Atomic thermal motions studied by variable-temperature X-ray diffraction and related to non-linear optical properties of crystalline meta-di-nitrobenzene

The meta-dinitrobenzene crystal structure has been determined at five temperatures in the 100-300 K temperature range. The thermal expansion coefficients have been calculated from the temperature variation of the lattice parameters. Rigid-body motion analysis with allowance for large-amplitude internal motions provided the T, L and S tensors' values at the temperatures studied and was used to characterize the torsional motion of two nitro groups in the molecule. Frequencies of the translational and librational modes and of the torsional modes of the nitro groups have been compared with the wave numbers at the maximum of bands in the low-frequency Raman and IR spectra. Ab initio calculations were performed in order to assess the contribution from large-amplitude internal motions to the static first-order hyperpolarizability of the m-dinitrobenzene molecule.

Computing details

Data collection: KUMA KM4CCD software, 1999 for 100; KUMA Diffraction Km4CCD software, 1999 for 130; KUMA Diffraction KM4CCD software, 1999 for 160, 200, 300. Cell refinement: KUMA KM4CCD software, 1999 for 100; KUMA Diffraction Km4CCD software, 1999 for 130; KUMA Diffraction KM4CCD software, 1999 for 160, 200, 300. Data reduction: KUMA KM4CCD software, 1999 for 100; KUMA Diffraction Km4CCD software, 1999 for 130; KUMA Diffraction KM4CCD software, 1999 for 160, 200, 300. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for 100; SHELXS97 (Sheldrick, 1990) for 130, 160, 200, 300. For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEP-3 (Farrugia, 1997) for 100, 160, 200, 300; ORTEP-3 (Farrugia,1997) for 130. Software used to prepare material for publication: SHELXL97 (SHeldrick, 1997) for 100; SHELXL97 (Sheldrick, 1997) for 130, 160, 200, 300.

Figures

(100) 1,3-dinitrobenzene

Crystal data

C6H4N2O4	Dx = 1.643 Mg m^−3
Mr = 168.11	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 1717 reflections
a = 14.024 (2) Å	θ = 3.4–22.6°
b = 13.182 (2) Å	µ = 0.14 mm^−1
c = 3.677 (1) Å	T = 100 K
V = 679.7 (2) Å^3	Prism, colourless
Z = 4	0.72 × 0.33 × 0.23 mm
F(000) = 344

Data collection

KUMA Diffraction KM4CCD diffractometer	1388 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.069
Graphite monochromator	θmax = 31.2°, θmin = 3.3°
ω scan	h = −20→20
5634 measured reflections	k = −19→18
1448 independent reflections	l = −5→3

