Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005555/wn6144sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005555/wn6144Isup2.hkl |
CCDC reference: 209955
The title compound, (I), was synthesized according to a literature procedure (Nishiwaki et al., 1988), with minor modification. The product was dissolved in CHCl3 and the solution was set aside at room temprature. As the solvent slowly evaporated, crystals of (I) were formed.
H atoms attached to C atoms were placed in geometrically idealized positions, with Csp2—H = 0.93 Å and Csp3—H = 0.96 Å, and were constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(C), respectively.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 2000); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.
C7H5Cl3N2O3 | F(000) = 1088 |
Mr = 271.48 | Dx = 1.733 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3073 reflections |
a = 11.590 (4) Å | θ = 2.9–27.2° |
b = 10.603 (3) Å | µ = 0.87 mm−1 |
c = 16.935 (5) Å | T = 193 K |
V = 2081.2 (11) Å3 | Block, yellow |
Z = 8 | 0.20 × 0.20 × 0.20 mm |
Bruker SMART 1K CCD area-detector diffractometer | 1574 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 25.0°, θmin = 2.4° |
ω scans | h = −13→12 |
7949 measured reflections | k = −11→12 |
1837 independent reflections | l = −18→20 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0553P)2 + 0.8439P] where P = (Fo2 + 2Fc2)/3 |
1837 reflections | (Δ/σ)max = 0.001 |
137 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C7H5Cl3N2O3 | V = 2081.2 (11) Å3 |
Mr = 271.48 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.590 (4) Å | µ = 0.87 mm−1 |
b = 10.603 (3) Å | T = 193 K |
c = 16.935 (5) Å | 0.20 × 0.20 × 0.20 mm |
Bruker SMART 1K CCD area-detector diffractometer | 1574 reflections with I > 2σ(I) |
7949 measured reflections | Rint = 0.029 |
1837 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.33 e Å−3 |
1837 reflections | Δρmin = −0.19 e Å−3 |
137 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O2 | 0.2386 (2) | −0.0288 (2) | 1.05488 (14) | 0.0763 (7) | |
Cl1 | 0.43332 (7) | 0.09579 (9) | 0.70167 (5) | 0.0686 (3) | |
Cl2 | 0.66325 (7) | 0.18290 (9) | 0.67657 (5) | 0.0706 (3) | |
Cl3 | 0.62763 (9) | −0.05161 (8) | 0.75825 (6) | 0.0760 (3) | |
C3 | 0.4904 (2) | 0.1345 (2) | 0.88368 (15) | 0.0399 (6) | |
C4 | 0.4192 (2) | 0.0315 (3) | 0.88783 (16) | 0.0434 (6) | |
H4 | 0.4102 | −0.0310 | 0.8498 | 0.052* | |
N2 | 0.2791 (2) | −0.0471 (2) | 0.98913 (16) | 0.0556 (7) | |
N1 | 0.47657 (19) | 0.2036 (2) | 0.95299 (13) | 0.0434 (5) | |
C2 | 0.5735 (2) | 0.1735 (3) | 0.82389 (17) | 0.0467 (7) | |
C5 | 0.3628 (2) | 0.0394 (3) | 0.96037 (17) | 0.0429 (6) | |
O1 | 0.6432 (2) | 0.2557 (2) | 0.83321 (14) | 0.0774 (7) | |
C1 | 0.5730 (2) | 0.1024 (3) | 0.74347 (17) | 0.0501 (7) | |
C6 | 0.3992 (2) | 0.1462 (3) | 0.99869 (17) | 0.0454 (7) | |
H6 | 0.3743 | 0.1737 | 1.0480 | 0.054* | |
C7 | 0.5283 (3) | 0.3257 (3) | 0.97263 (19) | 0.0615 (8) | |
H7A | 0.4935 | 0.3580 | 1.0199 | 0.092* | |
H7B | 0.5155 | 0.3838 | 0.9300 | 0.092* | |
H7C | 0.6097 | 0.3153 | 0.9808 | 0.092* | |
O3 | 0.2513 (2) | −0.1352 (2) | 0.94712 (16) | 0.0864 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0714 (16) | 0.0900 (18) | 0.0675 (15) | 0.0037 (13) | 0.0308 (13) | 0.0150 (13) |
Cl1 | 0.0538 (5) | 0.1008 (7) | 0.0513 (5) | −0.0077 (4) | −0.0042 (4) | −0.0021 (4) |
Cl2 | 0.0628 (5) | 0.0948 (7) | 0.0542 (5) | −0.0062 (4) | 0.0178 (4) | 0.0103 (4) |
Cl3 | 0.0930 (7) | 0.0576 (5) | 0.0775 (6) | 0.0200 (5) | 0.0132 (5) | −0.0045 (4) |
