Two symmetry-independent but geometrically similar, essentially planar molecules of the title compound, C
9H
8INO
4, are linked
via C—I
O=C interactions [I
O = 2.981 (6) and 3.006 (5) Å] into infinite chains running along the
b axis. The independent molecules alternate within the chain, so that only one independent chain is formed in the crystal structure.
Supporting information
CCDC reference: 651479
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.011 Å
- R factor = 0.050
- wR factor = 0.096
- Data-to-parameter ratio = 13.5
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT431_ALERT_2_A Short Inter HL..A Contact I1 .. O34 .. 2.98 Ang.
| Author Response: We agree that there are two unusally short intermolecular contacts
between I1..O34 and I2..O13 but these are the minimized structures. Since the
reaction was a bromo - iodo exchange, we investigated the possibility of the
Bromo derivative by both NMR and mass spectrometry and experimental evidence
supports the iodo derivative. The protons ortho to the halogen shift upon
coversion to the iodo-derivative and the mass spectrum (electrospray
ionization-poisitve ion mode) showed only two peaks at 344 (M + Na+) and 360
(M + K+). No molecular ion was observed in either postive or negative mode.
Also, no peaks that could be attributed to the Br-derivative were observed.
|
Alert level B
PLAT431_ALERT_2_B Short Inter HL..A Contact I2 .. O13 .. 3.01 Ang.
| Author Response: We agree that there are two unusally short intermolecular contacts
between I1..O34 and I2..O13 but these are the minimized structures. Since the
reaction was a bromo - iodo exchange, we investigated the possibility of the
Bromo derivative by both NMR and mass spectrometry and experimental evidence
supports the iodo derivative. The protons ortho to the halogen shift upon
coversion to the iodo-derivative and the mass spectrum (electrospray
ionization-poisitve ion mode) showed only two peaks at 344 (M + Na+) and 360
(M + K+). No molecular ion was observed in either postive or negative mode.
Also, no peaks that could be attributed to the Br-derivative were observed.
|
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.38
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 11
1 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 2005); software used to prepare material for publication: PLATON (Spek, 2003).
dimethyl 4-iodopyridine-2,6-dicarboxylate
top
Crystal data top
C9H8INO4 | Z = 4 |
Mr = 321.07 | F(000) = 616 |
Triclinic, P1 | Dx = 2.024 Mg m−3 |
Hall symbol: -P 1 | Melting point: 173 K |
