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1,3-Diiodo-5-nitrobenzene, C
6H
3I
2NO
2, and 1,3-dibromo-5-nitrobenzene, C
6H
3Br
2NO
2, crystallize in the centrosymmetric space group
P2
1/
m, and are isostructural with 1,3-dichloro-5-nitrobenzene, C
6H
3Cl
2NO
2, that has been redetermined at 100 K for consistency. While the three-dimensional packing in all three structures is similar, the size of the halogen atom affects the nonbonded close contacts observed between molecules. Thus, the structure of 1,3-diiodo-5-nitrobenzene features a close Type 1 I
I contact, the structure of 1,3-dibromo-5-nitrobenzene features a self-complementary nitro-O
Br close contact, while the structure of 1,3-dichloro-5-nitrobenzene also has a self-complementary nitro-O
Cl interaction, as well as a bifurcated C—H
O(nitro) close contact. Notably, the major energetically attractive intermolecular interaction between adjacent molecules in each of the three structures corresponds to a π-stacked interaction. The self-complementary halogen
O(nitro) and C—H
O(nitro) interactions correspond to significant cohesive attraction between molecules in each structure, while the Type 1 halogen–halogen contact is weakly cohesive.
Supporting information
CCDC references: 2208447; 2208446; 2208445
For all structures, data collection: SMART (Bruker, 2014); cell refinement: SMART (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: X-SEED (Barbour, 2020); software used to prepare material for publication: X-SEED (Barbour, 2020).
1,3-Diiodo-5-nitrobenzene (1)
top
Crystal data top
C6H3I2NO2 | F(000) = 336 |
Mr = 374.89 | Dx = 2.933 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
a = 4.1810 (5) Å | Cell parameters from 4388 reflections |
b = 15.0336 (17) Å | θ = 2.7–27.2° |
c = 6.7970 (8) Å | µ = 7.36 mm−1 |
β = 96.506 (2)° | T = 100 K |
V = 424.48 (9) Å3 | Trapezoidal, colourless |
Z = 2 | 0.20 × 0.20 × 0.20 mm |
Data collection top
Bruker APEX-I CCD diffractometer | 982 independent reflections |
Radiation source: fine-focus sealed tube | 974 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 8.3660 pixels mm-1 | θmax = 27.2°, θmin = 2.7° |
phi and ω scans | h = −5→5 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | k = −19→19 |
Tmin = 0.406, Tmax = 0.746 | l = −8→8 |
5377 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.019 | H-atom parameters constrained |
wR(F2) = 0.040 | w = 1/[σ2(Fo2) + 1.4021P] where P = (Fo2 + 2Fc2)/3 |
S = 1.35 | (Δ/σ)max = 0.001 |
982 reflections | Δρmax = 0.77 e Å−3 |
55 parameters | Δρmin = −0.75 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. |
Refinement. Single crystals of each were mounted on a Kryoloop using viscous
hydrocarbon oil. Data were collected at 100 K using a Bruker Apex1 CCD
diffractometer equipped with Mo Kα radiation with λ = 0.71073 Å. Low
temperature data collection was facilitated by use of a Kryoflex system with
an accuracy of ±1 K. Initial data processing was carried out using the Apex 2
software suite [Bruker, 2014]. Structures were solved using SHELXT-2018
(Sheldrick, 2015a) and refined against F2 using SHELXL-2018
(Sheldrick,
2015b). The program X-Seed was used as a graphical
