1-Chloro-3,4-dinitro­benzene–1,4-dioxane (1/1)

Barnett, S.A.; Pradon, J.; Lewis, T.C.; Tocher, D.A.

doi:10.1107/S1600536806011226

organic compounds

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ISSN: 2056-9890

Volume 62| Part 4| April 2006| Pages o1662-o1663

https://doi.org/10.1107/S1600536806011226

1-Chloro-3,4-dinitrobenzene–1,4-dioxane (1/1)

Sarah A. Barnett,^a ^* Juliette Pradon,^a Thomas C. Lewis ^a and Derek A. Tocher ^a

^aDepartment of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, England
^*Correspondence e-mail: sarah.barnett@ucl.ac.uk

(Received 21 March 2006; accepted 28 March 2006; online 31 March 2006)

The solvate structure of 1-chloro-3,4-dinitrobenzene with 1,4-dioxane, C₆H₃ClN₂O₄·C₄H₈N₂, is reported. Alternating molecules of 3,4-dinitro-1-chlorobenzene and 1,4-dioxane are linked by C—H⋯O hydrogen bonds into a continuous two-dimensional sheet.

Comment

The title compound, (I), was produced during an experimental crystallization polymorph screen on 1-chloro-3,4-dinitrobenzene (3,4-DNCB). Compound (I) crystallizes in the space group P $[\overline{1}]$ with one molecule of 3,4-DNCB and one molecule of 1,4-dioxane in the asymmetric unit (Fig. 1).

The crystal structure of (I) is characterized by alternating molecules of 3,4-DNCB and 1,4-dioxane, linked by a series of C—H⋯O hydrogen bonds (Table 1) into a continuous two-dimensional sheet which lies parallel to the (11 $[\overline{1}]$ ) plane (Fig. 2). Alternating 3,4-DNCB molecules and 1,4-dioxane are linked by pairwise C—H⋯O hydrogen bonds, forming a chain which runs parallel to the body diagonal (111). These chains are then hydrogen-bonded together, forming a sheet via two C—H⋯O interactions between two 3,4-DNCB molecules and one C—H⋯O interaction between the 3,4-DNCB molecule and a 1,4-dioxane molecule of the adjacent chain. Viewing the crystal structure down the a axis reveals that there are alternating layers of 3,4-DNCB and 1,4-dioxane (Fig. 3).

Figure 1
The structure of the asymmetric unit of (I)

, showing the numbering scheme used. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
The two-dimensional network formed by compound (I)

, showing the intermolecular interactions as thin pale-blue lines. Key: C grey, N blue, O red, Cl green and H black.

Figure 3
Packing diagram, showing the stacking of the sheets. C—H⋯O interactions are shown as thin pale-blue lines. Key: C grey, N blue, O red, Cl green and H black.

Experimental

The title compound was recrystallized from 1,4-dioxane solution by slow evaporation at 298 K.

Crystal data

C₆H₃ClN₂O₄·C₄H₈O₂
M_r = 290.66
Triclinic, $[P \overline 1]$
a = 8.2976 (12) Å
b = 8.7112 (13) Å
c = 8.8015 (13) Å
α = 103.661 (2)°
β = 103.909 (2)°
γ = 91.718 (2)°
V = 597.52 (15) Å³
Z = 2
D_x = 1.616 Mg m⁻³
Mo Kα radiation
Cell parameters from 3669 reflections
θ = 2.5–28.2°
μ = 0.35 mm⁻¹
T = 150 (2) K
Block, yellow
0.86 × 0.67 × 0.45 mm

Data collection

Bruker SMART APEX diffractometer
Narrow–frame ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.738, T_max = 0.856
4424 measured reflections
2650 independent reflections
2529 reflections with I > 2σ(I)
R_int = 0.014
θ_max = 28.2°
h = −10 → 10
k = −11 → 11
l = −11 → 11

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.084
S = 1.07
2647 reflections
216 parameters
All H-atom parameters refined
w = 1/[σ²(F_o²) + (0.0478P)² + 0.1587P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O5	0.938 (15)	2.331 (15)	3.2553 (14)	168.3 (13)
C5—H5⋯O4ⁱ	0.969 (17)	2.697 (18)	3.6166 (16)	158.7 (13)
C6—H6⋯O6ⁱⁱ	0.949 (15)	2.468 (15)	3.4017 (14)	168.1 (12)
C7—H7B⋯O4	0.990 (17)	2.624 (17)	3.4618 (16)	142.5 (13)
C8—H8B⋯O1ⁱⁱⁱ	0.996 (19)	2.446 (18)	3.2604 (16)	138.6 (13)
C9—H9B⋯O3^iv	0.951 (18)	2.649 (18)	3.5930 (16)	172.3 (14)
Symmetry codes: (i) x-1, y, z; (ii) x-1, y-1, z-1; (iii) x+1, y+1, z+1; (iv) x, y+1, z+1.

