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The title compound packs with two crystallographically independent mol­ecules, both symmetry 1, with the same bond lengths and angles within experimental error. The mol­ecules form a four-membered cyclamer held together by I...CN intermolecular Lewis acid–base interactions. The two independent N...I distances are 3.263 (6) and 3.344 (6) Å. The independent mol­ecules are not related by any pseudosymmetry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010923/om6026sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010923/om6026Isup2.hkl
Contains datablock I

CCDC reference: 170896

Key indicators

  • Single-crystal X-ray study
  • T = 174 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.043
  • wR factor = 0.109
  • Data-to-parameter ratio = 14.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(11) - C(17) = 1.45 Ang. PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(21) - C(27) = 1.44 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

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).

Experimental top

The compound was obtained from Lancaster Synthesis, Inc. The crystals grew as plates from acetone, with {001} as the prominent form.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The two independent C6H3F(CN)I molecules. Displacement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. The packing of C6H3F(CN)I. View along the b axis. The CN···I interactions are shown as heavy dashed lines. One tetrameric cyclamer can be traced out in the figure. The light dashed lines show the N···H and F···H interactions.
2-fluoro-6-iodobenzonitrile top
Crystal data top
C7H3FINZ = 4
Mr = 247.00F(000) = 456
Triclinic, P1Dx = 2.099 Mg m3
a = 8.0270 (8) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.0435 (8) ÅCell parameters from 4333 reflections
c = 13.8493 (13) Åθ = 4.0–24.8°
α = 82.232 (2)°µ = 4.04 mm1
β = 82.359 (2)°T = 174 K
γ = 62.242 (2)°Plates, colorless
V = 781.52 (15) Å30.40 × 0.40 × 0.10 mm
Data collection top
Siemens SMART area detector
diffractometer
2689 independent reflections
Radiation source: fine-focus sealed tube2241 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
ω scansθmax = 24.9°, θmin = 1.5°
Absorption correction: multi-scan
SADABS; Sheldrick, 1996; Blessing, 1995
h = 98
Tmin = 0.23, Tmax = 0.67k = 99
5149 measured reflectionsl = 1610
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-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 reflectionsΔρmax = 1.07 e Å3
182 parametersΔρmin = 1.49 e Å3
0 restraintsExtinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0042 (9)
Crystal data top
C7H3FINγ = 62.242 (2)°
Mr = 247.00V = 781.52 (15) Å3
Triclinic, P1Z = 4
a = 8.0270 (8) ÅMo Kα radiation
b = 8.0435 (8) ŵ = 4.04 mm1
c = 13.8493 (13) ÅT = 174 K
α = 82.232 (2)°0.40 × 0.40 × 0.10 mm
β = 82.359 (2)°
Data collection top
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 = 0.67Rint = 0.042
5149 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 0.98Δρmax = 1.07 e Å3
2689 reflectionsΔρmin = 1.49 e Å3
182 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C110.5937 (8)0.1731 (7)0.9932 (4)0.0323 (13)
C120.6131 (9)0.1171 (8)1.0923 (5)0.0405 (15)
C130.7563 (9)0.0514 (8)1.1275 (5)0.0422 (15)
H130.76490.08621.19560.051*
C140.8879 (9)0.1685 (8)1.0588 (5)0.0420 (15)
H140.98840.28461.08080.050*
C150.8744 (8)0.1183 (7)0.9584 (4)0.0356 (13)
H150.96460.20090.91320.043*
C160.7289 (7)0.0532 (7)0.9242 (4)0.0297 (12)
C170.4378 (8)0.3517 (8)0.9629 (5)0.0375 (14)
N10.3139 (8)0.4922 (7)0.9413 (5)0.0538 (15)
F10.4826 (6)0.2349 (6)1.1569 (3)0.0592 (11)
I10.71568 (5)0.13079 (5)0.77437 (3)0.03923 (19)
C210.0373 (7)0.7327 (7)0.5300 (4)0.0258 (11)
C220.1832 (8)0.7908 (7)0.4690 (4)0.0315 (12)
C230.3414 (8)0.7649 (8)0.4956 (5)0.0398 (15)
H230.43780.80540.45220.048*
C240.3556 (8)0.6783 (8)0.5873 (5)0.0448 (16)
H240.46340.65860.60700.054*
C250.2151 (9)0.6194 (8)0.6514 (5)0.0408 (15)
H250.22800.56100.71440.049*
C260.0560 (7)0.6463 (7)0.6230 (4)0.0286 (12)
C270.1227 (8)0.7652 (7)0.4949 (4)0.0276 (11)
N20.2498 (7)0.7919 (7)0.4631 (4)0.0398 (12)
F20.1647 (5)0.8751 (5)0.3794 (3)0.0446 (8)
I20.15372 (6)0.56019 (5)0.72122 (3)0.04304 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C110.032 (3)0.026 (2)0.037 (4)0.012 (2)0.000 (2)0.002 (2)
C120.043 (3)0.048 (3)0.031 (4)0.021 (3)0.007 (3)0.013 (3)
C130.056 (4)0.046 (3)0.025 (3)0.025 (3)0.005 (3)0.005 (3)
C140.045 (3)0.029 (3)0.046 (4)0.013 (3)0.007 (3)0.003 (3)
C150.031 (3)0.031 (3)0.034 (4)0.006 (2)0.002 (2)0.003 (2)
C160.028 (3)0.033 (3)0.029 (3)0.014 (2)0.002 (2)0.004 (2)
C170.033 (3)0.036 (3)0.043 (4)0.013 (3)0.004 (3)0.013 (3)
N10.045 (3)0.036 (3)0.071 (5)0.006 (3)0.014 (3)0.016 (3)
F10.062 (2)0.063 (2)0.039 (2)0.019 (2)0.0154 (19)0.0195 (19)
I10.0413 (3)0.0410 (3)0.0274 (3)0.01357 (19)0.00255 (17)0.00255 (17)
C210.023 (3)0.023 (2)0.030 (3)0.009 (2)0.001 (2)0.004 (2)
C220.032 (3)0.026 (3)0.034 (3)0.012 (2)0.001 (2)0.003 (2)
C230.027 (3)0.039 (3)0.055 (4)0.013 (2)0.004 (3)0.016 (3)
C240.029 (3)0.045 (3)0.060 (5)0.017 (3)0.013 (3)0.018 (3)
C250.046 (4)0.039 (3)0.033 (4)0.018 (3)0.015 (3)0.010 (3)
C260.033 (3)0.027 (2)0.022 (3)0.011 (2)0.001 (2)0.007 (2)
C270.030 (3)0.030 (3)0.023 (3)0.013 (2)0.004 (2)0.002 (2)
N20.036 (3)0.045 (3)0.042 (3)0.023 (2)0.008 (2)0.005 (2)
F20.048 (2)0.056 (2)0.033 (2)0.0261 (17)0.0154 (16)0.0071 (16)
I20.0549 (3)0.0411 (3)0.0282 (3)0.0165 (2)0.01199 (19)0.00089 (17)
Geometric parameters (Å, º) top
C11—C121.391 (9)C21—C221.397 (8)
C11—C161.421 (7)C21—C261.402 (7)
C11—C171.452 (8)C21—C271.437 (8)
C12—F11.360 (7)C22—F21.357 (7)
C12—C131.384 (9)C22—C231.375 (8)
C13—C141.399 (9)C23—C241.381 (10)
C13—H130.9500C23—H230.9500
C14—C151.398 (9)C24—C251.393 (10)
C14—H140.9500C24—H240.9500
C15—C161.400 (7)C25—C261.390 (8)
C15—H150.9500C25—H250.9500
C16—I12.087 (6)C26—I22.106 (6)
C17—N11.139 (7)C27—N21.158 (7)
C12—C11—C16118.7 (5)C22—C21—C26117.8 (5)
C12—C11—C17119.6 (5)C22—C21—C27118.6 (5)
C16—C11—C17121.8 (6)C26—C21—C27123.6 (5)
F1—C12—C13119.2 (6)F2—C22—C23119.5 (5)
F1—C12—C11117.5 (5)F2—C22—C21117.5 (5)
C13—C12—C11123.3 (5)C23—C22—C21123.0 (6)
C12—C13—C14117.5 (6)C22—C23—C24118.0 (6)
C12—C13—H13121.3C22—C23—H23121.0
C14—C13—H13121.3C24—C23—H23121.0
C15—C14—C13121.3 (5)C23—C24—C25121.3 (6)
C15—C14—H14119.3C23—C24—H24119.3
C13—C14—H14119.3C25—C24—H24119.3
C14—C15—C16120.4 (5)C26—C25—C24119.8 (6)
C14—C15—H15119.8C26—C25—H25120.1
C16—C15—H15119.8C24—C25—H25120.1
C15—C16—C11118.8 (5)C25—C26—C21120.1 (6)
C15—C16—I1120.0 (4)C25—C26—I2119.5 (4)
C11—C16—I1121.1 (4)C21—C26—I2120.4 (4)
N1—C17—C11178.4 (7)N2—C27—C21177.5 (6)

