Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804006452/na6306sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536804006452/na63064sup2.hkl |
CCDC reference: 231737
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- R factor = 0.052
- wR factor = 0.094
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low .... 33 Perc.
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.137 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.14 PLAT230_ALERT_2_C Hirshfeld Test Diff for Cl2 - C8 .. 5.84 su PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 6
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 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 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C22H18Cl2N4 | F(000) = 1696 |
Mr = 409.30 | Dx = 1.368 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 8102 reflections |
a = 12.0008 (11) Å | θ = 1.5–24.1° |
b = 27.4501 (16) Å | µ = 0.34 mm−1 |
c = 12.068 (3) Å | T = 293 K |
V = 3975.4 (10) Å3 | Plate, colourless |
Z = 8 | 0.50 × 0.35 × 0.04 mm |
Stoe IPDS 2 diffractometer | 3901 independent reflections |
Radiation source: sealed X-ray tube | 1304 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.137 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 1.5° |
ω scans | h = −14→14 |
Absorption correction: integration (X-RED; Stoe & Cie, 2002) | k = −30→33 |
Tmin = 0.866, Tmax = 0.986 | l = −14→14 |
26654 measured reflections |
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)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.0112P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
3901 reflections | Δρmax = 0.34 e Å−3 |
248 parameters | Δρmin = −0.42 e Å−3 |
74 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00079 (10) |
Experimental. Melting points were determined on a Büchi oil heated melting point apparatus and are uncorrected. 1H NMR and 13C NMR spectra (s, p.p.m.) were recorded on a Varian 200 A s pectrometer using tetramethylsilane as the internal reference. IR spectra (ν, cm-1) were run on a Perkin-Elmer 1600 FTIR spectrophotometer in KBr pellets. The UV absorption measurements were carried out in 1.10-4-1.10-6 M ethanolic solutions and the spectra were measured between 200 and 400 nm with a Shimadzu 1201 spectrophotometer using 10 mm quartz cells. Combustion analyses were performed on a Carlo Erba 1106 elemental analyzer. The necessary chemicals were obtained from Merck and Fluka. |
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 | ||
Cl1 | 0.23394 (7) | 0.35384 (4) | 0.06790 (9) | 0.0994 (4) | |
Cl2 | 0.63722 (8) | 0.43631 (4) | 0.00082 (9) | 0.0974 (4) | |