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.123	Calculated w = 1/[σ^2(Fo^2) + (0.0769P)^2 + 0.0678P] where P = (Fo^2 + 2Fc^2)/3
S = 1.16	(Δ/σ)max < 0.001
1448 reflections	Δρmax = 0.28 e Å^−3
109 parameters	Δρmin = −0.32 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.7 (14)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.13529 (10)	0.63651 (11)	0.0893 (5)	0.0160 (3)
C2	0.05064 (10)	0.67924 (12)	−0.0312 (5)	0.0163 (3)
H2	0.0012	0.6402	−0.1254	0.020*
C3	0.04439 (10)	0.78380 (12)	−0.0025 (5)	0.0176 (3)
C4	0.11756 (12)	0.84440 (11)	0.1306 (6)	0.0206 (3)
H4	0.1104	0.9144	0.1463	0.025*
C5	0.20157 (11)	0.79778 (12)	0.2396 (6)	0.0207 (3)
H5	0.2521	0.8371	0.3233	0.025*
C6	0.21083 (10)	0.69298 (12)	0.2247 (5)	0.0190 (3)
H46	0.2664	0.6614	0.3037	0.023*
N1	0.14534 (10)	0.52547 (10)	0.0758 (5)	0.0205 (3)
N2	−0.04511 (10)	0.83199 (12)	−0.1209 (5)	0.0227 (3)
O1	0.21261 (10)	0.48722 (10)	0.2385 (6)	0.0343 (4)
O2	0.08674 (10)	0.47695 (10)	−0.0975 (5)	0.0305 (4)
O3	−0.10001 (9)	0.78134 (12)	−0.3058 (5)	0.0316 (4)
O4	−0.06021 (10)	0.91926 (10)	−0.0261 (6)	0.0374 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0168 (6)	0.0165 (6)	0.0146 (7)	0.0002 (4)	0.0007 (5)	−0.0001 (6)
C2	0.0137 (6)	0.0192 (6)	0.0159 (7)	−0.0022 (4)	−0.0003 (5)	0.0005 (6)
C3	0.0140 (6)	0.0200 (7)	0.0186 (8)	0.0015 (4)	0.0010 (6)	0.0035 (7)
C4	0.0221 (7)	0.0189 (6)	0.0207 (9)	−0.0025 (5)	0.0026 (6)	−0.0006 (6)
C5	0.0194 (6)	0.0231 (7)	0.0196 (8)	−0.0064 (5)	−0.0012 (7)	−0.0026 (7)
C6	0.0142 (6)	0.0261 (7)	0.0165 (8)	−0.0005 (5)	−0.0012 (6)	0.0000 (7)
N1	0.0228 (6)	0.0186 (6)	0.0201 (7)	0.0024 (4)	0.0038 (5)	−0.0010 (5)
N2	0.0188 (6)	0.0261 (7)	0.0233 (8)	0.0046 (5)	0.0015 (6)	0.0077 (6)
O1	0.0375 (7)	0.0284 (6)	0.0370 (9)	0.0125 (5)	−0.0073 (7)	0.0021 (7)
O2	0.0316 (6)	0.0216 (6)	0.0382 (9)	−0.0039 (4)	−0.0009 (6)	−0.0069 (6)
O3	0.0189 (5)	0.0437 (8)	0.0322 (9)	0.0041 (5)	−0.0066 (6)	0.0027 (7)
O4	0.0348 (7)	0.0250 (6)	0.0524 (11)	0.0126 (5)	0.0022 (8)	0.0062 (7)

Geometric parameters (Å, º)

C1—C2	1.387 (2)	C4—C5	1.388 (2)
C1—C6	1.387 (2)	C5—C6	1.389 (2)
C1—N1	1.4713 (19)	N1—O2	1.221 (2)
C2—C3	1.385 (2)	N1—O1	1.226 (2)
C3—C4	1.389 (2)	N2—O4	1.221 (2)
C3—N2	1.4725 (19)	N2—O3	1.225 (2)
C2—C1—C6	123.40 (14)	C4—C5—C6	120.57 (14)
C2—C1—N1	118.37 (14)	C1—C6—C5	118.46 (14)
C6—C1—N1	118.22 (14)	O2—N1—O1	123.88 (15)
C3—C2—C1	115.72 (14)	O2—N1—C1	118.32 (15)
C2—C3—C4	123.51 (14)	O1—N1—C1	117.81 (15)
C2—C3—N2	117.44 (13)	O4—N2—O3	124.28 (15)
C4—C3—N2	119.05 (14)	O4—N2—C3	118.04 (16)
C5—C4—C3	118.30 (13)	O3—N2—C3	117.68 (15)
C6—C1—C2—C3	−1.2 (3)	C4—C5—C6—C1	1.7 (3)
N1—C1—C2—C3	178.29 (17)	C2—C1—N1—O2	12.6 (2)
C1—C2—C3—C4	1.2 (3)	C6—C1—N1—O2	−167.81 (17)
C1—C2—C3—N2	−178.81 (17)	C2—C1—N1—O1	−167.69 (18)
C2—C3—C4—C5	0.2 (3)	C6—C1—N1—O1	11.8 (3)
N2—C3—C4—C5	−179.74 (17)	C2—C3—N2—O4	164.3 (2)
C3—C4—C5—C6	−1.8 (3)	C4—C3—N2—O4	−15.8 (3)
C2—C1—C6—C5	−0.2 (3)	C2—C3—N2—O3	−15.1 (3)
N1—C1—C6—C5	−179.72 (16)	C4—C3—N2—O3	164.90 (17)

