A structural and computational comparison of close contacts and related inter­molecular energies of inter­action in the structures of 1,3-di­iodo-5-nitro­benzene, 1,3-di­bromo-5-nitro­benzene, and 1,3-di­chloro-5-nitro­benzene

1,3-Di­iodo-5-nitro­benzene, C₆H₃I₂NO₂, and 1,3-di­bromo-5-nitro­benzene, C₆H₃Br₂NO₂, crystallize in the centrosymmetric space group P2₁/m, and are iso­structural with 1,3-di­chloro-5-nitro­benzene, C₆H₃Cl₂NO₂, 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.

Computing details

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)

Crystal data

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) Å^3	Trapezoidal, colourless
Z = 2	0.20 × 0.20 × 0.20 mm

Data collection

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

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.019	H-atom parameters constrained
wR(F^2) = 0.040	w = 1/[σ^2(Fo^2) + 1.4021P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—C2^i	1.387 (4)
O1^i—N1—O1	123.9 (4)	C3—C2—H2	121.4
O1^i—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—C2^i	123.4 (4)	C2—C3—I1	119.3 (2)
C2—C1—N1	118.3 (2)	C3^i—C4—C3	119.1 (4)
C2^i—C1—N1	118.3 (2)	C3^i—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)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···I1^ii	0.95	3.25	4.172 (3)	165

Symmetry code: (ii) −x+1, −y+1, −z+1.

1,3-Dibromo-5-nitrobenzene (2)

Crystal data

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) Å^3	Cut plate, colourless
Z = 2	0.38 × 0.26 × 0.09 mm

Data collection

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

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.081	w = 1/[σ^2(Fo^2) + (0.0519P)^2] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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
O1^i—N1—O1	123.8 (4)	C4—C3—Br1	119.2 (3)
O1^i—N1—C1	118.1 (2)	C2^i—C1—C2	123.4 (5)
O1—N1—C1	118.1 (2)	C2^i—C1—N1	118.3 (2)
C3—C2—C1	117.0 (3)	C2—C1—N1	118.3 (2)
C3—C2—H2	121.5	C3^i—C4—C3	118.7 (5)
C1—C2—H2	121.5	C3^i—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)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Br1^ii	0.95	3.09	3.997 (3)	161

Symmetry code: (ii) −x+1, −y+1, −z+1.

1,3-Dichloro-5-nitrobenzene (3)

Crystal data

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) Å^3	Cut rod, colourless
Z = 2	0.37 × 0.13 × 0.03 mm

Data collection

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

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0398P)^2 + 0.1267P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Cl1—C3	1.7306 (15)	C4—H4	0.9500
O1—N1	1.2242 (14)	C1—C2^i	1.3864 (17)
N1—C1	1.477 (3)	C1—C2	1.3865 (17)
C4—C3^i	1.3885 (18)	C3—C2	1.392 (2)
C4—C3	1.3885 (18)	C2—H2	0.9500
O1—N1—O1^i	123.75 (18)	C2—C1—N1	117.96 (10)
O1—N1—C1	118.12 (9)	C4—C3—C2	121.72 (14)
O1^i—N1—C1	118.12 (9)	C4—C3—Cl1	119.39 (12)
C3^i—C4—C3	118.91 (19)	C2—C3—Cl1	118.89 (11)
C3^i—C4—H4	120.5	C1—C2—C3	116.80 (14)
C3—C4—H4	120.5	C1—C2—H2	121.6
C2^i—C1—C2	124.05 (19)	C3—C2—H2	121.6
C2^i—C1—N1	117.96 (10)

Symmetry code: (i) x, −y+1/2, z.