N1 | 0.6103 (2) | 0.33255 (15) | −0.2429 (3) | 0.0844 (11) | |
N2 | 0.6284 (3) | 0.37772 (16) | −0.2878 (3) | 0.0878 (11) | |
N3 | 0.4664 (2) | 0.37917 (13) | −0.2064 (2) | 0.0598 (8) | |
N4 | 0.3703 (2) | 0.39825 (11) | −0.1578 (2) | 0.0729 (9) | |
H4 | 0.3055 | 0.3955 | −0.1876 | 0.087* | |
C1 | 0.5415 (3) | 0.40637 (19) | −0.2666 (3) | 0.0700 (11) | |
C2 | 0.5127 (3) | 0.33453 (17) | −0.1929 (3) | 0.0633 (10) | |
C3 | 0.4389 (3) | 0.39158 (14) | 0.0361 (3) | 0.0572 (10) | |
C4 | 0.3760 (3) | 0.35828 (16) | 0.0943 (3) | 0.0697 (11) | |
C5 | 0.4227 (4) | 0.32729 (17) | 0.1730 (3) | 0.0922 (14) | |
H5 | 0.3787 | 0.3045 | 0.2097 | 0.111* | |
C6 | 0.5321 (5) | 0.33078 (19) | 0.1953 (4) | 0.1038 (16) | |
H6 | 0.5637 | 0.3099 | 0.2473 | 0.125* | |
C7 | 0.5968 (4) | 0.36369 (18) | 0.1443 (3) | 0.0893 (14) | |
H7 | 0.6721 | 0.3661 | 0.1618 | 0.107* | |
C8 | 0.5503 (3) | 0.39404 (14) | 0.0652 (3) | 0.0673 (10) | |
C9 | 0.3884 (3) | 0.42273 (13) | −0.0545 (3) | 0.0655 (10) | |
H9A | 0.3176 | 0.4353 | −0.0283 | 0.079* | |
H9B | 0.4370 | 0.4504 | −0.0674 | 0.079* | |
C10 | 0.4643 (3) | 0.29276 (15) | −0.1348 (3) | 0.0612 (10) | |
C11 | 0.5343 (3) | 0.26407 (17) | −0.0713 (3) | 0.0757 (12) | |
H11 | 0.6098 | 0.2715 | −0.0679 | 0.091* | |
C12 | 0.4947 (3) | 0.22527 (17) | −0.0139 (3) | 0.0811 (12) | |
H12 | 0.5433 | 0.2069 | 0.0293 | 0.097* | |
C13 | 0.3832 (4) | 0.21254 (17) | −0.0184 (3) | 0.0951 (10) | |
C14 | 0.3137 (3) | 0.24096 (16) | −0.0831 (3) | 0.0740 (11) | |
H14 | 0.2387 | 0.2328 | −0.0879 | 0.089* | |
C15 | 0.3520 (3) | 0.28078 (15) | −0.1405 (3) | 0.0626 (10) | |
H15 | 0.3033 | 0.2995 | −0.1827 | 0.075* | |
C16 | 0.3434 (3) | 0.16967 (15) | 0.0428 (3) | 0.0951 (10) | |
H16A | 0.4045 | 0.1551 | 0.0819 | 0.143* | |
H16B | 0.3127 | 0.1465 | −0.0084 | 0.143* | |
H16C | 0.2870 | 0.1794 | 0.0946 | 0.143* | |
C17 | 0.5287 (4) | 0.45646 (19) | −0.2986 (3) | 0.0763 (12) | |
C18 | 0.4300 (4) | 0.47469 (19) | −0.3396 (3) | 0.0936 (14) | |
H18 | 0.3686 | 0.4543 | −0.3458 | 0.112* | |
C19 | 0.4208 (5) | 0.5234 (2) | −0.3720 (4) | 0.1231 (19) | |
H19 | 0.3528 | 0.5350 | −0.3979 | 0.148* | |
C20 | 0.5107 (5) | 0.5547 (2) | −0.3663 (4) | 0.133 (2) | |
H20 | 0.5057 | 0.5868 | −0.3907 | 0.160* | |
C21 | 0.6071 (5) | 0.5365 (2) | −0.3232 (4) | 0.123 (2) | |
H21 | 0.6676 | 0.5573 | −0.3143 | 0.147* | |
C22 | 0.6190 (4) | 0.4875 (2) | −0.2917 (3) | 0.1025 (15) | |
H22 | 0.6873 | 0.4761 | −0.2664 | 0.123* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0761 (7) | 0.1224 (11) | 0.0997 (8) | −0.0150 (7) | 0.0312 (6) | −0.0128 (8) |