(130) 1,3-dinitrobenzene

Crystal data

C6H4N2O4	Dx = 1.630 Mg m^−3
Mr = 168.11	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 826 reflections
a = 14.040 (4) Å	θ = 3.3–17.3°
b = 13.208 (4) Å	µ = 0.14 mm^−1
c = 3.694 (1) Å	T = 130 K
V = 685.0 (3) Å^3	Prism, colourless
Z = 4	0.72 × 0.33 × 0.23 mm
F(000) = 344

Data collection

Kuma Diffraction KM4CCD diffractometer	1322 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.059
Graphite monochromator	θmax = 31.2°, θmin = 4.2°
ω scan	h = −20→20
5088 measured reflections	k = −19→18
1422 independent reflections	l = −5→3

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.142	Calculated w = 1/[σ^2(Fo^2) + (0.0504P)^2 + 0.5159P] where P = (Fo^2 + 2Fc^2)/3
S = 1.18	(Δ/σ)max < 0.001
1422 reflections	Δρmax = 0.32 e Å^−3
109 parameters	Δρmin = −0.29 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 1 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.36493 (17)	0.63705 (17)	0.1135 (8)	0.0197 (5)
C2	0.44924 (16)	0.67942 (18)	−0.0072 (8)	0.0195 (4)
H2	0.4985	0.6403	−0.1010	0.023*
C3	0.45566 (17)	0.78366 (18)	0.0203 (8)	0.0210 (5)
C4	0.38288 (19)	0.84386 (19)	0.1526 (8)	0.0249 (5)
H4	0.3900	0.9138	0.1668	0.030*
C5	0.29903 (18)	0.7976 (2)	0.2638 (9)	0.0266 (5)
H5	0.2488	0.8368	0.3495	0.032*
C6	0.28984 (16)	0.69346 (19)	0.2476 (8)	0.0226 (5)
H6	0.2342	0.6620	0.3254	0.027*
N1	0.35452 (16)	0.52611 (16)	0.0997 (8)	0.0261 (5)
N2	0.54514 (16)	0.83197 (19)	−0.0992 (8)	0.0293 (5)
O1	0.28751 (18)	0.48792 (17)	0.2605 (9)	0.0445 (6)
O2	0.41332 (16)	0.47723 (15)	−0.0721 (8)	0.0382 (6)
O3	0.59999 (15)	0.7809 (2)	−0.2807 (8)	0.0404 (6)
O4	0.56027 (18)	0.91928 (16)	−0.0059 (10)	0.0494 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0208 (10)	0.0193 (10)	0.0190 (11)	−0.0011 (7)	−0.0017 (9)	−0.0005 (9)
C2	0.0165 (9)	0.0228 (10)	0.0192 (11)	0.0019 (7)	0.0004 (9)	0.0001 (10)
C3	0.0180 (10)	0.0244 (11)	0.0207 (12)	−0.0003 (8)	−0.0014 (9)	0.0028 (11)
C4	0.0273 (11)	0.0220 (10)	0.0253 (13)	0.0039 (9)	−0.0044 (10)	−0.0012 (11)
C5	0.0231 (11)	0.0305 (13)	0.0262 (13)	0.0095 (9)	0.0004 (12)	−0.0045 (12)
C6	0.0145 (9)	0.0327 (12)	0.0205 (12)	0.0005 (8)	0.0013 (10)	−0.0014 (11)
N1	0.0277 (10)	0.0246 (10)	0.0259 (11)	−0.0025 (8)	−0.0050 (10)	−0.0006 (10)
N2	0.0218 (10)	0.0359 (12)	0.0302 (13)	−0.0059 (8)	−0.0020 (10)	0.0091 (11)
O1	0.0503 (13)	0.0341 (11)	0.0492 (15)	−0.0174 (9)	0.0097 (13)	0.0028 (12)
O2	0.0399 (11)	0.0251 (10)	0.0495 (17)	0.0057 (8)	0.0008 (12)	−0.0077 (10)
O3	0.0245 (9)	0.0550 (14)	0.0417 (15)	−0.0068 (9)	0.0089 (11)	0.0026 (12)
O4	0.0460 (13)	0.0297 (11)	0.072 (2)	−0.0158 (9)	−0.0011 (15)	0.0065 (13)