H atoms were located in a difference Fourier map and refined freely [C—H = 0.938 (15)–0.996 (19) Å]. The three reflections with the greatest discrepancies were omitted from the refinement.

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000 ) and MERCURY (Bruno et al., 2002 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806011226/wn2016sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806011226/wn2016Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000) and OLEX (Dolomanov et al., 2003); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

4-Chloro-1,2-dinitrobenzene–1,4-dioxane (1/1) top

Crystal data top

C₆H₃ClN₂O₄·C₄H₈O₂	Z = 2
M_r = 290.66	F(000) = 300
Triclinic, P1	D_x = 1.616 Mg m⁻³
a = 8.2976 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7112 (13) Å	Cell parameters from 3669 reflections
c = 8.8015 (13) Å	θ = 2.5–28.2°
α = 103.661 (2)°	µ = 0.35 mm⁻¹
β = 103.909 (2)°	T = 150 K
γ = 91.718 (2)°	Block, yellow
V = 597.52 (15) Å³	0.86 × 0.67 × 0.45 mm

Data collection top

Bruker SMART APEX diffractometer	2650 independent reflections
Radiation source: fine-focus sealed tube	2529 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
Narrow–frame ω scans	θ_max = 28.2°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
T_min = 0.738, T_max = 0.856	k = −11→11
4424 measured reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: Direct methods
Least-squares matrix: full	Secondary atom site location: Difference Fourier synthesis
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: Found from delta-F
wR(F²) = 0.084	All H-atom parameters refined
S = 1.07	w = 1/[σ²(F_o²) + (0.0478P)² + 0.1587P] where P = (F_o² + 2F_c²)/3
2647 reflections	(Δ/σ)_max < 0.001
216 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.32 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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.01692 (14)	0.14991 (13)	0.38735 (13)	0.0189 (2)
C2	0.13820 (13)	0.25986 (13)	0.49998 (13)	0.0182 (2)
C3	0.09882 (14)	0.37166 (13)	0.62157 (13)	0.0198 (2)
H3	0.1791 (19)	0.4482 (18)	0.6968 (18)	0.024 (4)*
C4	−0.06714 (14)	0.36928 (13)	0.62793 (13)	0.0205 (2)
C5	−0.18948 (14)	0.25951 (15)	0.51873 (14)	0.0233 (2)
H5	−0.304 (2)	0.262 (2)	0.526 (2)	0.035 (4)*
C6	−0.14693 (14)	0.14773 (14)	0.39675 (14)	0.0218 (2)
H6	−0.2275 (19)	0.0712 (18)	0.3186 (18)	0.022 (3)*
Cl1	−0.11770 (4)	0.50731 (4)	0.78178 (4)	0.02978 (11)
N1	0.05511 (12)	0.04236 (11)	0.24729 (11)	0.0204 (2)
O1	−0.00297 (12)	−0.09537 (10)	0.21122 (11)	0.0300 (2)
O2	0.13920 (12)	0.09876 (11)	0.17386 (10)	0.0295 (2)
N2	0.31546 (12)	0.25335 (12)	0.50183 (11)	0.0217 (2)
O3	0.36588 (11)	0.12279 (11)	0.46586 (11)	0.0301 (2)
