Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680100232X/ob6027sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680100232X/ob6027Isup2.hkl |
CCDC reference: 159848
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (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
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
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
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.
All H-atom positional and Uiso parameters were refined. C—H bond lengths lie between 0.91 (2) and 0.99 (2) Å.
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).
Fig. 1. An ORTEPII (Johnson, 1976) drawing of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
C14H16Cl2N2O2 | F(000) = 328 |
Mr = 315.19 | Dx = 1.565 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 5.9247 (7) Å | θ = 18.5–25.3° |
b = 13.5925 (11) Å | µ = 0.49 mm−1 |
c = 8.3407 (7) Å | T = 100 K |
β = 95.452 (8)° | Prism, colourless |
V = 668.7 (7) Å3 | 0.18 × 0.16 × 0.12 mm |
Z = 2 |
Enraf-Nonius CAD-4 diffractometer | 1076 reflections with I > 2σ(I) |
Radiation source: X-ray tube | Rint = 0.025 |
Graphite monochromator | θmax = 26.3°, θmin = 2.0° |
θ/2θ scans | h = −7→7 |
Absorption correction: ψ scan (North et al., 1968) | k = −16→0 |
Tmin = 0.920, Tmax = 0.968 | l = 0→10 |
1527 measured reflections | 3 standard reflections every 120 min |
1364 independent reflections | intensity decay: none |
Refinement on F2 | 0 constraints |
Least-squares matrix: full | All 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 = 1.02 | Δρmax = 0.32 e Å−3 |
1364 reflections | Δρmin = −0.24 e Å−3 |
132 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0055 (12) |
C14H16Cl2N2O2 | V = 668.7 (7) Å3 |
Mr = 315.19 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.9247 (7) Å | µ = 0.49 mm−1 |
b = 13.5925 (11) Å | T = 100 K |
c = 8.3407 (7) Å | 0.18 × 0.16 × 0.12 mm |
β = 95.452 (8)° |
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 = 0.968 | 3 standard reflections every 120 min |
1527 measured reflections | intensity decay: none |
1364 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.083 | All H-atom parameters refined |
S = 1.02 | Δρmax = 0.32 e Å−3 |
1364 reflections | Δρmin = −0.24 e Å−3 |
132 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.07717 (8) | 0.54022 (4) | 0.29490 (7) | 0.0200 (2) | |
O2 | 0.3945 (2) | 0.39708 (10) | 0.58190 (10) | 0.0185 (4) | |
N3 | 0.4637 (3) | 0.45571 (11) | 0.47899 (10) | 0.0142 (4) | |
C4 | 0.5147 (3) | 0.30110 (15) | 0.1130 (2) | 0.0206 (6) | |
C5 | 0.2828 (3) | 0.47482 (14) | 0.1910 (2) | 0.0144 (5) | |
C6 | 0.1749 (3) | 0.38287 (15) | 0.1062 (2) | 0.0176 (5) | |
C7 | 0.4425 (3) | 0.31681 (14) | 0.2817 (2) | 0.0176 (5) | |
C8 | 0.4774 (3) | 0.42849 (14) | 0.3083 (2) | 0.0144 (5) | |
C9 | 0.3574 (3) | 0.34093 (15) | 0.0093 (2) | 0.0195 (6) | |
C10 | 0.1834 (3) | 0.30986 (15) | 0.2465 (2) | 0.0181 (5) | |
H1 | 0.652 (5) | 0.275 (2) | 0.090 (3) | 0.036 (7)* | |