Geometric parameters (Å, º)

C1—C6	1.383 (3)	C4—C5	1.389 (4)
C1—C2	1.383 (3)	C5—C6	1.382 (4)
C1—N1	1.473 (3)	N1—O1	1.221 (3)
C2—C3	1.384 (3)	N1—O2	1.225 (3)
C3—C4	1.384 (4)	N2—O4	1.222 (3)
C3—N2	1.477 (3)	N2—O3	1.223 (4)
C6—C1—C2	123.4 (2)	C6—C5—C4	120.3 (2)
C6—C1—N1	118.2 (2)	C5—C6—C1	118.7 (2)
C2—C1—N1	118.4 (2)	O1—N1—O2	123.6 (2)
C1—C2—C3	115.8 (2)	O1—N1—C1	118.1 (2)
C2—C3—C4	123.3 (2)	O2—N1—C1	118.4 (2)
C2—C3—N2	117.6 (2)	O4—N2—O3	124.4 (3)
C4—C3—N2	119.0 (2)	O4—N2—C3	118.1 (3)
C3—C4—C5	118.5 (2)	O3—N2—C3	117.5 (2)
C6—C1—C2—C3	1.3 (4)	N1—C1—C6—C5	179.6 (3)
N1—C1—C2—C3	−178.5 (3)	C6—C1—N1—O1	−11.9 (4)
C1—C2—C3—C4	−1.2 (4)	C2—C1—N1—O1	168.0 (3)
C1—C2—C3—N2	178.9 (2)	C6—C1—N1—O2	168.1 (3)
C2—C3—C4—C5	0.0 (4)	C2—C1—N1—O2	−12.1 (4)
N2—C3—C4—C5	179.9 (3)	C2—C3—N2—O4	−164.4 (3)
C3—C4—C5—C6	1.2 (5)	C4—C3—N2—O4	15.7 (4)
C4—C5—C6—C1	−1.1 (5)	C2—C3—N2—O3	14.5 (4)
C2—C1—C6—C5	−0.2 (4)	C4—C3—N2—O3	−165.5 (3)

(160) 1,3-dinitrobenzene

Crystal data

C6H4N2O4	Dx = 1.618 Mg m^−3
Mr = 168.11	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 958 reflections
a = 14.052 (4) Å	θ = 3.3–16.8°
b = 13.224 (4) Å	µ = 0.14 mm^−1
c = 3.714 (1) Å	T = 160 K
V = 690.1 (3) Å^3	Prism, colourless
Z = 4	0.72 × 0.33 × 0.23 mm
F(000) = 344

Data collection

KUMA Diffraction KM4CCD diffractometer	1077 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.100
Graphite monochromator	θmax = 31.2°, θmin = 4.2°
ω scan	h = −18→20
3208 measured reflections	k = −18→15
1212 independent reflections	l = −5→2

