Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010923/om6026sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010923/om6026Isup2.hkl |
CCDC reference: 170896
The compound was obtained from Lancaster Synthesis, Inc. The crystals grew as plates from acetone, with {001} as the prominent form.
The matrix (110/110/001) converts the triclinic unit cell to a C-centered cell that is metrically close to monoclinic. However, if the symmetry is assumed to be monoclinic, Rint = 0.432, which rules out the monoclinic alternative.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1994); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C7H3FIN | Z = 4 |
Mr = 247.00 | F(000) = 456 |
Triclinic, P1 | Dx = 2.099 Mg m−3 |
a = 8.0270 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.0435 (8) Å | Cell parameters from 4333 reflections |
c = 13.8493 (13) Å | θ = 4.0–24.8° |
α = 82.232 (2)° | µ = 4.04 mm−1 |
β = 82.359 (2)° | T = 174 K |
γ = 62.242 (2)° | Plates, colorless |
V = 781.52 (15) Å3 | 0.40 × 0.40 × 0.10 mm |
Siemens SMART area detector diffractometer | 2689 independent reflections |
Radiation source: fine-focus sealed tube | 2241 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans | θmax = 24.9°, θmin = 1.5° |
Absorption correction: multi-scan SADABS; Sheldrick, 1996; Blessing, 1995 | h = −9→8 |
Tmin = 0.23, Tmax = 0.67 | k = −9→9 |
5149 measured reflections | l = −16→10 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0625P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max = 0.002 |
2689 reflections | Δρmax = 1.07 e Å−3 |
182 parameters | Δρmin = −1.49 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0042 (9) |
C7H3FIN | γ = 62.242 (2)° |
Mr = 247.00 | V = 781.52 (15) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.0270 (8) Å | Mo Kα radiation |
b = 8.0435 (8) Å | µ = 4.04 mm−1 |
c = 13.8493 (13) Å | T = 174 K |
α = 82.232 (2)° | 0.40 × 0.40 × 0.10 mm |
β = 82.359 (2)° |
Siemens SMART area detector diffractometer | 2689 independent reflections |
Absorption correction: multi-scan SADABS; Sheldrick, 1996; Blessing, 1995 | 2241 reflections with I > 2σ(I) |
Tmin = 0.23, Tmax = 0.67 | Rint = 0.042 |
5149 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 0.98 | Δρmax = 1.07 e Å−3 |
2689 reflections | Δρmin = −1.49 e Å−3 |
182 parameters |
x | y | z | Uiso*/Ueq | ||
C11 | 0.5937 (8) | 0.1731 (7) | 0.9932 (4) | 0.0323 (13) | |
C12 | 0.6131 (9) | 0.1171 (8) | 1.0923 (5) | 0.0405 (15) | |
C13 | 0.7563 (9) | −0.0514 (8) | 1.1275 (5) | 0.0422 (15) | |
H13 | 0.7649 | −0.0862 | 1.1956 | 0.051* | |
C14 | 0.8879 (9) | −0.1685 (8) | 1.0588 (5) | 0.0420 (15) | |
H14 | 0.9884 | −0.2846 | 1.0808 | 0.050* | |
C15 | 0.8744 (8) | −0.1183 (7) | 0.9584 (4) | 0.0356 (13) | |
H15 | 0.9646 | −0.2009 | 0.9132 | 0.043* | |
C16 | 0.7289 (7) | 0.0532 (7) | 0.9242 (4) | 0.0297 (12) | |
C17 | 0.4378 (8) | 0.3517 (8) | 0.9629 (5) | 0.0375 (14) | |
N1 | 0.3139 (8) | 0.4922 (7) | 0.9413 (5) | 0.0538 (15) | |
F1 | 0.4826 (6) | 0.2349 (6) | 1.1569 (3) | 0.0592 (11) | |
I1 | 0.71568 (5) | 0.13079 (5) | 0.77437 (3) | 0.03923 (19) | |
C21 | −0.0373 (7) | 0.7327 (7) | 0.5300 (4) | 0.0258 (11) | |
C22 | −0.1832 (8) | 0.7908 (7) | 0.4690 (4) | 0.0315 (12) | |
C23 | −0.3414 (8) | 0.7649 (8) | 0.4956 (5) | 0.0398 (15) | |
H23 | −0.4378 | 0.8054 | 0.4522 | 0.048* | |
C24 | −0.3556 (8) | 0.6783 (8) | 0.5873 (5) | 0.0448 (16) | |
H24 | −0.4634 | 0.6586 | 0.6070 | 0.054* | |
C25 | −0.2151 (9) | 0.6194 (8) | 0.6514 (5) | 0.0408 (15) | |
H25 | −0.2280 | 0.5610 | 0.7144 | 0.049* | |
C26 | −0.0560 (7) | 0.6463 (7) | 0.6230 (4) | 0.0286 (12) | |
