1—C1 | 1.428 (7) | C9—H9 | 0.9500 |
N2—C11 | 1.420 (7) | C11—C15 | 1.381 (8) |
C1—C5 | 1.391 (8) | C11—C14 | 1.407 (8) |
C1—C9 | 1.403 (8) | C12—C14 | 1.398 (8) |
C3—C16 | 1.505 (8) | C12—C10B | 1.484 (19) |
C3—Br3 | 1.935 (5) | C12—C10 | 1.495 (9) |
C4—C16 | 1.383 (7) | C14—H14 | 0.9500 |
C4—C6 | 1.392 (8) | C15—H15 | 0.9500 |
C4—H4 | 0.9500 | C10—Br4 | 1.954 (7) |
C5—C16 | 1.394 (7) | C10—Br5 | 1.960 (6) |
C5—H5 | 0.9500 | C10—H10 | 1.0000 |
C6—C9 | 1.381 (8) | C10B—Br4B | 1.86 (2) |
C6—H6 | 0.9500 | C10B—Br5B | 1.95 (3) |
C7—C8 | 1.374 (9) | C10B—H10B | 1.0000 |
C7—C15 | 1.394 (8) | | |
| | | |
N2—N1—C1 | 113.7 (5) | C15—C11—C14 | 120.3 (5) |
N1—N2—C11 | 115.5 (5) | C15—C11—N2 | 115.8 (5) |
C5—C1—C9 | 119.9 (5) | C14—C11—N2 | 123.9 (5) |
C5—C1—N1 | 115.8 (5) | C8—C12—C14 | 120.3 (6) |
C9—C1—N1 | 124.2 (5) | C8—C12—C10B | 116.3 (10) |
C16—C3—Br3 | 115.2 (4) | C14—C12—C10B | 122.8 (11) |
C16—C3—Br1 | 110.3 (3) | C8—C12—C10 | 122.6 (6) |
Br3—C3—Br1 | 106.9 (3) | C14—C12—C10 | 117.1 (6) |
C16—C3—Br2 | 110.6 (3) | C12—C14—C11 | 118.7 (5) |
Br3—C3—Br2 | 107.0 (2) | C12—C14—H14 | 120.7 |
Br1—C3—Br2 | 106.4 (2) | C11—C14—H14 | 120.7 |
C16—C4—C6 | 120.8 (5) | C11—C15—C7 | 120.3 (6) |
C16—C4—H4 | 119.6 | C11—C15—H15 | 119.9 |
C6—C4—H4 | 119.6 | C7—C15—H15 | 119.9 |
C1—C5—C16 | 120.7 (5) | C4—C16—C5 | 118.8 (5) |
C1—C5—H5 | 119.6 | C4—C16—C3 | 124.0 (5) |
C16—C5—H5 | 119.6 | C5—C16—C3 | 117.1 (5) |
C9—C6—C4 | 120.7 (5) | C12—C10—Br4 | 111.1 (4) |
C9—C6—H6 | 119.7 | C12—C10—Br5 | 112.4 (4) |
C4—C6—H6 | 119.7 | Br4—C10—Br5 | 107.9 (3) |
C8—C7—C15 | 119.9 (6) | C12—C10—H10 | 108.4 |
C8—C7—H7 | 120.0 | Br4—C10—H10 | 108.4 |
C15—C7—H7 | 120.0 | Br5—C10—H10 | 108.4 |
C7—C8—C12 | 120.4 (6) | C12—C10B—Br4B | 110.8 (14) |
C7—C8—H8 | 119.8 | C12—C10B—Br5B | 107.0 (18) |
C12—C8—H8 | 119.8 | Br4B—C10B—Br5B | 115 (2) |
C6—C9—C1 | 119.1 (5) | C12—C10B—H10B | 108.1 |
C6—C9—H9 | 120.5 | Br4B—C10B—H10B | 108.1 |
C1—C9—H9 | 120.5 | Br5B—C10B—H10B | 108.1 |
| | | |
C1—N1—N2—C11 | −179.5 (4) | N2—C11—C15—C7 | 179.4 (5) |
N2—N1—C1—C5 | 179.9 (4) | C8—C7—C15—C11 | 0.6 (8) |
N2—N1—C1—C9 | −0.3 (7) | C6—C4—C16—C5 | −0.6 (8) |
C9—C1—C5—C16 | 0.0 (8) | C6—C4—C16—C3 | 178.8 (5) |
N1—C1—C5—C16 | 179.8 (4) | C1—C5—C16—C4 | 0.3 (8) |
C16—C4—C6—C9 | 0.7 (8) | C1—C5—C16—C3 | −179.2 (4) |
C15—C7—C8—C12 | 0.7 (8) | Br3—C3—C16—C4 | 1.6 (7) |
C4—C6—C9—C1 | −0.5 (8) | Br1—C3—C16—C4 | −119.5 (5) |
C5—C1—C9—C6 | 0.1 (8) | Br2—C3—C16—C4 | 123.0 (5) |
N1—C1—C9—C6 | −179.7 (5) | Br3—C3—C16—C5 | −179.0 (4) |
N1—N2—C11—C15 | −177.1 (5) | Br1—C3—C16—C5 | 59.9 (5) |
N1—N2—C11—C14 | 3.4 (7) | Br2—C3—C16—C5 | −57.5 (5) |
C7—C8—C12—C14 | −1.6 (8) | C8—C12—C10—Br4 | −58.4 (7) |
C7—C8—C12—C10B | −173 (2) | C14—C12—C10—Br4 | 120.5 (5) |