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.155	Calculated w = 1/[σ^2(Fo^2) + (0.0717P)^2 + 0.2515P] where P = (Fo^2 + 2Fc^2)/3
S = 1.17	(Δ/σ)max < 0.001
1212 reflections	Δρmax = 0.29 e Å^−3
109 parameters	Δρmin = −0.32 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.36491 (18)	0.63742 (18)	0.1775 (8)	0.0248 (5)
C2	0.44928 (17)	0.6793 (2)	0.2991 (8)	0.0258 (5)
H2	0.4983	0.6401	0.3927	0.031*
C3	0.45593 (18)	0.7836 (2)	0.2724 (8)	0.0271 (5)
C4	0.3837 (2)	0.8442 (2)	0.1412 (9)	0.0325 (6)
H4	0.3909	0.9140	0.1290	0.039*
C5	0.29996 (19)	0.7981 (2)	0.0279 (9)	0.0328 (6)
H5	0.2501	0.8375	−0.0587	0.039*
C6	0.29026 (17)	0.6937 (2)	0.0434 (8)	0.0288 (5)
H6	0.2347	0.6625	−0.0350	0.035*
N1	0.35429 (18)	0.52676 (18)	0.1913 (8)	0.0334 (5)
N2	0.54545 (17)	0.8311 (2)	0.3934 (9)	0.0366 (6)
O1	0.28720 (19)	0.48880 (18)	0.0329 (10)	0.0555 (7)
O2	0.41256 (18)	0.47775 (17)	0.3635 (8)	0.0482 (7)
O3	0.59988 (16)	0.7797 (2)	0.5720 (9)	0.0507 (7)
O4	0.5604 (2)	0.9186 (2)	0.3036 (11)	0.0614 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0265 (11)	0.0251 (11)	0.0227 (10)	0.0007 (8)	0.0027 (9)	0.0007 (10)
C2	0.0232 (11)	0.0294 (12)	0.0246 (11)	0.0033 (8)	−0.0005 (10)	−0.0004 (10)
C3	0.0236 (12)	0.0301 (13)	0.0275 (12)	−0.0025 (8)	0.0022 (10)	−0.0036 (12)
C4	0.0346 (13)	0.0294 (13)	0.0335 (14)	0.0044 (10)	0.0034 (12)	0.0008 (12)
C5	0.0292 (12)	0.0373 (15)	0.0319 (13)	0.0086 (10)	−0.0014 (12)	0.0055 (13)
C6	0.0212 (10)	0.0400 (14)	0.0251 (11)	−0.0005 (9)	0.0004 (10)	−0.0004 (12)
N1	0.0368 (13)	0.0288 (11)	0.0346 (12)	−0.0037 (9)	0.0042 (11)	−0.0001 (10)
N2	0.0283 (12)	0.0422 (14)	0.0393 (13)	−0.0085 (9)	0.0030 (11)	−0.0094 (12)
O1	0.0605 (15)	0.0437 (13)	0.0623 (16)	−0.0211 (11)	−0.0136 (15)	−0.0017 (14)
O2	0.0506 (13)	0.0312 (11)	0.0628 (18)	0.0064 (9)	−0.0032 (14)	0.0103 (12)
O3	0.0282 (10)	0.0694 (17)	0.0546 (16)	−0.0091 (10)	−0.0103 (12)	−0.0042 (14)
O4	0.0560 (15)	0.0400 (14)	0.088 (3)	−0.0194 (10)	0.0015 (17)	−0.0105 (16)

Geometric parameters (Å, º)

C1—C6	1.380 (4)	C4—C5	1.390 (4)
C1—C2	1.385 (3)	C5—C6	1.388 (4)
C1—N1	1.472 (3)	N1—O1	1.219 (4)
C2—C3	1.385 (4)	N1—O2	1.225 (3)
C3—C4	1.382 (4)	N2—O3	1.219 (4)
C3—N2	1.476 (3)	N2—O4	1.222 (4)
C6—C1—C2	123.6 (2)	C6—C5—C4	120.4 (2)
C6—C1—N1	118.2 (2)	C1—C6—C5	118.5 (2)
C2—C1—N1	118.3 (2)	O1—N1—O2	123.4 (3)
C1—C2—C3	115.6 (2)	O1—N1—C1	118.1 (3)
C4—C3—C2	123.6 (2)	O2—N1—C1	118.5 (2)
C4—C3—N2	119.1 (2)	O3—N2—O4	124.6 (3)
C2—C3—N2	117.3 (2)	O3—N2—C3	117.6 (3)
C3—C4—C5	118.3 (2)	O4—N2—C3	117.8 (3)
C6—C1—C2—C3	−1.2 (4)	C4—C5—C6—C1	0.8 (5)
N1—C1—C2—C3	178.7 (3)	C6—C1—N1—O1	11.4 (4)
C1—C2—C3—C4	1.3 (4)	C2—C1—N1—O1	−168.5 (3)
C1—C2—C3—N2	−179.0 (3)	C6—C1—N1—O2	−167.9 (3)
C2—C3—C4—C5	−0.4 (5)	C2—C1—N1—O2	12.2 (4)
N2—C3—C4—C5	179.9 (3)	C4—C3—N2—O3	165.7 (3)
C3—C4—C5—C6	−0.7 (5)	C2—C3—N2—O3	−14.1 (4)
C2—C1—C6—C5	0.2 (5)	C4—C3—N2—O4	−15.3 (4)
N1—C1—C6—C5	−179.7 (3)	C2—C3—N2—O4	165.0 (3)