H2 | 0.345 (3) | 0.5219 (14) | 0.121 (2) | 0.004 (4)* | |
H3 | 0.030 (4) | 0.3962 (16) | 0.048 (3) | 0.020 (6)* | |
H4 | 0.511 (4) | 0.2745 (16) | 0.364 (2) | 0.014 (5)* | |
H5 | 0.616 (4) | 0.4480 (15) | 0.282 (2) | 0.013 (5)* | |
H6 | 0.358 (4) | 0.3484 (17) | −0.103 (3) | 0.022 (6)* | |
H7 | 0.138 (4) | 0.2416 (17) | 0.216 (3) | 0.016 (5)* | |
H8 | 0.105 (4) | 0.3324 (15) | 0.336 (2) | 0.012 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0176 (2) | 0.0217 (3) | 0.0205 (3) | 0.0061 (2) | 0.0000 (2) | −0.0011 (2) |
O2 | 0.0218 (7) | 0.0170 (7) | 0.0167 (7) | −0.0029 (6) | 0.0012 (5) | 0.0028 (5) |
N3 | 0.0143 (7) | 0.0135 (7) | 0.0142 (7) | 0.0001 (6) | −0.0021 (6) | −0.0005 (6) |
C4 | 0.0213 (10) | 0.0174 (10) | 0.0234 (10) | −0.0005 (8) | 0.0037 (8) | −0.0074 (8) |
C5 | 0.0150 (8) | 0.0147 (9) | 0.0137 (9) | 0.0013 (7) | 0.0018 (7) | 0.0010 (7) |
C6 | 0.0169 (9) | 0.0209 (10) | 0.0142 (9) | −0.0022 (8) | −0.0020 (7) | −0.0014 (8) |
C7 | 0.0216 (10) | 0.0138 (9) | 0.0167 (9) | 0.0029 (8) | −0.0025 (7) | −0.0012 (8) |
C8 | 0.0133 (8) | 0.0158 (9) | 0.0138 (9) | −0.0002 (7) | −0.0007 (7) | −0.0020 (7) |
C9 | 0.0244 (10) | 0.0178 (10) | 0.0165 (10) | −0.0062 (8) | 0.0034 (8) | −0.0049 (8) |
C10 | 0.0215 (9) | 0.0164 (10) | 0.0165 (9) | −0.0046 (8) | 0.0022 (8) | −0.0021 (8) |
Cl1—C5 | 1.796 (2) | C7—C8 | 1.545 (3) |
O2—N3 | 1.268 (2) | C7—C10 | 1.538 (3) |
N3—C8 | 1.481 (2) | C4—H1 | 0.92 (3) |
N3—N3i | 1.315 (2) | C5—H2 | 0.963 (18) |
C4—C7 | 1.524 (3) | C6—H3 | 0.96 (2) |
C4—C9 | 1.325 (3) | C7—H4 | 0.96 (2) |
C5—C6 | 1.544 (3) | C8—H5 | 0.91 (2) |
C5—C8 | 1.571 (3) | C9—H6 | 0.94 (2) |
C6—C9 | 1.522 (3) | C10—H7 | 0.99 (2) |
C6—C10 | 1.531 (3) | C10—H8 | 0.97 (2) |
Cl1···N3 | 2.873 (3) | C6···H4ix | 3.04 (2) |
Cl1···O2i | 3.312 (3) | C9···H2x | 2.851 (18) |
Cl1···N3i | 3.160 (3) | C9···H4ix | 2.77 (2) |
Cl1···O2ii | 3.184 (3) | C9···H5 | 2.996 (19) |
Cl1···H5iii | 3.00 (2) | H1···O2viii | 2.75 (3) |
Cl1···H8 | 2.85 (2) | H1···H8viii | 2.57 (3) |
Cl1···H3iv | 3.00 (2) | H2···C9x | 2.851 (18) |
O2···C10 | 3.183 (3) | H2···H6x | 2.51 (3) |
O2···Cl1ii | 3.184 (3) | H3···Cl1iv | 3.00 (2) |
O2···Cl1i | 3.312 (3) | H4···O2 | 2.61 (2) |
O2···C5i | 3.096 (3) | H4···C6vii | 3.04 (2) |
O2···H4 | 2.61 (2) | H4···C9vii | 2.77 (2) |
O2···H6v | 2.74 (2) | H5···Cl1xi | 3.00 (2) |
O2···H8 | 2.69 (2) | H5···C9 | 2.996 (19) |
O2···H5i | 2.40 (2) | H5···O2i | 2.40 (2) |
O2···H1vi | 2.75 (3) | H6···O2xii | 2.74 (2) |
O2···H7vii | 2.56 (2) | H6···H2x | 2.51 (3) |
N3···Cl1 | 2.873 (3) | H7···O2ix | 2.56 (2) |
N3···Cl1i | 3.160 (3) | H8···Cl1 | 2.85 (2) |
N3···H8 | 2.88 (2) | H8···O2 | 2.69 (2) |
C5···O2i | 3.096 (3) | H8···N3 | 2.88 (2) |
C10···O2 | 3.183 (3) | H8···C4vi | 3.025 (19) |
C4···H8viii | 3.025 (19) | H8···H1vi | 2.57 (3) |
O2—N3—C8 | 123.01 (14) | Cl1—C5—H2 | 106.3 (11) |
O2—N3—N3i | 120.92 (10) | C6—C5—H2 | 115.2 (11) |
N3i—N3—C8 | 116.02 (12) | C8—C5—H2 | 110.1 (11) |
C7—C4—C9 | 107.68 (16) | C5—C6—H3 | 112.9 (13) |
Cl1—C5—C6 | 110.55 (12) | C9—C6—H3 | 116.5 (15) |
