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The title compound, 1,2-bis(5-chloro­norbornen-6-yl)­diazene 1,2-dioxide, C14H16Cl2N2O2, has a crystallographic centre of symmetry. The norbornane cages are trans-oriented and the nitroso groups are in positions 3 and 6. This compound might be used as a starting point for the construction of two different polymeric structures due to the photochromism observed in the solid state.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680100232X/ob6027sup1.cif
Contains datablocks global, 1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680100232X/ob6027Isup2.hkl
Contains datablock I

CCDC reference: 159848

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.030
  • wR factor = 0.083
  • Data-to-parameter ratio = 10.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Amber Alert Alert Level B:
CELLV_02 Alert B The supplied cell volume s.u. differs from that calculated from the cell parameter s.u.'s by > 4 Calculated cell volume su = 1.11 Cell volume su given = 7.00
Yellow Alert Alert Level C:
PLAT_734 Alert C Contact Calc 3.3120(13), Rep 3.312(3) .... 2.31 s.u-Ratio CL1 -O2 1.555 3.666 PLAT_734 Alert C Contact Calc 3.1839(13), Rep 3.184(3) .... 2.31 s.u-Ratio CL1 -O2 1.555 3.566 PLAT_734 Alert C Contact Calc 3.1839(13), Rep 3.184(3) .... 2.31 s.u-Ratio O2 -CL1 1.555 3.566 PLAT_734 Alert C Contact Calc 3.3120(13), Rep 3.312(3) .... 2.31 s.u-Ratio O2 -CL1 1.555 3.666
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
4 Alert Level C = Please check

Comment top

Recently, we found that the monomer–dimer equilibrium of C-nitroso compounds could be used as a system for supramolecular self-assembly (see below, monomer–dimer equilibrium of C-nitroso compounds), because the azodioxyde dimer affords photochromism in the solid state (Vančik et al., 2001). Basic nitroso monomeric units convenient for the construction of supramolecular structures should have a rigid carbon skeleton with two azo groups which serve as chemical receptors oriented in proper spatial positions.

Here we propose the polymeric structures that may have nitroso groups on 2- and 6- (MOTIF 1) or on 3- and 6- (MOTIF 2) positions of the norbornane skeleton. Possibilities of such structures depend on the stereochemistry of the basic motif, such as the title structure, (I) (see below), which has only one azodioxide group. The CC double bond on each norbornene unit is a functionality on which additional nitroso groups, necessary for the polymer formation, could be added.

The inversion centre is located in the midpoint of the NN bond which connects two monomeric units into the dimer structure (Fig. 1). The norbornene cages are trans-oriented.

Experimental top

The title compound was prepared by direct addition of NOCl to norbornadiene (Ciattoni et al., 1964; Metzger et al., 1971, ibid. 1990; Miller, 1961). Crystals of (I) were obtained by evaporation from a dichloromethane solution containing a few drops of tetrahydrofuran at 277 K.

Refinement top

All H-atom positional and Uiso parameters were refined. C—H bond lengths lie between 0.91 (2) and 0.99 (2) Å.

Computing details top

Data collection: CAD-4 Software (Enraf Nonius, 1989); cell refinement: SET4 and CELDIM in CAD-4 Software (Enraf-Nonius, 1989); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SIR97 (Altomare et al.,1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. An ORTEPII (Johnson, 1976) drawing of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
5-chloro-6-nitroso-2-norbornene dimer or 1,2-bis(5-chloronorbornen-6-yl)diazene 1,2-dioxide top
Crystal data top
C14H16Cl2N2O2F(000) = 328
Mr = 315.19Dx = 1.565 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 5.9247 (7) Åθ = 18.5–25.3°
b = 13.5925 (11) ŵ = 0.49 mm1
c = 8.3407 (7) ÅT = 100 K
β = 95.452 (8)°Prism, colourless
V = 668.7 (7) Å30.18 × 0.16 × 0.12 mm
Z = 2
Data collection top
Enraf-Nonius CAD-4
diffractometer
1076 reflections with I > 2σ(I)
Radiation source: X-ray tubeRint = 0.025
Graphite monochromatorθmax = 26.3°, θmin = 2.0°
θ/2θ scansh = 77
Absorption correction: ψ scan
(North et al., 1968)
k = 160
Tmin = 0.920, Tmax = 0.968l = 010
1527 measured reflections3 standard reflections every 120 min
1364 independent reflections intensity decay: none
Refinement top
Refinement on F20 constraints
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.030 w = 1/[σ2(Fo2) + (0.0407P)2 + 0.4P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.083(Δ/σ)max = 0.011
S = 1.02Δρmax = 0.32 e Å3
1364 reflectionsΔρmin = 0.24 e Å3
132 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0055 (12)
Crystal data top
C14H16Cl2N2O2V = 668.7 (7) Å3
Mr = 315.19Z = 2
Monoclinic, P21/nMo Kα radiation
a = 5.9247 (7) ŵ = 0.49 mm1
b = 13.5925 (11) ÅT = 100 K
c = 8.3407 (7) Å0.18 × 0.16 × 0.12 mm
β = 95.452 (8)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
1076 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.025
Tmin = 0.920, Tmax = 0.9683 standard reflections every 120 min
1527 measured reflections intensity decay: none
1364 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.083All H-atom parameters refined
S = 1.02Δρmax = 0.32 e Å3
1364 reflectionsΔρmin = 0.24 e Å3
132 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