C27 | 0.1227 (8) | 0.7652 (7) | 0.4949 (4) | 0.0276 (11) | |
N2 | 0.2498 (7) | 0.7919 (7) | 0.4631 (4) | 0.0398 (12) | |
F2 | −0.1647 (5) | 0.8751 (5) | 0.3794 (3) | 0.0446 (8) | |
I2 | 0.15372 (6) | 0.56019 (5) | 0.72122 (3) | 0.04304 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C11 | 0.032 (3) | 0.026 (2) | 0.037 (4) | −0.012 (2) | 0.000 (2) | −0.002 (2) |
C12 | 0.043 (3) | 0.048 (3) | 0.031 (4) | −0.021 (3) | 0.007 (3) | −0.013 (3) |
C13 | 0.056 (4) | 0.046 (3) | 0.025 (3) | −0.025 (3) | −0.005 (3) | 0.005 (3) |
C14 | 0.045 (3) | 0.029 (3) | 0.046 (4) | −0.013 (3) | −0.007 (3) | 0.003 (3) |
C15 | 0.031 (3) | 0.031 (3) | 0.034 (4) | −0.006 (2) | 0.002 (2) | −0.003 (2) |
C16 | 0.028 (3) | 0.033 (3) | 0.029 (3) | −0.014 (2) | −0.002 (2) | −0.004 (2) |
C17 | 0.033 (3) | 0.036 (3) | 0.043 (4) | −0.013 (3) | −0.004 (3) | −0.013 (3) |
N1 | 0.045 (3) | 0.036 (3) | 0.071 (5) | −0.006 (3) | −0.014 (3) | −0.016 (3) |
F1 | 0.062 (2) | 0.063 (2) | 0.039 (2) | −0.019 (2) | 0.0154 (19) | −0.0195 (19) |
I1 | 0.0413 (3) | 0.0410 (3) | 0.0274 (3) | −0.01357 (19) | −0.00255 (17) | 0.00255 (17) |
C21 | 0.023 (3) | 0.023 (2) | 0.030 (3) | −0.009 (2) | 0.001 (2) | −0.004 (2) |
C22 | 0.032 (3) | 0.026 (3) | 0.034 (3) | −0.012 (2) | −0.001 (2) | −0.003 (2) |
C23 | 0.027 (3) | 0.039 (3) | 0.055 (4) | −0.013 (2) | −0.004 (3) | −0.016 (3) |
C24 | 0.029 (3) | 0.045 (3) | 0.060 (5) | −0.017 (3) | 0.013 (3) | −0.018 (3) |
C25 | 0.046 (4) | 0.039 (3) | 0.033 (4) | −0.018 (3) | 0.015 (3) | −0.010 (3) |
C26 | 0.033 (3) | 0.027 (2) | 0.022 (3) | −0.011 (2) | 0.001 (2) | −0.007 (2) |
C27 | 0.030 (3) | 0.030 (3) | 0.023 (3) | −0.013 (2) | −0.004 (2) | −0.002 (2) |
N2 | 0.036 (3) | 0.045 (3) | 0.042 (3) | −0.023 (2) | −0.008 (2) | 0.005 (2) |
F2 | 0.048 (2) | 0.056 (2) | 0.033 (2) | −0.0261 (17) | −0.0154 (16) | 0.0071 (16) |
I2 | 0.0549 (3) | 0.0411 (3) | 0.0282 (3) | −0.0165 (2) | −0.01199 (19) | 0.00089 (17) |
C11—C12 | 1.391 (9) | C21—C22 | 1.397 (8) |
C11—C16 | 1.421 (7) | C21—C26 | 1.402 (7) |
C11—C17 | 1.452 (8) | C21—C27 | 1.437 (8) |
C12—F1 | 1.360 (7) | C22—F2 | 1.357 (7) |
C12—C13 | 1.384 (9) | C22—C23 | 1.375 (8) |
C13—C14 | 1.399 (9) | C23—C24 | 1.381 (10) |
C13—H13 | 0.9500 | C23—H23 | 0.9500 |
C14—C15 | 1.398 (9) | C24—C25 | 1.393 (10) |
C14—H14 | 0.9500 | C24—H24 | 0.9500 |
C15—C16 | 1.400 (7) | C25—C26 | 1.390 (8) |
C15—H15 | 0.9500 | C25—H25 | 0.9500 |
C16—I1 | 2.087 (6) | C26—I2 | 2.106 (6) |
C17—N1 | 1.139 (7) | C27—N2 | 1.158 (7) |
C12—C11—C16 | 118.7 (5) | C22—C21—C26 | 117.8 (5) |
C12—C11—C17 | 119.6 (5) | C22—C21—C27 | 118.6 (5) |
C16—C11—C17 | 121.8 (6) | C26—C21—C27 | 123.6 (5) |
F1—C12—C13 | 119.2 (6) | F2—C22—C23 | 119.5 (5) |
F1—C12—C11 | 117.5 (5) | F2—C22—C21 | 117.5 (5) |
C13—C12—C11 | 123.3 (5) | C23—C22—C21 | 123.0 (6) |
C12—C13—C14 | 117.5 (6) | C22—C23—C24 | 118.0 (6) |
C12—C13—H13 | 121.3 | C22—C23—H23 | 121.0 |
C14—C13—H13 | 121.3 | C24—C23—H23 | 121.0 |
C15—C14—C13 | 121.3 (5) | C23—C24—C25 | 121.3 (6) |
C15—C14—H14 | 119.3 | C23—C24—H24 | 119.3 |
C13—C14—H14 | 119.3 | C25—C24—H24 | 119.3 |
C14—C15—C16 | 120.4 (5) | C26—C25—C24 | 119.8 (6) |
C14—C15—H15 | 119.8 | C26—C25—H25 | 120.1 |
C16—C15—H15 | 119.8 | C24—C25—H25 | 120.1 |
C15—C16—C11 | 118.8 (5) | C25—C26—C21 | 120.1 (6) |
C15—C16—I1 | 120.0 (4) | C25—C26—I2 | 119.5 (4) |
C11—C16—I1 | 121.1 (4) | C21—C26—I2 | 120.4 (4) |
N1—C17—C11 | 178.4 (7) | N2—C27—C21 | 177.5 (6) |
Experimental details
Crystal data | |
Chemical formula | C7H3FIN |
Mr | 247.00 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 174 |