interface (Barbour, 2020). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
I1 | 0.83316 (5) | 0.44977 (2) | 0.22023 (3) | 0.01726 (8) | |
O1 | 0.2670 (7) | 0.32177 (18) | 0.8563 (4) | 0.0290 (6) | |
N1 | 0.3365 (10) | 0.250000 | 0.7879 (6) | 0.0166 (8) | |
C1 | 0.5032 (11) | 0.250000 | 0.6066 (7) | 0.0138 (9) | |
C2 | 0.5755 (8) | 0.3312 (2) | 0.5256 (5) | 0.0145 (6) | |
H2 | 0.524333 | 0.385788 | 0.585351 | 0.017* | |
C3 | 0.7255 (8) | 0.3296 (2) | 0.3537 (5) | 0.0139 (6) | |
C4 | 0.8033 (11) | 0.250000 | 0.2672 (7) | 0.0150 (9) | |
H4 | 0.908365 | 0.250000 | 0.150367 | 0.018* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.02045 (12) | 0.01361 (12) | 0.01868 (12) | −0.00068 (8) | 0.00633 (8) | 0.00277 (8) |
O1 | 0.0447 (17) | 0.0197 (14) | 0.0264 (14) | 0.0007 (12) | 0.0202 (12) | −0.0062 (11) |
N1 | 0.017 (2) | 0.017 (2) | 0.0154 (19) | 0.000 | 0.0019 (16) | 0.000 |
C1 | 0.012 (2) | 0.018 (2) | 0.012 (2) | 0.000 | 0.0009 (17) | 0.000 |
C2 | 0.0142 (15) | 0.0134 (15) | 0.0157 (15) | 0.0008 (12) | 0.0009 (12) | −0.0009 (12) |
C3 | 0.0134 (14) | 0.0120 (15) | 0.0161 (15) | −0.0018 (12) | 0.0009 (12) | 0.0020 (12) |
C4 | 0.012 (2) | 0.021 (2) | 0.012 (2) | 0.000 | 0.0019 (17) | 0.000 |
Geometric parameters (Å, º) top
I1—C3 | 2.094 (3) | C2—C3 | 1.388 (5) |
O1—N1 | 1.223 (3) | C2—H2 | 0.9500 |
N1—C1 | 1.483 (6) | C3—C4 | 1.388 (4) |
C1—C2 | 1.387 (4) | C4—H4 | 0.9500 |
C1—C2i | 1.387 (4) | | |
| | | |
O1i—N1—O1 | 123.9 (4) | C3—C2—H2 | 121.4 |
O1i—N1—C1 | 118.0 (2) | C4—C3—C2 | 121.5 (3) |
O1—N1—C1 | 118.0 (2) | C4—C3—I1 | 119.2 (2) |
C2—C1—C2i | 123.4 (4) | C2—C3—I1 | 119.3 (2) |
C2—C1—N1 | 118.3 (2) | C3i—C4—C3 | 119.1 (4) |
C2i—C1—N1 | 118.3 (2) | C3i—C4—H4 | 120.5 |
C1—C2—C3 | 117.2 (3) | C3—C4—H4 | 120.5 |
C1—C2—H2 | 121.4 | | |
Symmetry code: (i) x, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···I1ii | 0.95 | 3.25 | 4.172 (3) | 165 |
Symmetry code: (ii) −x+1, −y+1, −z+1. |
1,3-Dibromo-5-nitrobenzene (2)
top
Crystal data top
C6H3Br2NO2 | F(000) = 264 |
Mr = 280.91 | Dx = 2.455 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
a = 3.9721 (7) Å | Cell parameters from 2304 reflections |
b = 14.164 (2) Å | θ = 2.9–27.1° |
c = 6.7971 (11) Å | µ = 10.61 mm−1 |
β = 96.486 (2)° | T = 100 K |
V = 379.97 (11) Å3 | Cut plate, colourless |
Z = 2 | 0.38 × 0.26 × 0.09 mm |
Data collection top
Bruker APEX-I CCD diffractometer | 874 independent reflections |
Radiation source: fine-focus sealed tube | 764 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
Detector resolution: 8.3660 pixels mm-1 | θmax = 27.1°, θmin = 2.9° |
phi and ω scans | h = −5→5 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | k = −18→18 |
Tmin = 0.343, Tmax = 0.746 | l = −8→8 |
4446 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0519P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
874 reflections | Δρmax = 1.04 e Å−3 |
55 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. |
Refinement. Single crystals of each were mounted on a Kryoloop using viscous
hydrocarbon oil. Data were collected at 100 K using a Bruker Apex1 CCD
diffractometer equipped with Mo Kα radiation with λ = 0.71073 Å. Low
temperature data collection was facilitated by use of a Kryoflex system with