Examination of the data with PLATON (Spek, 1990) showed that there was no solvent accesible voids inside the structure.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.07717 (8)0.54022 (4)0.29490 (7)0.0200 (2)
O20.3945 (2)0.39708 (10)0.58190 (10)0.0185 (4)
N30.4637 (3)0.45571 (11)0.47899 (10)0.0142 (4)
C40.5147 (3)0.30110 (15)0.1130 (2)0.0206 (6)
C50.2828 (3)0.47482 (14)0.1910 (2)0.0144 (5)
C60.1749 (3)0.38287 (15)0.1062 (2)0.0176 (5)
C70.4425 (3)0.31681 (14)0.2817 (2)0.0176 (5)
C80.4774 (3)0.42849 (14)0.3083 (2)0.0144 (5)
C90.3574 (3)0.34093 (15)0.0093 (2)0.0195 (6)
C100.1834 (3)0.30986 (15)0.2465 (2)0.0181 (5)
H10.652 (5)0.275 (2)0.090 (3)0.036 (7)*
H20.345 (3)0.5219 (14)0.121 (2)0.004 (4)*
H30.030 (4)0.3962 (16)0.048 (3)0.020 (6)*
H40.511 (4)0.2745 (16)0.364 (2)0.014 (5)*
H50.616 (4)0.4480 (15)0.282 (2)0.013 (5)*
H60.358 (4)0.3484 (17)0.103 (3)0.022 (6)*
H70.138 (4)0.2416 (17)0.216 (3)0.016 (5)*
H80.105 (4)0.3324 (15)0.336 (2)0.012 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0176 (2)0.0217 (3)0.0205 (3)0.0061 (2)0.0000 (2)0.0011 (2)
O20.0218 (7)0.0170 (7)0.0167 (7)0.0029 (6)0.0012 (5)0.0028 (5)
N30.0143 (7)0.0135 (7)0.0142 (7)0.0001 (6)0.0021 (6)0.0005 (6)
C40.0213 (10)0.0174 (10)0.0234 (10)0.0005 (8)0.0037 (8)0.0074 (8)
C50.0150 (8)0.0147 (9)0.0137 (9)0.0013 (7)0.0018 (7)0.0010 (7)
C60.0169 (9)0.0209 (10)0.0142 (9)0.0022 (8)0.0020 (7)0.0014 (8)
C70.0216 (10)0.0138 (9)0.0167 (9)0.0029 (8)0.0025 (7)0.0012 (8)
C80.0133 (8)0.0158 (9)0.0138 (9)0.0002 (7)0.0007 (7)0.0020 (7)
C90.0244 (10)0.0178 (10)0.0165 (10)0.0062 (8)0.0034 (8)0.0049 (8)
C100.0215 (9)0.0164 (10)0.0165 (9)0.0046 (8)0.0022 (8)0.0021 (8)
Geometric parameters (Å, º) top
Cl1—C51.796 (2)C7—C81.545 (3)
O2—N31.268 (2)C7—C101.538 (3)
N3—C81.481 (2)C4—H10.92 (3)
N3—N3i1.315 (2)C5—H20.963 (18)
C4—C71.524 (3)C6—H30.96 (2)
C4—C91.325 (3)C7—H40.96 (2)
C5—C61.544 (3)C8—H50.91 (2)
C5—C81.571 (3)C9—H60.94 (2)
C6—C91.522 (3)C10—H70.99 (2)
C6—C101.531 (3)C10—H80.97 (2)
Cl1···N32.873 (3)C6···H4ix3.04 (2)
Cl1···O2i3.312 (3)C9···H2x2.851 (18)
Cl1···N3i3.160 (3)C9···H4ix2.77 (2)
Cl1···O2ii3.184 (3)C9···H52.996 (19)
Cl1···H5iii3.00 (2)H1···O2viii2.75 (3)
Cl1···H82.85 (2)H1···H8viii2.57 (3)
Cl1···H3iv3.00 (2)H2···C9x2.851 (18)
O2···C103.183 (3)H2···H6x2.51 (3)
O2···Cl1ii3.184 (3)H3···Cl1iv3.00 (2)
O2···Cl1i3.312 (3)H4···O22.61 (2)
O2···C5i3.096 (3)H4···C6vii3.04 (2)
O2···H42.61 (2)H4···C9vii2.77 (2)
O2···H6v2.74 (2)H5···Cl1xi3.00 (2)
O2···H82.69 (2)H5···C92.996 (19)
O2···H5i2.40 (2)H5···O2i2.40 (2)
O2···H1vi2.75 (3)H6···O2xii2.74 (2)
O2···H7vii2.56 (2)H6···H2x2.51 (3)
N3···Cl12.873 (3)H7···O2ix2.56 (2)
N3···Cl1i3.160 (3)H8···Cl12.85 (2)
N3···H82.88 (2)H8···O22.69 (2)
C5···O2i3.096 (3)H8···N32.88 (2)
C10···O23.183 (3)H8···C4vi3.025 (19)
C4···H8viii3.025 (19)H8···H1vi2.57 (3)