C3 | 0.0419 (14) | 0.0399 (14) | 0.0379 (14) | 0.0022 (11) | 0.0001 (11) | 0.0022 (11) |
C4 | 0.0428 (15) | 0.0405 (15) | 0.0468 (16) | 0.0038 (12) | 0.0007 (12) | 0.0009 (12) |
N2 | 0.0477 (15) | 0.0505 (15) | 0.0686 (18) | 0.0073 (12) | 0.0147 (13) | 0.0145 (14) |
N1 | 0.0477 (13) | 0.0400 (12) | 0.0424 (12) | 0.0035 (10) | −0.0021 (10) | 0.0005 (10) |
C2 | 0.0483 (16) | 0.0423 (15) | 0.0493 (17) | 0.0006 (13) | 0.0019 (13) | 0.0024 (13) |
C5 | 0.0368 (14) | 0.0433 (15) | 0.0486 (16) | 0.0065 (12) | 0.0026 (12) | 0.0117 (13) |
O1 | 0.0844 (16) | 0.0751 (16) | 0.0727 (15) | −0.0386 (14) | 0.0210 (13) | −0.0142 (13) |
C1 | 0.0455 (16) | 0.0566 (18) | 0.0481 (17) | −0.0007 (14) | 0.0067 (13) | 0.0046 (14) |
C6 | 0.0476 (16) | 0.0489 (16) | 0.0396 (15) | 0.0094 (13) | 0.0033 (12) | 0.0049 (13) |
C7 | 0.076 (2) | 0.0511 (18) | 0.0573 (19) | −0.0070 (16) | −0.0014 (17) | −0.0099 (14) |
O3 | 0.0916 (19) | 0.0610 (15) | 0.107 (2) | −0.0274 (14) | 0.0374 (16) | −0.0118 (15) |
O2—N2 | 1.224 (3) | N2—C5 | 1.421 (4) |
Cl1—C1 | 1.769 (3) | N1—C6 | 1.331 (3) |
Cl2—C1 | 1.762 (3) | N1—C7 | 1.465 (4) |
Cl3—C1 | 1.769 (3) | C2—O1 | 1.199 (3) |
C3—C4 | 1.371 (4) | C2—C1 | 1.556 (4) |
C3—N1 | 1.393 (3) | C5—C6 | 1.372 (4) |
C3—C2 | 1.457 (4) | C6—H6 | 0.9300 |
C4—C5 | 1.394 (4) | C7—H7A | 0.9600 |
C4—H4 | 0.9300 | C7—H7B | 0.9600 |
N2—O3 | 1.217 (3) | C7—H7C | 0.9600 |
C4—C3—N1 | 107.8 (2) | C4—C5—N2 | 125.7 (3) |
C4—C3—C2 | 131.3 (2) | C2—C1—Cl2 | 109.0 (2) |
N1—C3—C2 | 120.8 (2) | C2—C1—Cl1 | 111.87 (19) |
C3—C4—C5 | 106.3 (2) | Cl2—C1—Cl1 | 107.77 (16) |
C3—C4—H4 | 126.9 | C2—C1—Cl3 | 108.8 (2) |
C5—C4—H4 | 126.9 | Cl2—C1—Cl3 | 109.01 (16) |
O3—N2—O2 | 123.5 (3) | Cl1—C1—Cl3 | 110.32 (17) |
O3—N2—C5 | 118.4 (3) | N1—C6—C5 | 108.0 (2) |
O2—N2—C5 | 118.1 (3) | N1—C6—H6 | 126.0 |
C6—N1—C3 | 109.1 (2) | C5—C6—H6 | 126.0 |
C6—N1—C7 | 123.2 (2) | N1—C7—H7A | 109.5 |
C3—N1—C7 | 127.5 (2) | N1—C7—H7B | 109.5 |
O1—C2—C3 | 124.0 (3) | H7A—C7—H7B | 109.5 |
O1—C2—C1 | 118.0 (3) | N1—C7—H7C | 109.5 |
C3—C2—C1 | 118.0 (2) | H7A—C7—H7C | 109.5 |
C6—C5—C4 | 108.8 (2) | H7B—C7—H7C | 109.5 |
C6—C5—N2 | 125.5 (3) | ||
N1—C3—C4—C5 | −0.2 (3) | O2—N2—C5—C6 | −3.0 (4) |
C2—C3—C4—C5 | 177.0 (3) | O3—N2—C5—C4 | −1.5 (4) |
C4—C3—N1—C6 | −0.2 (3) | O2—N2—C5—C4 | 178.8 (3) |
C2—C3—N1—C6 | −177.8 (2) | O1—C2—C1—Cl2 | −10.6 (3) |
C4—C3—N1—C7 | −175.1 (3) | C3—C2—C1—Cl2 | 170.4 (2) |
C2—C3—N1—C7 | 7.3 (4) | O1—C2—C1—Cl1 | −129.7 (3) |
C4—C3—C2—O1 | −168.0 (3) | C3—C2—C1—Cl1 | 51.3 (3) |
N1—C3—C2—O1 | 9.0 (4) | O1—C2—C1—Cl3 | 108.2 (3) |
C4—C3—C2—C1 | 10.9 (4) | C3—C2—C1—Cl3 | −70.8 (3) |
N1—C3—C2—C1 | −172.1 (2) | C3—N1—C6—C5 | 0.5 (3) |
C3—C4—C5—C6 | 0.5 (3) | C7—N1—C6—C5 | 175.6 (2) |
C3—C4—C5—N2 | 179.0 (2) | C4—C5—C6—N1 | −0.6 (3) |
O3—N2—C5—C6 | 176.7 (3) | N2—C5—C6—N1 | −179.1 (2) |
Experimental details
Crystal data | |
Chemical formula | C7H5Cl3N2O3 |
Mr | 271.48 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 193 |
a, b, c (Å) | 11.590 (4), 10.603 (3), 16.935 (5) |
V (Å3) | 2081.2 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.87 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7949, 1837, 1574 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.112, 1.09 |
No. of reflections | 1837 |
No. of parameters | 137 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.19 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 2000), SHELXL97 (Sheldrick, 2000), SHELXTL/PC (Sheldrick, 1999), SHELXTL/PC.