Experimental details

Crystal data
Chemical formulaC7H3FIN
Mr247.00
Crystal system, space groupTriclinic, 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)
V3)781.52 (15)
Z4
Radiation typeMo Kα
µ (mm1)4.04
Crystal size (mm)0.40 × 0.40 × 0.10
Data collection
DiffractometerSiemens SMART area detector
diffractometer
Absorption correctionMulti-scan
SADABS; Sheldrick, 1996; Blessing, 1995
Tmin, Tmax0.23, 0.67
No. of measured, independent and
observed [I > 2σ(I)] reflections
5149, 2689, 2241
Rint0.042
(sin θ/λ)max1)0.592
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.109, 0.98
No. of reflections2689
No. of parameters182
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.07, 1.49

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXTL (Sheldrick, 1994), SHELXTL.

Distances and angles (Å, °) in the CN···IC contacts top
NICN···IN···IN···IC
N1I2119.0 (5)3.344 (6)154.9 (6)
N2I1i114.9 (5)3.267 (6)172.6 (7)
%T {σymcodesfn (i) $ 1-x, 1-y, 1-z$.}
Intermolecular hydrogen contacts (Å, °) C-H···X-Y top
CHXYC-HH···XC···XC-H···XH···X-Y
C13H13F2iC22i0.952.633.550 (7)164.5144
C25H25F1iiC12ii0.952.603.164 (6)119175
C15H15N1iiiC17iii0.952.773.464 (7)130167
C23H23N2ivC27iv0.952.633.274 (7)134160
%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$.}
 

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