a, b, c (Å) | 8.0270 (8), 8.0435 (8), 13.8493 (13) |
α, β, γ (°) | 82.232 (2), 82.359 (2), 62.242 (2) |
V (Å3) | 781.52 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.04 |
Crystal size (mm) | 0.40 × 0.40 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART area detector diffractometer |
Absorption correction | Multi-scan SADABS; Sheldrick, 1996; Blessing, 1995 |
Tmin, Tmax | 0.23, 0.67 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5149, 2689, 2241 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.592 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.109, 0.98 |
No. of reflections | 2689 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.07, −1.49 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXTL (Sheldrick, 1994), SHELXTL.
N | I | CN···I | N···I | N···IC |
N1 | I2 | 119.0 (5) | 3.344 (6) | 154.9 (6) |
N2 | I1i | 114.9 (5) | 3.267 (6) | 172.6 (7) |
%T {σymcodesfn (i) $ 1-x, 1-y, 1-z$.} |
C | H | X | Y | C-H | H···X | C···X | C-H···X | H···X-Y |
C13 | H13 | F2i | C22i | 0.95 | 2.63 | 3.550 (7) | 164.5 | 144 |
C25 | H25 | F1ii | C12ii | 0.95 | 2.60 | 3.164 (6) | 119 | 175 |
C15 | H15 | N1iii | C17iii | 0.95 | 2.77 | 3.464 (7) | 130 | 167 |
C23 | H23 | N2iv | C27iv | 0.95 | 2.63 | 3.274 (7) | 134 | 160 |
%T {σymcodesfn (i) $ 1+x,y-1,1+z$; (ii) $ -x,1-y,2-z$; (iii) $ 1_x,y-1,z$; (iv) $ x-1,y,z$.} |
In the structure of p-iodobenzonitrile (Schlemper & Britton, 1965; Desiraju & Harlow, 1989) the CN group on one molecule points directly toward the I atom in the next molecule giving a linear C—I···NC arrangement. Similar arrangements, sometimes only approximately linear, occur in a number of other crystals (see Ojala et al., 1999), but in o-iodobenzonitrile (Lam & Britton, 1974) the important intermolecular interactions are between iodine atoms; there are no I···CN contacts at all. To look at another example of an o-iodobenzonitrile, the structure of 2-fluoro-6-iodobenzonitrile (I) has been determined and is reported here.
There are two molecules in the asymmetric unit; using the notation suggested by Zorky and coworkers (Zorky at al., 1967; Belsky et al., 1995; Zorky, 1996) the structure is in P1, Z = 4 (12). ORTEP drawings showing the atom labelling of the two independent molecules are given in Fig. 1. The bond lengths and angles are all normal and agree between the two molecules within experimental uncertainty.
A cyclamer is formed by the association of four monomers through weak intermolecular CN···I Lewis acid-base interactions. This can be seen in Fig. 2. These interactions are summarized in Table 1. The CN···I distances are what would be expected from the non-spherical radii of Nyburg & Faerman (1985). The angles at the iodine atoms are approximately linear, as expected for this type of interaction, but the angles at the nitrogen atoms are closer to trigonal. This is a less common arrangement but has been observed before (see Table 4 in Ojala et al., 1999).
In addition to the CN···I interactions, there are two weak C—H···F interactions and two weak C—H···N interactions. These are also shown in Fig. 2. The metric data for these interactions are given in Table 2. None of the four interaction distances is especially short; they are very weak interactions. Nevertheless, they all involve attractive interactions and play their part in the overall packing. For discussions of C—H···F interactions, see Howard et al. (1996); Dunitz & Taylor, 1997; Thalladi et al. (1998). For a more wide-ranging discussion of C—H···X interactions, see Desiraju & Steiner, 1999).