a = 4.2120 (12) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.359 (2) Å | Cell parameters from 3723 reflections |
c = 19.236 (2) Å | θ = 1.6–25.3° |
α = 99.936 (5)° | µ = 3.03 mm−1 |
β = 94.326 (6)° | T = 173 K |
γ = 96.790 (6)° | Needle, yellow |
V = 1053.6 (4) Å3 | 0.08 × 0.04 × 0.02 mm |
Data collection top
Nonius KappaCCD diffractometer | 3723 independent reflections |
Radiation source: fine-focus sealed tube | 2296 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ω and φ scans | θmax = 25.3°, θmin = 1.6° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −5→5 |
Tmin = 0.793, Tmax = 0.942 | k = −14→15 |
5334 measured reflections | l = −22→22 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0255P)2 + 0.5615P] where P = (Fo2 + 2Fc2)/3 |
3723 reflections | (Δ/σ)max = 0.001 |
275 parameters | Δρmax = 1.08 e Å−3 |
0 restraints | Δρmin = −0.78 e Å−3 |
Special details top
Experimental. C9H8INO4: 1H NMR (300 MHz, CDCl3) δ 8.67 (s, 2H), 4.03 (s, 6H). C9H8BrNO4: 1H NMR (300 MHz, CDCl3) δ 8.48 (s, 2H), 4.05 (s, 6H) |
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 (Å2) top | x | y | z | Uiso*/Ueq | |
I1 | 0.73413 (12) | 0.45939 (4) | 0.22152 (3) | 0.03075 (19) | |
I2 | 0.02699 (12) | 0.06208 (4) | 0.71406 (3) | 0.0333 (2) | |
O8 | −0.2442 (13) | 0.0395 (4) | 0.0700 (3) | 0.0400 (16) | |
O11 | −0.1904 (13) | 0.2729 (4) | −0.0806 (3) | 0.0389 (16) | |
O13 | 0.0551 (14) | 0.0694 (5) | 0.1748 (3) | 0.0502 (18) | |
O14 | 0.1561 (15) | 0.4174 (5) | −0.0580 (3) | 0.054 (2) | |
O28 | −0.1482 (12) | 0.2288 (4) | 0.4081 (3) | 0.0365 (15) | |
O31 | 0.6008 (12) | 0.4504 (4) | 0.5677 (3) | 0.0321 (14) | |
O33 | −0.4145 (13) | 0.0875 (5) | 0.4358 (3) | 0.0428 (17) | |
O34 | 0.8312 (12) | 0.4006 (4) | 0.6636 (3) | 0.0333 (15) | |
N1 | 0.0042 (14) | 0.2205 (5) | 0.0411 (3) | 0.0235 (16) | |
N21 | 0.2139 (14) | 0.2712 (5) | 0.5325 (3) | 0.0230 (16) | |
C2 | 0.1335 (18) | 0.3126 (6) | 0.0300 (4) | 0.026 (2) | |
C3 | 0.3483 (17) | 0.3824 (7) | 0.0778 (4) | 0.031 (2) | |
H3 | 0.4326 | 0.4460 | 0.0650 | 0.037* | |
C4 | 0.4358 (18) | 0.3555 (6) | 0.1421 (4) | 0.027 (2) | |
C5 | 0.3105 (17) | 0.2621 (7) | 0.1552 (4) | 0.029 (2) | |
H5 | 0.3737 | 0.2432 | 0.1997 | 0.035* | |
C6 | 0.0979 (18) | 0.1974 (7) | 0.1043 (4) | 0.026 (2) | |
C7 | −0.031 (2) | 0.0956 (7) | 0.1207 (5) | 0.036 (2) | |
C9 | −0.375 (2) | −0.0599 (7) | 0.0838 (4) | 0.038 (2) | |
H9A | −0.5355 | −0.0940 | 0.0448 | 0.046* | |
H9B | −0.4762 | −0.0507 | 0.1283 | 0.046* | |
H9C | −0.2015 | −0.1021 | 0.0876 | 0.046* | |
C10 | 0.0372 (19) | 0.3402 (7) | −0.0409 (4) | 0.029 (2) | |
C12 | −0.288 (2) | 0.2975 (7) | −0.1486 (4) | 0.044 (3) | |