(200) 1,3-dinitrobenzene

Crystal data

C6H4N2O4	Dx = 1.603 Mg m^−3
Mr = 168.11	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 1607 reflections
a = 14.069 (2) Å	θ = 3.4–24.2°
b = 13.245 (2) Å	µ = 0.14 mm^−1
c = 3.738 (1) Å	T = 200 K
V = 696.6 (2) Å^3	Prism, colourless
Z = 4	0.72 × 0.33 × 0.23 mm
F(000) = 344

Data collection

KUMA Diffraction KM4CCD diffractometer	1330 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.068
Graphite monochromator	θmax = 31.2°, θmin = 4.2°
ω scan	h = −20→20
5386 measured reflections	k = −19→18
1475 independent reflections	l = −3→5

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.146	Calculated w = 1/[σ^2(Fo^2) + (0.0747P)^2 + 0.2161P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1475 reflections	Δρmax = 0.21 e Å^−3
109 parameters	Δρmin = −0.22 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.13479 (14)	0.36197 (14)	0.5644 (7)	0.0291 (4)
C2	0.05067 (13)	0.32061 (15)	0.4418 (6)	0.0294 (4)
H2	0.0020	0.3600	0.3479	0.035*
C3	0.04367 (14)	0.21651 (16)	0.4682 (7)	0.0321 (4)
C4	0.11587 (17)	0.15622 (16)	0.5992 (8)	0.0391 (5)
H4	0.1086	0.0865	0.6108	0.047*
C5	0.19935 (15)	0.20174 (18)	0.7130 (8)	0.0402 (5)
H5	0.2490	0.1623	0.7992	0.048*
C6	0.20904 (14)	0.30558 (17)	0.6989 (7)	0.0348 (4)
H6	0.2644	0.3367	0.7784	0.042*
N2	−0.04551 (14)	0.16957 (17)	0.3447 (7)	0.0450 (5)
N1	0.14572 (14)	0.47250 (14)	0.5495 (7)	0.0401 (5)
O1	0.21314 (16)	0.51008 (15)	0.7081 (9)	0.0687 (7)
O2	0.08791 (15)	0.52161 (13)	0.3799 (7)	0.0585 (6)
O3	−0.10015 (14)	0.2206 (2)	0.1703 (8)	0.0635 (7)
O4	−0.06067 (17)	0.08222 (16)	0.4317 (11)	0.0768 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0295 (8)	0.0290 (8)	0.0289 (9)	−0.0010 (6)	0.0013 (8)	0.0010 (8)
C2	0.0254 (8)	0.0320 (9)	0.0306 (9)	0.0041 (6)	−0.0007 (8)	−0.0013 (8)
C3	0.0287 (8)	0.0347 (9)	0.0330 (10)	−0.0005 (7)	0.0018 (8)	−0.0045 (10)
C4	0.0427 (11)	0.0319 (9)	0.0428 (13)	0.0057 (8)	0.0054 (10)	0.0006 (10)
C5	0.0340 (9)	0.0447 (12)	0.0418 (12)	0.0141 (8)	−0.0018 (10)	0.0057 (11)
C6	0.0252 (8)	0.0464 (11)	0.0328 (10)	0.0005 (7)	−0.0023 (8)	0.0009 (10)
N2	0.0345 (9)	0.0514 (12)	0.0490 (12)	−0.0103 (8)	0.0035 (9)	−0.0129 (11)
N1	0.0439 (10)	0.0348 (8)	0.0418 (11)	−0.0049 (7)	0.0068 (9)	0.0002 (9)
O1	0.0746 (14)	0.0520 (11)	0.0795 (17)	−0.0278 (10)	−0.0154 (14)	−0.0036 (13)
O2	0.0630 (12)	0.0345 (9)	0.0779 (18)	0.0066 (8)	−0.0013 (12)	0.0112 (10)
O3	0.0357 (9)	0.0848 (14)	0.0699 (16)	−0.0090 (9)	−0.0148 (10)	−0.0041 (14)
O4	0.0666 (13)	0.0492 (11)	0.115 (3)	−0.0255 (9)	0.0003 (16)	−0.0139 (15)