O4	0.40217 (11)	0.37924 (11)	0.54379 (12)	0.0318 (2)
C7	0.50812 (15)	0.71687 (15)	0.86037 (14)	0.0265 (3)
H7A	0.512 (2)	0.821 (2)	0.8349 (19)	0.034 (4)*
H7B	0.533 (2)	0.635 (2)	0.772 (2)	0.036 (4)*
C8	0.62967 (15)	0.72245 (16)	1.01944 (15)	0.0264 (3)
H8A	0.6304 (19)	0.6196 (19)	1.0408 (18)	0.026 (4)*
H8B	0.746 (2)	0.756 (2)	1.020 (2)	0.040 (4)*
C9	0.42101 (16)	0.79512 (16)	1.15303 (14)	0.0273 (3)
H9A	0.414 (2)	0.695 (2)	1.1806 (18)	0.029 (4)*
H9B	0.398 (2)	0.875 (2)	1.237 (2)	0.039 (4)*
C10	0.29983 (16)	0.78846 (16)	0.99319 (15)	0.0272 (3)
H10A	0.297 (2)	0.891 (2)	0.970 (2)	0.037 (4)*
H10B	0.186 (2)	0.757 (2)	0.991 (2)	0.035 (4)*
O5	0.34241 (11)	0.67501 (10)	0.86581 (10)	0.0258 (2)
O6	0.58807 (11)	0.83433 (11)	1.14873 (10)	0.0273 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0205 (5)	0.0180 (5)	0.0177 (5)	0.0016 (4)	0.0039 (4)	0.0044 (4)
C2	0.0155 (5)	0.0194 (5)	0.0203 (5)	0.0011 (4)	0.0046 (4)	0.0058 (4)
C3	0.0193 (5)	0.0190 (5)	0.0204 (5)	0.0002 (4)	0.0045 (4)	0.0046 (4)
C4	0.0223 (5)	0.0211 (5)	0.0207 (5)	0.0051 (4)	0.0083 (4)	0.0068 (4)
C5	0.0170 (5)	0.0298 (6)	0.0248 (5)	0.0025 (4)	0.0055 (4)	0.0099 (5)
C6	0.0179 (5)	0.0246 (6)	0.0211 (5)	−0.0012 (4)	0.0014 (4)	0.0067 (4)
Cl1	0.02999 (17)	0.03041 (18)	0.02956 (17)	0.00620 (12)	0.01481 (12)	0.00096 (12)
N1	0.0198 (4)	0.0199 (5)	0.0190 (4)	0.0023 (3)	0.0018 (3)	0.0031 (4)
O1	0.0339 (5)	0.0195 (4)	0.0312 (4)	−0.0023 (3)	0.0049 (4)	0.0000 (3)
O2	0.0367 (5)	0.0284 (5)	0.0260 (4)	0.0016 (4)	0.0151 (4)	0.0047 (3)
N2	0.0168 (4)	0.0261 (5)	0.0198 (4)	0.0005 (4)	0.0047 (3)	0.0017 (4)
O3	0.0229 (4)	0.0300 (5)	0.0334 (5)	0.0083 (3)	0.0067 (4)	0.0005 (4)
O4	0.0217 (4)	0.0307 (5)	0.0390 (5)	−0.0074 (4)	0.0089 (4)	0.0010 (4)
C7	0.0261 (6)	0.0276 (6)	0.0228 (5)	−0.0011 (5)	0.0077 (5)	−0.0002 (5)
C8	0.0224 (6)	0.0268 (6)	0.0258 (6)	0.0001 (5)	0.0058 (4)	−0.0009 (5)
C9	0.0252 (6)	0.0327 (7)	0.0218 (5)	−0.0001 (5)	0.0070 (5)	0.0017 (5)
C10	0.0240 (6)	0.0301 (6)	0.0242 (6)	0.0034 (5)	0.0061 (5)	0.0002 (5)
O5	0.0224 (4)	0.0267 (4)	0.0223 (4)	−0.0012 (3)	0.0034 (3)	−0.0027 (3)
O6	0.0239 (4)	0.0292 (5)	0.0225 (4)	−0.0033 (3)	0.0045 (3)	−0.0036 (3)

Geometric parameters (Å, º) top

C1—C6	1.3816 (16)	N2—O3	1.2210 (14)
C1—C2	1.3881 (15)	C7—O5	1.4267 (14)
C1—N1	1.4691 (14)	C7—C8	1.5052 (18)
C2—C3	1.3768 (15)	C7—H7A	0.982 (17)
C2—N2	1.4700 (14)	C7—H7B	0.990 (17)
C3—C4	1.3913 (15)	C8—O6	1.4314 (14)
C3—H3	0.938 (15)	C8—H8A	0.958 (16)
C4—C5	1.3811 (16)	C8—H8B	0.996 (19)
C4—Cl1	1.7291 (11)	C9—O6	1.4292 (15)
C5—C6	1.3908 (17)	C9—C10	1.5071 (17)
C5—H5	0.969 (17)	C9—H9A	0.962 (17)
C6—H6	0.949 (15)	C9—H9B	0.951 (18)
N1—O1	1.2184 (13)	C10—O5	1.4306 (14)
N1—O2	1.2215 (13)	C10—H10A	0.964 (18)
N2—O4	1.2208 (13)	C10—H10B	0.973 (17)