O2—N2 | 1.224 (3) | N2—O3 | 1.217 (3) |
Cl1—C1 | 1.769 (3) | N2—C5 | 1.421 (4) |
Cl2—C1 | 1.762 (3) | N1—C6 | 1.331 (3) |
Cl3—C1 | 1.769 (3) | N1—C7 | 1.465 (4) |
C3—C4 | 1.371 (4) | C2—O1 | 1.199 (3) |
C3—N1 | 1.393 (3) | C2—C1 | 1.556 (4) |
C3—C2 | 1.457 (4) | C5—C6 | 1.372 (4) |
C4—C5 | 1.394 (4) | ||
C4—C3—N1 | 107.8 (2) | C6—C5—C4 | 108.8 (2) |
C4—C3—C2 | 131.3 (2) | C6—C5—N2 | 125.5 (3) |
N1—C3—C2 | 120.8 (2) | C4—C5—N2 | 125.7 (3) |
C3—C4—C5 | 106.3 (2) | C2—C1—Cl2 | 109.0 (2) |
O3—N2—C5 | 118.4 (3) | C2—C1—Cl1 | 111.87 (19) |
O2—N2—C5 | 118.1 (3) | Cl2—C1—Cl1 | 107.77 (16) |
C6—N1—C3 | 109.1 (2) | C2—C1—Cl3 | 108.8 (2) |
O1—C2—C3 | 124.0 (3) | Cl2—C1—Cl3 | 109.01 (16) |
O1—C2—C1 | 118.0 (3) | Cl1—C1—Cl3 | 110.32 (17) |
C3—C2—C1 | 118.0 (2) | N1—C6—C5 | 108.0 (2) |
N1—C3—C4—C5 | −0.2 (3) | N1—C3—C2—O1 | 9.0 (4) |
C2—C3—C4—C5 | 177.0 (3) | C4—C3—C2—C1 | 10.9 (4) |
C4—C3—N1—C6 | −0.2 (3) | N1—C3—C2—C1 | −172.1 (2) |
C2—C3—N1—C6 | −177.8 (2) | C3—C4—C5—C6 | 0.5 (3) |
C4—C3—N1—C7 | −175.1 (3) | C3—C4—C5—N2 | 179.0 (2) |
C2—C3—N1—C7 | 7.3 (4) | C3—N1—C6—C5 | 0.5 (3) |
C4—C3—C2—O1 | −168.0 (3) |
In the past decade, Dervan and co-workers have discovered that polyamides with certain numbers of N-methylpyrrole carboxamides and N-methylimidazole carboxamides can recognize and bind in the minor groove of predetermined DNA sequences with high affinity and specificity, comparable to naturally occurring DNA-binding proteins, and further regulate gene expression (Dervan & Büril, 1999; Simon et al., 2000). These properties stimulated our interest in this field. Crystals of the title compound, (I), were obtained as an intermediate in our synthetic investigations of polyamides.
The molecular structure and a packing diagram of (I) are illustrated in Figs. 1 and 2, respectively. Selected geometric parameters of (I) are listed in Table 1. Inspection of these values indicates that there is delocalization of the π-electron density in the pyrrole ring. Furthermore, there are no significant differences from the geometry found in a similar pyrrole (Lu et al., 2003). The 12 atoms N1–N2, O1–O3 and C1–C7 are essentially coplanar, the r.m.s. deviation being 0.088 Å and the maximum deviation from the plane 0.217 (3) Å for O1. There is a strong interaction between O3 and Cl2(1 − x, −1 − y, 1 − z), with an O3···Cl2A distance of 3.015 (2) Å.