Geometric parameters (Å, º)

C1—C6	1.379 (3)	C4—C5	1.387 (3)
C1—C2	1.382 (3)	C5—C6	1.383 (3)
C1—N1	1.473 (3)	N2—O3	1.213 (4)
C2—C3	1.386 (3)	N2—O4	1.221 (3)
C3—C4	1.382 (3)	N1—O2	1.219 (3)
C3—N2	1.474 (3)	N1—O1	1.224 (3)
C6—C1—C2	123.69 (17)	C6—C5—C4	120.26 (19)
C6—C1—N1	118.23 (18)	C1—C6—C5	118.55 (19)
C2—C1—N1	118.08 (18)	O3—N2—O4	124.1 (2)
C1—C2—C3	115.57 (18)	O3—N2—C3	118.2 (2)
C4—C3—C2	123.22 (19)	O4—N2—C3	117.7 (2)
C4—C3—N2	119.5 (2)	O2—N1—O1	123.5 (2)
C2—C3—N2	117.24 (19)	O2—N1—C1	118.7 (2)
C3—C4—C5	118.69 (19)	O1—N1—C1	117.8 (2)
C6—C1—C2—C3	1.2 (4)	C4—C5—C6—C1	−1.1 (4)
N1—C1—C2—C3	−178.9 (2)	C4—C3—N2—O3	−166.3 (3)
C1—C2—C3—C4	−1.5 (3)	C2—C3—N2—O3	13.0 (4)
C1—C2—C3—N2	179.2 (2)	C4—C3—N2—O4	15.3 (4)
C2—C3—C4—C5	0.5 (4)	C2—C3—N2—O4	−165.4 (3)
N2—C3—C4—C5	179.8 (2)	C6—C1—N1—O2	168.3 (2)
C3—C4—C5—C6	0.8 (4)	C2—C1—N1—O2	−11.6 (3)
C2—C1—C6—C5	0.0 (4)	C6—C1—N1—O1	−11.4 (4)
N1—C1—C6—C5	−179.9 (2)	C2—C1—N1—O1	168.7 (3)

(300) 1,3-dinitrobenzene

Crystal data

C6H4N2O4	Dx = 1.569 Mg m^−3
Mr = 168.11	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 739 reflections
a = 14.084 (4) Å	θ = 3.3–18.7°
b = 13.292 (4) Å	µ = 0.14 mm^−1
c = 3.802 (1) Å	T = 300 K
V = 711.8 (3) Å^3	Prism, colourless
Z = 4	0.72 × 0.33 × 0.23 mm
F(000) = 344

Data collection

KUMA Difffraction KM4CCD diffractometer	1177 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 31.1°, θmin = 3.3°
ω scan	h = −20→20
5456 measured reflections	k = −19→19
1486 independent reflections	l = −3→5