an accuracy of ±1 K. Initial data processing was carried out using the Apex 2
software suite [Bruker, 2014]. Structures were solved using SHELXT-2018
(Sheldrick, 2015a) and refined against F2 using SHELXL-2018
(Sheldrick,
2015b). The program X-Seed was used as a graphical
interface (Barbour, 2020). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.84325 (8) | 0.55011 (2) | 0.22435 (5) | 0.02091 (17) | |
O1 | 0.2977 (7) | 0.67372 (17) | 0.8585 (4) | 0.0301 (6) | |
N1 | 0.3658 (10) | 0.750000 | 0.7878 (7) | 0.0198 (9) | |
C2 | 0.6006 (8) | 0.6637 (2) | 0.5205 (5) | 0.0175 (7) | |
H2 | 0.550372 | 0.605683 | 0.581154 | 0.021* | |
C3 | 0.7459 (8) | 0.6659 (2) | 0.3462 (6) | 0.0171 (7) | |
C1 | 0.5304 (11) | 0.750000 | 0.6038 (7) | 0.0169 (9) | |
C4 | 0.8204 (11) | 0.750000 | 0.2566 (8) | 0.0212 (11) | |
H4 | 0.920583 | 0.750000 | 0.136165 | 0.025* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0237 (3) | 0.0141 (2) | 0.0254 (3) | 0.00110 (11) | 0.00482 (17) | −0.00274 (12) |
O1 | 0.0464 (16) | 0.0191 (12) | 0.0271 (15) | −0.0050 (12) | 0.0135 (13) | 0.0044 (11) |
N1 | 0.021 (2) | 0.018 (2) | 0.019 (2) | 0.000 | −0.0016 (16) | 0.000 |
C2 | 0.0163 (15) | 0.0153 (14) | 0.0197 (18) | −0.0004 (12) | −0.0030 (13) | −0.0006 (13) |
C3 | 0.0130 (14) | 0.0127 (15) | 0.0246 (19) | 0.0015 (11) | −0.0024 (13) | −0.0037 (13) |
C1 | 0.014 (2) | 0.020 (2) | 0.016 (2) | 0.000 | −0.0011 (19) | 0.000 |
C4 | 0.015 (2) | 0.028 (3) | 0.021 (3) | 0.000 | 0.002 (2) | 0.000 |
Geometric parameters (Å, º) top
Br1—C3 | 1.897 (3) | C2—C1 | 1.389 (4) |
O1—N1 | 1.225 (3) | C2—H2 | 0.9500 |
N1—C1 | 1.475 (6) | C3—C4 | 1.385 (4) |
C2—C3 | 1.375 (5) | C4—H4 | 0.9500 |
| | | |
O1i—N1—O1 | 123.8 (4) | C4—C3—Br1 | 119.2 (3) |
O1i—N1—C1 | 118.1 (2) | C2i—C1—C2 | 123.4 (5) |
O1—N1—C1 | 118.1 (2) | C2i—C1—N1 | 118.3 (2) |
C3—C2—C1 | 117.0 (3) | C2—C1—N1 | 118.3 (2) |
C3—C2—H2 | 121.5 | C3i—C4—C3 | 118.7 (5) |
C1—C2—H2 | 121.5 | C3i—C4—H4 | 120.7 |
C2—C3—C4 | 122.0 (3) | C3—C4—H4 | 120.7 |
C2—C3—Br1 | 118.9 (2) | | |
Symmetry code: (i) x, −y+3/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Br1ii | 0.95 | 3.09 | 3.997 (3) | 161 |
Symmetry code: (ii) −x+1, −y+1, −z+1. |
1,3-Dichloro-5-nitrobenzene (3)
top
Crystal data top
C6H3Cl2NO2 | F(000) = 192 |
Mr = 191.99 | Dx = 1.783 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
a = 3.8115 (3) Å | Cell parameters from 2128 reflections |
b = 13.6452 (11) Å | θ = 3.0–26.9° |
c = 6.8976 (5) Å | µ = 0.85 mm−1 |
β = 94.632 (1)° | T = 100 K |
V = 357.56 (5) Å3 | Cut rod, colourless |
Z = 2 | 0.37 × 0.13 × 0.03 mm |
Data collection top
Bruker APEX-I CCD diffractometer | 813 independent reflections |
Radiation source: fine-focus sealed tube | 747 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 8.3660 pixels mm-1 | θmax = 27.1°, θmin = 3.0° |
phi and ω scans | h = −4→4 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | k = −17→17 |
Tmin = 0.702, Tmax = 0.746 | l = −8→8 |
4560 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.0398P)2 + 0.1267P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
813 reflections | Δρmax = 0.37 e Å−3 |