H12A | −0.4579 | 0.2444 | −0.1739 | 0.053* | |
H12B | −0.1031 | 0.3007 | −0.1766 | 0.053* | |
H12C | −0.3686 | 0.3640 | −0.1415 | 0.053* | |
C22 | 0.3829 (18) | 0.2921 (6) | 0.5959 (4) | 0.027 (2) | |
C23 | 0.3453 (17) | 0.2334 (6) | 0.6479 (4) | 0.025 (2) | |
H23 | 0.4792 | 0.2516 | 0.6920 | 0.030* | |
C24 | 0.1164 (17) | 0.1478 (7) | 0.6353 (4) | 0.027 (2) | |
C25 | −0.0624 (17) | 0.1227 (6) | 0.5693 (4) | 0.027 (2) | |
H25 | −0.2195 | 0.0626 | 0.5596 | 0.033* | |
C26 | −0.0044 (18) | 0.1866 (6) | 0.5201 (4) | 0.027 (2) | |
C27 | −0.2121 (19) | 0.1609 (7) | 0.4508 (4) | 0.027 (2) | |
C29 | −0.358 (2) | 0.2119 (7) | 0.3423 (4) | 0.043 (3) | |
H29A | −0.2842 | 0.2618 | 0.3133 | 0.052* | |
H29B | −0.5782 | 0.2201 | 0.3532 | 0.052* | |
H29C | −0.3534 | 0.1423 | 0.3163 | 0.052* | |
C30 | 0.6308 (19) | 0.3850 (6) | 0.6136 (4) | 0.026 (2) | |
C32 | 0.8238 (19) | 0.5442 (6) | 0.5832 (5) | 0.038 (2) | |
H32A | 0.7637 | 0.5904 | 0.5515 | 0.046* | |
H32B | 1.0415 | 0.5283 | 0.5759 | 0.046* | |
H32C | 0.8173 | 0.5774 | 0.6325 | 0.046* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.0308 (3) | 0.0292 (4) | 0.0284 (4) | −0.0050 (3) | −0.0046 (3) | 0.0040 (3) |
I2 | 0.0346 (4) | 0.0328 (4) | 0.0329 (4) | −0.0036 (3) | −0.0010 (3) | 0.0145 (3) |
O8 | 0.052 (4) | 0.025 (4) | 0.039 (4) | −0.017 (3) | −0.013 (3) | 0.016 (3) |
O11 | 0.047 (4) | 0.031 (4) | 0.033 (4) | −0.013 (3) | −0.019 (3) | 0.009 (3) |
O13 | 0.074 (4) | 0.037 (4) | 0.034 (4) | −0.020 (3) | −0.013 (3) | 0.019 (3) |
O14 | 0.072 (5) | 0.044 (5) | 0.039 (4) | −0.025 (4) | −0.018 (3) | 0.023 (4) |
O28 | 0.045 (4) | 0.031 (4) | 0.030 (3) | −0.008 (3) | −0.010 (3) | 0.013 (3) |
O31 | 0.038 (3) | 0.017 (3) | 0.038 (3) | −0.010 (3) | −0.013 (3) | 0.011 (3) |
O33 | 0.053 (4) | 0.028 (4) | 0.041 (4) | −0.020 (3) | −0.007 (3) | 0.010 (3) |
O34 | 0.034 (3) | 0.029 (4) | 0.033 (3) | −0.006 (3) | −0.014 (3) | 0.012 (3) |
N1 | 0.024 (4) | 0.022 (4) | 0.022 (4) | −0.002 (3) | −0.004 (3) | 0.001 (3) |
N21 | 0.027 (4) | 0.017 (4) | 0.025 (4) | 0.002 (3) | 0.000 (3) | 0.007 (3) |
C2 | 0.032 (5) | 0.021 (5) | 0.025 (5) | −0.002 (4) | −0.004 (4) | 0.010 (4) |
C3 | 0.026 (5) | 0.034 (6) | 0.026 (5) | −0.012 (4) | 0.000 (4) | 0.001 (4) |
C4 | 0.034 (5) | 0.029 (6) | 0.016 (4) | 0.002 (4) | −0.001 (4) | 0.004 (4) |
C5 | 0.026 (5) | 0.035 (6) | 0.028 (5) | 0.004 (4) | −0.002 (4) | 0.011 (5) |
C6 | 0.031 (5) | 0.030 (6) | 0.018 (5) | −0.001 (4) | 0.002 (4) | 0.008 (4) |
C7 | 0.045 (6) | 0.029 (6) | 0.031 (5) | 0.001 (5) | −0.006 (5) | 0.007 (5) |
C9 | 0.045 (5) | 0.032 (6) | 0.034 (5) | −0.005 (5) | −0.001 (4) | 0.006 (5) |