Cl1—C5—C8 | 112.90 (11) | C10—C6—H3 | 118.1 (14) |
C6—C5—C8 | 102.00 (15) | C4—C7—H4 | 116.2 (12) |
C5—C6—C9 | 105.21 (15) | C8—C7—H4 | 116.5 (12) |
C5—C6—C10 | 101.13 (14) | C10—C7—H4 | 116.6 (14) |
C9—C6—C10 | 100.95 (15) | N3—C8—H5 | 107.0 (11) |
C4—C7—C8 | 102.99 (14) | C5—C8—H5 | 111.0 (12) |
C4—C7—C10 | 100.24 (13) | C7—C8—H5 | 111.3 (13) |
C8—C7—C10 | 101.84 (15) | C4—C9—H6 | 128.6 (15) |
N3—C8—C5 | 113.24 (15) | C6—C9—H6 | 123.9 (14) |
N3—C8—C7 | 111.39 (14) | C6—C10—H7 | 114.9 (14) |
C5—C8—C7 | 102.95 (14) | C6—C10—H8 | 113.7 (12) |
C4—C9—C6 | 107.29 (15) | C7—C10—H7 | 110.3 (14) |
C6—C10—C7 | 93.77 (14) | C7—C10—H8 | 112.2 (13) |
C7—C4—H1 | 125.1 (16) | H7—C10—H8 | 110.9 (19) |
C9—C4—H1 | 126.8 (16) | ||
O2—N3—C8—C5 | 104.52 (19) | C6—C5—C8—N3 | −123.96 (15) |
O2—N3—C8—C7 | −10.9 (2) | C6—C5—C8—C7 | −3.56 (16) |
N3i—N3—C8—C5 | −78.0 (2) | C8—C5—C6—C10 | 39.13 (16) |
N3i—N3—C8—C7 | 166.55 (15) | Cl1—C5—C8—N3 | −5.3 (2) |
O2—N3—N3i—O2i | 180.0 (4) | C5—C6—C10—C7 | −58.46 (15) |
O2—N3—N3i—C8i | −2.4 (3) | C5—C6—C9—C4 | 72.25 (19) |
C8—N3—N3i—O2i | 2.4 (3) | C10—C6—C9—C4 | −32.6 (2) |
C8—N3—N3i—C8i | −180.00 (15) | C9—C6—C10—C7 | 49.61 (16) |
C9—C4—C7—C10 | 33.6 (2) | C4—C7—C8—C5 | 70.61 (16) |
C7—C4—C9—C6 | −0.8 (2) | C10—C7—C8—N3 | 88.69 (16) |
C9—C4—C7—C8 | −71.17 (19) | C4—C7—C10—C6 | −49.76 (16) |
C8—C5—C6—C9 | −65.59 (16) | C8—C7—C10—C6 | 55.98 (15) |
Cl1—C5—C6—C9 | 174.11 (12) | C10—C7—C8—C5 | −32.97 (16) |
Cl1—C5—C6—C10 | −81.18 (14) | C4—C7—C8—N3 | −167.74 (14) |
Cl1—C5—C8—C7 | 115.09 (13) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x−1, y, z; (iv) −x, −y+1, −z; (v) x, y, z+1; (vi) x−1/2, −y+1/2, z+1/2; (vii) x+1/2, −y+1/2, z+1/2; (viii) x+1/2, −y+1/2, z−1/2; (ix) x−1/2, −y+1/2, z−1/2; (x) −x+1, −y+1, −z; (xi) x+1, y, z; (xii) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C14H16Cl2N2O2 |
Mr | 315.19 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 5.9247 (7), 13.5925 (11), 8.3407 (7) |
β (°) | 95.452 (8) |
V (Å3) | 668.7 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.49 |
Crystal size (mm) | 0.18 × 0.16 × 0.12 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.920, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1527, 1364, 1076 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.083, 1.02 |
No. of reflections | 1364 |
No. of parameters | 132 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 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).
Cl1—C5 | 1.796 (2) | N3—C8 | 1.481 (2) |
O2—N3 | 1.268 (2) | N3—N3i | 1.315 (2) |
O2—N3—C8 | 123.01 (14) | Cl1—C5—C8 | 112.90 (11) |
O2—N3—N3i | 120.92 (10) | N3—C8—C5 | 113.24 (15) |
N3i—N3—C8 | 116.02 (12) | N3—C8—C7 | 111.39 (14) |
Cl1—C5—C6 | 110.55 (12) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
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 C═C 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 N═N bond which connects two monomeric units into the dimer structure (Fig. 1). The norbornene cages are trans-oriented.