C7—C8—C12—C10 | 177.3 (5) | C8—C12—C10—Br5 | 62.7 (7) |
C8—C12—C14—C11 | 1.1 (8) | C14—C12—C10—Br5 | −118.4 (5) |
C10B—C12—C14—C11 | 172 (2) | C8—C12—C10B—Br4B | 178.3 (15) |
C10—C12—C14—C11 | −177.9 (5) | C14—C12—C10B—Br4B | 7 (3) |
C15—C11—C14—C12 | 0.3 (8) | C8—C12—C10B—Br5B | 53 (3) |
N2—C11—C14—C12 | 179.7 (5) | C14—C12—C10B—Br5B | −118.3 (12) |
C14—C11—C15—C7 | −1.1 (8) | | |
Lattice energies (kJ mol-1) resulting from the various calculations for
compounds 5–9 top | 5 | 6 | 7 | 8 | 9 |
Mercury-UNI | -135.9 | -157.7 | -147.0 | -165.4 | -165.4 |
AA-CLP2015 (UNI) | -133.3 | -142.1 | -136.2 | -151.1 | -138.9 |
CLP/PIXEL/B3LYP | -116.7 | -123.3 | -117.7 | -130.2 | -111.4 |
CLP/PIXEL/MP2 | -113.3 | -120.1 | -114.1 | -127.3 | -107.2 |
CE-B3LYP | -146.7 | -145.4 | -139.7 | -151.8 | -142.1 |
Melting point (°C) | 146–148 | 151–153 | 120–121 | 142–143 | 130–132 |
Contact enrichment ratios in crystals of compound 5 topdi de | Br | H | C | N |
Br | 1.51 | 0.86 | 0 | 0 |
H | 1.35 | 0.68 | 1.99 | 1.90 |
C | 0 | 1.60 | 0 | 0 |
N | 0 | 1.59 | 0.15 | 0.48 |
Contact enrichment ratios in crystals of compound 6 topdi de | Br | H | C | N |
Br | 0.48 | 0.97 | 1.24 | 1.43 |
H | 1.55 | 0.82 | 0.73 | 1.10 |
C | 1.13 | 1.27 | 0.93 | 0 |
N | 1.23 | 1.22 | 0 | 0 |
Contact enrichment ratios in crystals of compound 7 topdi de | Br | H | C | N |
Br | 0.49 | 1.13 | 0 | 0.97 |
H | 1.87 | 0.73 | 1.21 | 1.07 |
C | 0.03 | 1.07 | 2.48 | 0.14 |
N | 1.05 | 0.88 | 0.14 | 3.91 |
Contact enrichment ratios in crystals of compound 8 topdi de | Br | H | C | N |
Br | 0.41 | 1.27 | 0.33 | 0.33 |
H | 2.03 | 0.68 | 0.95 | 0.23 |
C | 0.39 | 0.70 | 1.60 | 5.69 |
N | 0.33 | 0.18 | 5.69 | 0 |
Separate terms [correction factors for 6-31(d,p) basis set already included for
CE-B3LYP for comparability between the methods] in the total lattice energies
according to CLP/PIXEL/MP2 and CE/B3LYP (kJ mol-1) top | CE-B3LYP | | | | |
| ele | pol | disp | rep | tot |
5 | -90.9 | -8.7 | -169.5 | 122.4 | -146.7 |
6 | -87.7 | -6.0 | -180.6 | 128.9 | -145.4 |
7 | -80.0 | -4.4 | -165.5 | 110.2 | -139.7 |
8 | -79.5 | -7.6 | -191.3 | 126.6 | -151.8 |
9 | -82.8 | -3.2 | -186.5 | 130.4 | -142.1 |
| CLP PIXEL MP2 | | | | |
5 | -92.3 | -29.8 | -198.6 | 207.4 | -113.3 |
6 | -86.8 | -28 | -209 | 200.5 | -123.3 |
7 | -79.7 | -26.9 | -187.8 | 180.4 | -114.1 |
8 | -81.2 | -28.3 | -216.5 | 198.6 | -127.3 |
9 | -84.2 | -27 | -213.5 | 217.4 | -107.2 |
Contact enrichment ratios in crystals of compound 9 topdi de | Br | H | C | N |
Br | 0.75 | 1.24 | 0.02 | 0.91 |
H | 1.87 | 0.62 | 0.80 | 0.40 |
C | 0.02 | 0.79 | 4.27 | 1.37 |
N | 1.02 | 0.35 | 1.37 | 5.76 |
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