C10 | 0.030 (5) | 0.030 (6) | 0.021 (5) | −0.005 (4) | −0.002 (4) | −0.001 (4) |
C12 | 0.050 (6) | 0.053 (7) | 0.027 (5) | −0.015 (5) | −0.015 (5) | 0.022 (5) |
C22 | 0.026 (5) | 0.021 (5) | 0.035 (5) | 0.004 (4) | −0.008 (4) | 0.011 (4) |
C23 | 0.022 (4) | 0.033 (6) | 0.021 (4) | 0.007 (4) | 0.002 (4) | 0.008 (4) |
C24 | 0.026 (5) | 0.030 (6) | 0.026 (5) | 0.001 (4) | 0.010 (4) | 0.005 (4) |
C25 | 0.023 (4) | 0.026 (6) | 0.034 (5) | −0.002 (4) | 0.009 (4) | 0.013 (5) |
C26 | 0.029 (5) | 0.018 (5) | 0.034 (5) | 0.000 (4) | 0.006 (4) | 0.011 (4) |
C27 | 0.039 (5) | 0.017 (5) | 0.024 (5) | −0.001 (4) | 0.005 (4) | 0.007 (4) |
C29 | 0.057 (6) | 0.043 (7) | 0.023 (5) | −0.003 (5) | −0.020 (4) | 0.007 (5) |
C30 | 0.029 (5) | 0.024 (6) | 0.030 (5) | 0.013 (4) | 0.010 (4) | 0.004 (4) |
C32 | 0.049 (6) | 0.024 (6) | 0.038 (5) | −0.008 (5) | −0.011 (5) | 0.013 (5) |
Geometric parameters (Å, º) top
I1—C4 | 2.100 (8) | C5—C6 | 1.379 (11) |
I2—C24 | 2.081 (7) | C5—H5 | 0.9599 |
O8—C7 | 1.333 (10) | C6—C7 | 1.497 (11) |
O8—C9 | 1.450 (9) | C9—H9A | 0.9800 |
O11—C10 | 1.327 (9) | C9—H9B | 0.9800 |
O11—C12 | 1.445 (8) | C9—H9C | 0.9800 |
O13—C7 | 1.199 (8) | C12—H12A | 0.9800 |
O14—C10 | 1.201 (9) | C12—H12B | 0.9800 |
O28—C27 | 1.342 (9) | C12—H12C | 0.9800 |
O28—C29 | 1.455 (8) | C22—C23 | 1.380 (10) |
O31—C30 | 1.355 (9) | C22—C30 | 1.497 (11) |
O31—C32 | 1.446 (9) | C23—C24 | 1.380 (11) |
O33—C27 | 1.200 (9) | C23—H23 | 0.9601 |
O34—C30 | 1.203 (9) | C24—C25 | 1.392 (10) |
N1—C2 | 1.343 (9) | C25—C26 | 1.397 (10) |
N1—C6 | 1.347 (8) | C25—H25 | 0.9600 |
N21—C22 | 1.334 (9) | C26—C27 | 1.502 (11) |
N21—C26 | 1.344 (9) | C29—H29A | 0.9800 |
C2—C3 | 1.383 (10) | C29—H29B | 0.9800 |
C2—C10 | 1.512 (10) | C29—H29C | 0.9800 |
C3—C4 | 1.381 (9) | C32—H32A | 0.9800 |
C3—H3 | 0.9599 | C32—H32B | 0.9800 |
C4—C5 | 1.368 (10) | C32—H32C | 0.9800 |
| | | |
C7—O8—C9 | 115.5 (6) | O11—C12—H12C | 109.5 |
C10—O11—C12 | 115.1 (6) | H12A—C12—H12C | 109.5 |
C27—O28—C29 | 115.3 (6) | H12B—C12—H12C | 109.5 |
C30—O31—C32 | 115.6 (6) | N21—C22—C23 | 124.3 (8) |
C2—N1—C6 | 115.4 (7) | N21—C22—C30 | 119.2 (7) |
C22—N21—C26 | 116.1 (6) | C23—C22—C30 | 116.5 (7) |
N1—C2—C3 | 125.1 (7) | C24—C23—C22 | 119.3 (7) |
N1—C2—C10 | 116.7 (7) | C24—C23—H23 | 120.5 |
C3—C2—C10 | 118.2 (7) | C22—C23—H23 | 120.2 |
C4—C3—C2 | 117.4 (8) | C23—C24—C25 | 118.1 (7) |
C4—C3—H3 | 123.0 | C23—C24—I2 | 121.0 (6) |
C2—C3—H3 | 119.5 | C25—C24—I2 | 120.8 (6) |
C5—C4—C3 | 119.2 (7) | C24—C25—C26 | 118.2 (8) |
C5—C4—I1 | 119.9 (5) | C24—C25—H25 | 118.9 |
C3—C4—I1 | 120.8 (6) | C26—C25—H25 | 122.9 |
C4—C5—C6 | 119.2 (7) | N21—C26—C25 | 124.0 (7) |