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.080	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.238	Calculated w = 1/[σ^2(Fo^2) + (0.1144P)^2 + 0.1108P] where P = (Fo^2 + 2Fc^2)/3
S = 1.20	(Δ/σ)max < 0.001
1486 reflections	Δρmax = 0.25 e Å^−3
109 parameters	Δρmin = −0.33 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 3 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3658 (2)	0.8609 (2)	0.1919 (11)	0.0454 (7)
C2	0.4494 (2)	0.8203 (2)	0.3163 (9)	0.0466 (7)
H2	0.4974	0.8603	0.4095	0.056*
C3	0.4579 (2)	0.7167 (3)	0.2947 (12)	0.0499 (8)
C4	0.3859 (3)	0.6562 (3)	0.1637 (14)	0.0643 (10)
H4	0.3932	0.5867	0.1546	0.077*
C5	0.3029 (2)	0.7013 (3)	0.0464 (14)	0.0642 (11)
H5	0.2538	0.6616	−0.0405	0.077*
C6	0.2928 (2)	0.8039 (3)	0.0577 (12)	0.0563 (9)
H6	0.2376	0.8343	−0.0238	0.068*
N1	0.3538 (2)	0.9703 (2)	0.2061 (12)	0.0660 (9)
N2	0.5462 (3)	0.6720 (3)	0.4234 (13)	0.0744 (11)
O1	0.2861 (3)	1.0070 (2)	0.0531 (18)	0.1129 (16)
O2	0.4113 (3)	1.0203 (2)	0.3696 (14)	0.0948 (13)
O3	0.6010 (3)	0.7246 (4)	0.5850 (16)	0.1042 (15)
O4	0.5618 (3)	0.5846 (3)	0.348 (2)	0.133 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0466 (15)	0.0460 (14)	0.0435 (14)	0.0012 (11)	0.0053 (13)	−0.0018 (14)
C2	0.0400 (14)	0.0529 (17)	0.0468 (16)	−0.0089 (11)	0.0003 (14)	0.0008 (15)
C3	0.0428 (15)	0.0542 (17)	0.0529 (18)	0.0017 (12)	0.0035 (14)	0.0062 (18)
C4	0.073 (2)	0.0472 (17)	0.073 (3)	−0.0081 (15)	0.013 (2)	−0.002 (2)
C5	0.0539 (19)	0.068 (2)	0.070 (3)	−0.0192 (16)	0.000 (2)	−0.012 (2)
C6	0.0416 (15)	0.074 (2)	0.0529 (19)	−0.0026 (14)	−0.0026 (15)	−0.0006 (19)
N1	0.071 (2)	0.0582 (17)	0.069 (2)	0.0100 (15)	0.0096 (19)	0.0032 (18)
N2	0.0566 (19)	0.085 (3)	0.081 (3)	0.0206 (17)	0.0065 (19)	0.022 (2)
O1	0.126 (3)	0.082 (2)	0.131 (4)	0.046 (2)	−0.025 (3)	0.003 (3)
O2	0.107 (2)	0.0563 (17)	0.121 (4)	−0.0109 (16)	−0.007 (3)	−0.016 (2)
O3	0.0566 (17)	0.141 (3)	0.115 (4)	0.0212 (19)	−0.026 (2)	0.009 (3)
O4	0.115 (3)	0.084 (3)	0.199 (7)	0.044 (2)	−0.004 (4)	0.027 (4)

Geometric parameters (Å, º)

C1—C6	1.375 (5)	C4—C5	1.387 (6)
C1—C2	1.379 (5)	C5—C6	1.372 (6)
C1—N1	1.465 (4)	N1—O2	1.218 (5)
C2—C3	1.385 (5)	N1—O1	1.219 (5)
C3—C4	1.386 (6)	N2—O3	1.208 (6)
C3—N2	1.463 (5)	N2—O4	1.216 (6)
C6—C1—C2	123.3 (3)	C6—C5—C4	120.4 (3)
C6—C1—N1	118.3 (3)	C5—C6—C1	118.8 (3)
C2—C1—N1	118.3 (3)	O2—N1—O1	123.1 (4)
C1—C2—C3	116.3 (3)	O2—N1—C1	118.9 (3)
C2—C3—C4	122.3 (3)	O1—N1—C1	118.0 (4)
C2—C3—N2	117.2 (3)	O3—N2—O4	123.8 (4)
C4—C3—N2	120.4 (3)	O3—N2—C3	118.5 (4)
C3—C4—C5	118.8 (3)	O4—N2—C3	117.6 (5)
C6—C1—C2—C3	1.1 (6)	N1—C1—C6—C5	−179.4 (4)
N1—C1—C2—C3	−179.5 (3)	C6—C1—N1—O2	169.4 (5)
C1—C2—C3—C4	−1.5 (5)	C2—C1—N1—O2	−10.1 (6)
C1—C2—C3—N2	179.7 (4)	C6—C1—N1—O1	−10.4 (6)
C2—C3—C4—C5	0.8 (7)	C2—C1—N1—O1	170.1 (5)
N2—C3—C4—C5	179.5 (4)	C2—C3—N2—O3	10.2 (7)
C3—C4—C5—C6	0.5 (7)	C4—C3—N2—O3	−168.6 (5)
C4—C5—C6—C1	−0.9 (7)	C2—C3—N2—O4	−166.8 (5)
C2—C1—C6—C5	0.1 (6)	C4—C3—N2—O4	14.3 (7)