O2—N3—C8123.01 (14)Cl1—C5—H2106.3 (11)
O2—N3—N3i120.92 (10)C6—C5—H2115.2 (11)
N3i—N3—C8116.02 (12)C8—C5—H2110.1 (11)
C7—C4—C9107.68 (16)C5—C6—H3112.9 (13)
Cl1—C5—C6110.55 (12)C9—C6—H3116.5 (15)
Cl1—C5—C8112.90 (11)C10—C6—H3118.1 (14)
C6—C5—C8102.00 (15)C4—C7—H4116.2 (12)
C5—C6—C9105.21 (15)C8—C7—H4116.5 (12)
C5—C6—C10101.13 (14)C10—C7—H4116.6 (14)
C9—C6—C10100.95 (15)N3—C8—H5107.0 (11)
C4—C7—C8102.99 (14)C5—C8—H5111.0 (12)
C4—C7—C10100.24 (13)C7—C8—H5111.3 (13)
C8—C7—C10101.84 (15)C4—C9—H6128.6 (15)
N3—C8—C5113.24 (15)C6—C9—H6123.9 (14)
N3—C8—C7111.39 (14)C6—C10—H7114.9 (14)
C5—C8—C7102.95 (14)C6—C10—H8113.7 (12)
C4—C9—C6107.29 (15)C7—C10—H7110.3 (14)
C6—C10—C793.77 (14)C7—C10—H8112.2 (13)
C7—C4—H1125.1 (16)H7—C10—H8110.9 (19)
C9—C4—H1126.8 (16)
O2—N3—C8—C5104.52 (19)C6—C5—C8—N3123.96 (15)
O2—N3—C8—C710.9 (2)C6—C5—C8—C73.56 (16)
N3i—N3—C8—C578.0 (2)C8—C5—C6—C1039.13 (16)
N3i—N3—C8—C7166.55 (15)Cl1—C5—C8—N35.3 (2)
O2—N3—N3i—O2i180.0 (4)C5—C6—C10—C758.46 (15)
O2—N3—N3i—C8i2.4 (3)C5—C6—C9—C472.25 (19)
C8—N3—N3i—O2i2.4 (3)C10—C6—C9—C432.6 (2)
C8—N3—N3i—C8i180.00 (15)C9—C6—C10—C749.61 (16)
C9—C4—C7—C1033.6 (2)C4—C7—C8—C570.61 (16)
C7—C4—C9—C60.8 (2)C10—C7—C8—N388.69 (16)
C9—C4—C7—C871.17 (19)C4—C7—C10—C649.76 (16)
C8—C5—C6—C965.59 (16)C8—C7—C10—C655.98 (15)
Cl1—C5—C6—C9174.11 (12)C10—C7—C8—C532.97 (16)
Cl1—C5—C6—C1081.18 (14)C4—C7—C8—N3167.74 (14)
Cl1—C5—C8—C7115.09 (13)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+1; (iii) x1, y, z; (iv) x, y+1, z; (v) x, y, z+1; (vi) x1/2, y+1/2, z+1/2; (vii) x+1/2, y+1/2, z+1/2; (viii) x+1/2, y+1/2, z1/2; (ix) x1/2, y+1/2, z1/2; (x) x+1, y+1, z; (xi) x+1, y, z; (xii) x, y, z1.

Experimental details

Crystal data
Chemical formulaC14H16Cl2N2O2
Mr315.19
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)5.9247 (7), 13.5925 (11), 8.3407 (7)
β (°) 95.452 (8)
V3)668.7 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.49
Crystal size (mm)0.18 × 0.16 × 0.12
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.920, 0.968
No. of measured, independent and
observed [I > 2σ(I)] reflections
1527, 1364, 1076
Rint0.025
(sin θ/λ)max1)0.624
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.083, 1.02
No. of reflections1364
No. of parameters132
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.32, 0.24

Computer programs: CAD-4 Software (Enraf Nonius, 1989), SET4 and CELDIM in CAD-4 Software (Enraf-Nonius, 1989), HELENA (Spek, 1997), SIR97 (Altomare et al.,1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
Cl1—C51.796 (2)N3—C81.481 (2)
O2—N31.268 (2)N3—N3i1.315 (2)
O2—N3—C8123.01 (14)Cl1—C5—C8112.90 (11)
O2—N3—N3i120.92 (10)N3—C8—C5113.24 (15)
N3i—N3—C8116.02 (12)N3—C8—C7111.39 (14)
Cl1—C5—C6110.55 (12)
Symmetry code: (i) x+1, y+1, z+1.
 

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