C4—C5—H5 | 119.1 | N21—C26—C27 | 118.8 (6) |
C6—C5—H5 | 121.7 | C25—C26—C27 | 117.1 (7) |
N1—C6—C5 | 123.6 (7) | O33—C27—O28 | 124.0 (7) |
N1—C6—C7 | 118.9 (7) | O33—C27—C26 | 123.0 (7) |
C5—C6—C7 | 117.4 (7) | O28—C27—C26 | 113.0 (7) |
O13—C7—O8 | 124.6 (8) | O28—C29—H29A | 109.5 |
O13—C7—C6 | 121.7 (8) | O28—C29—H29B | 109.5 |
O8—C7—C6 | 113.7 (7) | H29A—C29—H29B | 109.5 |
O8—C9—H9A | 109.5 | O28—C29—H29C | 109.5 |
O8—C9—H9B | 109.5 | H29A—C29—H29C | 109.5 |
H9A—C9—H9B | 109.5 | H29B—C29—H29C | 109.5 |
O8—C9—H9C | 109.5 | O34—C30—O31 | 123.8 (8) |
H9A—C9—H9C | 109.5 | O34—C30—C22 | 123.8 (7) |
H9B—C9—H9C | 109.5 | O31—C30—C22 | 112.4 (7) |
O14—C10—O11 | 124.2 (7) | O31—C32—H32A | 109.5 |
O14—C10—C2 | 121.9 (7) | O31—C32—H32B | 109.5 |
O11—C10—C2 | 113.9 (7) | H32A—C32—H32B | 109.5 |
O11—C12—H12A | 109.5 | O31—C32—H32C | 109.5 |
O11—C12—H12B | 109.5 | H32A—C32—H32C | 109.5 |
H12A—C12—H12B | 109.5 | H32B—C32—H32C | 109.5 |
| | | |
C6—N1—C2—C3 | −0.2 (12) | C26—N21—C22—C23 | −0.2 (12) |
C6—N1—C2—C10 | 179.1 (7) | C26—N21—C22—C30 | 180.0 (7) |
N1—C2—C3—C4 | −0.2 (13) | N21—C22—C23—C24 | −1.1 (13) |
C10—C2—C3—C4 | −179.4 (7) | C30—C22—C23—C24 | 178.8 (7) |
C2—C3—C4—C5 | 0.5 (12) | C22—C23—C24—C25 | 1.7 (12) |
C2—C3—C4—I1 | −175.6 (6) | C22—C23—C24—I2 | −175.7 (6) |
C3—C4—C5—C6 | −0.5 (12) | C23—C24—C25—C26 | −1.2 (12) |
I1—C4—C5—C6 | 175.7 (6) | I2—C24—C25—C26 | 176.2 (6) |
C2—N1—C6—C5 | 0.2 (12) | C22—N21—C26—C25 | 0.7 (12) |
C2—N1—C6—C7 | −179.1 (7) | C22—N21—C26—C27 | 177.6 (7) |
C4—C5—C6—N1 | 0.1 (13) | C24—C25—C26—N21 | 0.0 (12) |
C4—C5—C6—C7 | 179.4 (8) | C24—C25—C26—C27 | −176.9 (7) |
C9—O8—C7—O13 | −0.1 (13) | C29—O28—C27—O33 | 4.0 (12) |
C9—O8—C7—C6 | −180.0 (7) | C29—O28—C27—C26 | −175.7 (7) |
N1—C6—C7—O13 | 176.8 (8) | N21—C26—C27—O33 | −179.3 (8) |
C5—C6—C7—O13 | −2.4 (13) | C25—C26—C27—O33 | −2.2 (13) |
N1—C6—C7—O8 | −3.3 (11) | N21—C26—C27—O28 | 0.4 (11) |
C5—C6—C7—O8 | 177.4 (8) | C25—C26—C27—O28 | 177.4 (7) |
C12—O11—C10—O14 | 1.0 (13) | C32—O31—C30—O34 | −1.5 (11) |
C12—O11—C10—C2 | 179.8 (7) | C32—O31—C30—C22 | 177.5 (7) |
N1—C2—C10—O14 | −174.7 (8) | N21—C22—C30—O34 | −166.6 (7) |
C3—C2—C10—O14 | 4.6 (13) | C23—C22—C30—O34 | 13.6 (12) |
N1—C2—C10—O11 | 6.4 (11) | N21—C22—C30—O31 | 14.4 (11) |
C3—C2—C10—O11 | −174.3 (7) | C23—C22—C30—O31 | −165.4 (7) |
Geometry of the intermolecular I···O contacts (Å, °). topCa | I | O | Cb | I···O | Ca—I···O | I···O—Cb |
C4 | I1i | O34ii | C30 | 2.981 (6) | 177.6 (2) | 152.0 (6) |
C24 | I2ii | O13i | C7 | 3.006 (5) | 175.5 (2) | 152.3 (6) |
Symmetry codes: (i) -x, -y, 1-z; (i) 2-x, 1-y, 1-z. |