C6—C1—C2	120.56 (10)	O5—C7—H7A	108.9 (10)
C6—C1—N1	117.89 (10)	C8—C7—H7A	110.4 (10)
C2—C1—N1	121.33 (10)	O5—C7—H7B	107.0 (10)
C3—C2—C1	121.33 (10)	C8—C7—H7B	110.9 (10)
C3—C2—N2	117.30 (9)	H7A—C7—H7B	109.0 (13)
C1—C2—N2	121.19 (10)	O6—C8—C7	110.89 (10)
C2—C3—C4	117.37 (10)	O6—C8—H8A	109.6 (9)
C2—C3—H3	122.1 (9)	C7—C8—H8A	110.3 (9)
C4—C3—H3	120.5 (9)	O6—C8—H8B	106.8 (10)
C5—C4—C3	122.32 (10)	C7—C8—H8B	111.9 (10)
C5—C4—Cl1	119.85 (9)	H8A—C8—H8B	107.3 (14)
C3—C4—Cl1	117.82 (9)	O6—C9—C10	111.09 (10)
C4—C5—C6	119.34 (10)	O6—C9—H9A	109.7 (10)
C4—C5—H5	120.1 (10)	C10—C9—H9A	110.3 (9)
C6—C5—H5	120.6 (10)	O6—C9—H9B	106.5 (11)
C1—C6—C5	119.06 (10)	C10—C9—H9B	110.7 (11)
C1—C6—H6	119.0 (9)	H9A—C9—H9B	108.3 (14)
C5—C6—H6	121.9 (9)	O5—C10—C9	110.50 (10)
O1—N1—O2	125.13 (10)	O5—C10—H10A	110.2 (10)
O1—N1—C1	117.35 (9)	C9—C10—H10A	110.8 (11)
O2—N1—C1	117.50 (9)	O5—C10—H10B	106.6 (10)
O4—N2—O3	124.94 (10)	C9—C10—H10B	113.0 (10)
O4—N2—C2	117.27 (10)	H10A—C10—H10B	105.5 (14)
O3—N2—C2	117.76 (9)	C7—O5—C10	109.34 (9)
O5—C7—C8	110.53 (10)	C9—O6—C8	109.74 (9)

C6—C1—C2—C3	−1.45 (17)	C2—C1—N1—O1	137.79 (11)
N1—C1—C2—C3	173.08 (10)	C6—C1—N1—O2	130.77 (11)
C6—C1—C2—N2	173.60 (10)	C2—C1—N1—O2	−43.91 (15)
N1—C1—C2—N2	−11.86 (16)	C3—C2—N2—O4	−37.51 (14)
C1—C2—C3—C4	0.51 (17)	C1—C2—N2—O4	147.24 (11)
N2—C2—C3—C4	−174.73 (10)	C3—C2—N2—O3	140.47 (11)
C2—C3—C4—C5	0.50 (17)	C1—C2—N2—O3	−34.78 (15)
C2—C3—C4—Cl1	179.11 (8)	O5—C7—C8—O6	−58.54 (13)
C3—C4—C5—C6	−0.58 (18)	O6—C9—C10—O5	57.95 (14)
Cl1—C4—C5—C6	−179.16 (9)	C8—C7—O5—C10	58.67 (13)
C2—C1—C6—C5	1.35 (17)	C9—C10—O5—C7	−58.31 (13)
N1—C1—C6—C5	−173.37 (10)	C10—C9—O6—C8	−56.48 (14)
C4—C5—C6—C1	−0.36 (17)	C7—C8—O6—C9	56.69 (13)
C6—C1—N1—O1	−47.53 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O5	0.938 (15)	2.331 (15)	3.2553 (14)	168.3 (13)
C5—H5···O4ⁱ	0.969 (17)	2.697 (18)	3.6166 (16)	158.7 (13)
C6—H6···O6ⁱⁱ	0.949 (15)	2.468 (15)	3.4017 (14)	168.1 (12)
C7—H7B···O4	0.990 (17)	2.624 (17)	3.4618 (16)	142.5 (13)
C8—H8B···O1ⁱⁱⁱ	0.996 (19)	2.446 (18)	3.2604 (16)	138.6 (13)
C9—H9B···O3^iv	0.951 (18)	2.649 (18)	3.5930 (16)	172.3 (14)

Symmetry codes: (i) x−1, y, z; (ii) x−1, y−1, z−1; (iii) x+1, y+1, z+1; (iv) x, y+1, z+1.

Acknowledgements

The authors acknowledge the Research Councils UK Basic Technology Programme for supporting `Control and Prediction of the Organic Solid State' (URL: www.cposs.org.uk).

References

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Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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