55 parameters | Δρmin = −0.21 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. |
Refinement. Single crystals of each were mounted on a Kryoloop using viscous
hydrocarbon oil. Data were collected at 100 K using a Bruker Apex1 CCD
diffractometer equipped with Mo Kα radiation with λ = 0.71073 Å. Low
temperature data collection was facilitated by use of a Kryoflex system with
an accuracy of ±1 K. Initial data processing was carried out using the Apex 2
software suite [Bruker, 2014]. Structures were solved using SHELXT-2018
(Sheldrick, 2015a) and refined against F2 using SHELXL-2018
(Sheldrick,
2015b). The program X-Seed was used as a graphical
interface (Barbour, 2020). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.86115 (10) | 0.44740 (3) | 0.23313 (5) | 0.02154 (16) | |
O1 | 0.3346 (3) | 0.32913 (8) | 0.86816 (17) | 0.0290 (3) | |
N1 | 0.3994 (5) | 0.250000 | 0.7954 (3) | 0.0179 (4) | |
C4 | 0.8446 (5) | 0.250000 | 0.2540 (3) | 0.0174 (4) | |
H4 | 0.942848 | 0.250000 | 0.131693 | 0.021* | |
C1 | 0.5603 (5) | 0.250000 | 0.6076 (3) | 0.0153 (4) | |
C3 | 0.7716 (4) | 0.33764 (10) | 0.3448 (2) | 0.0163 (3) | |
C2 | 0.6269 (4) | 0.33974 (11) | 0.5237 (2) | 0.0162 (3) | |
H2 | 0.576278 | 0.399770 | 0.585345 | 0.019* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0264 (2) | 0.0150 (2) | 0.0240 (2) | −0.00205 (13) | 0.00686 (15) | 0.00304 (13) |
O1 | 0.0442 (8) | 0.0215 (6) | 0.0230 (6) | 0.0070 (5) | 0.0124 (5) | −0.0011 (5) |
N1 | 0.0167 (9) | 0.0216 (9) | 0.0154 (9) | 0.000 | 0.0010 (6) | 0.000 |
C4 | 0.0143 (10) | 0.0213 (11) | 0.0165 (10) | 0.000 | 0.0014 (8) | 0.000 |
C1 | 0.0128 (9) | 0.0200 (10) | 0.0131 (9) | 0.000 | 0.0010 (7) | 0.000 |
C3 | 0.0141 (7) | 0.0150 (7) | 0.0194 (7) | −0.0019 (5) | 0.0000 (5) | 0.0020 (6) |
C2 | 0.0144 (7) | 0.0161 (7) | 0.0178 (7) | 0.0000 (5) | −0.0001 (5) | −0.0017 (6) |
Geometric parameters (Å, º) top
Cl1—C3 | 1.7306 (15) | C4—H4 | 0.9500 |
O1—N1 | 1.2242 (14) | C1—C2i | 1.3864 (17) |
N1—C1 | 1.477 (3) | C1—C2 | 1.3865 (17) |
C4—C3i | 1.3885 (18) | C3—C2 | 1.392 (2) |
C4—C3 | 1.3885 (18) | C2—H2 | 0.9500 |
| | | |
O1—N1—O1i | 123.75 (18) | C2—C1—N1 | 117.96 (10) |
O1—N1—C1 | 118.12 (9) | C4—C3—C2 | 121.72 (14) |
O1i—N1—C1 | 118.12 (9) | C4—C3—Cl1 | 119.39 (12) |
C3i—C4—C3 | 118.91 (19) | C2—C3—Cl1 | 118.89 (11) |
C3i—C4—H4 | 120.5 | C1—C2—C3 | 116.80 (14) |
C3—C4—H4 | 120.5 | C1—C2—H2 | 121.6 |
C2i—C1—C2 | 124.05 (19) | C3—C2—H2 | 121.6 |
C2i—C1—N1 | 117.96 (10) | | |
Symmetry code: (i) x, −y+1/2, z. |
Intermolecular energies of interaction, in kJ mol-1, for molecules within
3.8 Å of (1), (2) and (3), respectively, as related to
the intermolecular interaction within each pair of interacting molecules topMajor interaction with X = halogen | X = I | X = Br | X = Cl |
π–π stacking, (perp π–π)a | -31.5 (3.4909) | -29.0 (3.3990) | -23.6 (3.3710) |
Self-complementary X—O (X—O)b | -19.0 (3.492) | -15.2 (3.257) | -9.1 (3.2029) |
Bifurcated C—H···O (H···O)b | -12.0 (2.844) | -10.8 (2.759) | -10.9 (2.6717) |
Type I X—X (X—X)b | -0.7 (3.7599) | -3.3 (3.7048) | -1.7 (3.752) |
Notes: (a) perpendicular π–π separation in Å;
(b) separation between interacting atoms in Å. |
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