Cl2 | 0.0762 (6) | 0.1030 (9) | 0.1129 (8) | −0.0226 (7) | −0.0132 (7) | 0.0128 (8) |
N1 | 0.0480 (19) | 0.127 (3) | 0.078 (2) | 0.014 (2) | 0.0145 (16) | 0.002 (2) |
N2 | 0.054 (2) | 0.129 (3) | 0.081 (2) | 0.003 (2) | 0.0165 (19) | 0.008 (2) |
N3 | 0.0382 (16) | 0.089 (3) | 0.0523 (18) | 0.0039 (18) | −0.0002 (15) | −0.0019 (18) |
N4 | 0.0379 (16) | 0.124 (3) | 0.0568 (18) | 0.0181 (19) | −0.0036 (15) | −0.0171 (19) |
C1 | 0.043 (2) | 0.112 (4) | 0.055 (2) | −0.005 (3) | 0.006 (2) | 0.005 (3) |
C2 | 0.039 (2) | 0.097 (3) | 0.054 (2) | 0.007 (2) | −0.0036 (18) | −0.006 (2) |
C3 | 0.063 (2) | 0.058 (3) | 0.051 (2) | 0.000 (2) | 0.0045 (17) | −0.0051 (19) |
C4 | 0.074 (2) | 0.076 (3) | 0.060 (3) | −0.007 (2) | 0.016 (2) | −0.016 (2) |
C5 | 0.133 (4) | 0.091 (4) | 0.053 (3) | −0.020 (3) | 0.016 (3) | 0.003 (2) |
C6 | 0.133 (4) | 0.107 (4) | 0.072 (3) | 0.004 (4) | −0.015 (3) | 0.016 (3) |
C7 | 0.101 (3) | 0.100 (4) | 0.067 (3) | 0.003 (3) | −0.025 (2) | 0.004 (3) |
C8 | 0.069 (2) | 0.075 (3) | 0.058 (2) | −0.010 (2) | 0.002 (2) | −0.003 (2) |
C9 | 0.057 (2) | 0.073 (3) | 0.066 (2) | 0.004 (2) | 0.0099 (19) | −0.006 (2) |
C10 | 0.047 (2) | 0.084 (3) | 0.052 (2) | 0.014 (2) | −0.0011 (18) | −0.007 (2) |
C11 | 0.059 (2) | 0.098 (4) | 0.070 (3) | 0.010 (2) | −0.010 (2) | −0.007 (2) |
C12 | 0.083 (3) | 0.096 (4) | 0.064 (3) | 0.025 (3) | −0.015 (2) | −0.004 (2) |
C13 | 0.110 (2) | 0.092 (3) | 0.083 (2) | 0.003 (2) | −0.003 (2) | 0.0063 (18) |
C14 | 0.061 (2) | 0.094 (4) | 0.066 (3) | 0.003 (2) | 0.005 (2) | −0.008 (2) |
C15 | 0.048 (2) | 0.090 (3) | 0.050 (2) | 0.008 (2) | −0.0009 (19) | −0.002 (2) |
C16 | 0.110 (2) | 0.092 (3) | 0.083 (2) | 0.003 (2) | −0.003 (2) | 0.0063 (18) |
C17 | 0.061 (3) | 0.106 (4) | 0.062 (3) | −0.009 (3) | 0.011 (2) | 0.006 (3) |
C18 | 0.078 (3) | 0.114 (4) | 0.089 (3) | −0.006 (3) | 0.003 (3) | 0.011 (3) |
C19 | 0.130 (4) | 0.130 (5) | 0.109 (4) | 0.021 (4) | 0.013 (4) | 0.037 (4) |
C20 | 0.133 (5) | 0.146 (6) | 0.120 (4) | −0.015 (4) | 0.024 (4) | 0.005 (4) |
C21 | 0.130 (5) | 0.128 (5) | 0.110 (4) | −0.052 (4) | 0.028 (3) | 0.009 (4) |
C22 | 0.074 (3) | 0.143 (4) | 0.091 (3) | −0.031 (3) | 0.012 (3) | 0.010 (3) |
Cl1—C4 | 1.739 (4) | C10—C15 | 1.389 (4) |
Cl2—C8 | 1.743 (4) | C11—C12 | 1.357 (5) |
N1—C2 | 1.319 (4) | C11—H11 | 0.9300 |
N1—N2 | 1.370 (4) | C12—C13 | 1.384 (5) |
N2—C1 | 1.330 (4) | C12—H12 | 0.9300 |
N3—C2 | 1.355 (4) | C13—C14 | 1.383 (5) |
N3—C1 | 1.378 (4) | C13—C16 | 1.469 (5) |
N3—N4 | 1.395 (3) | C14—C15 | 1.373 (4) |
N4—C9 | 1.434 (4) | C14—H14 | 0.9300 |
N4—H4 | 0.8600 | C15—H15 | 0.9300 |
C1—C17 | 1.436 (5) | C16—H16A | 0.9600 |
C2—C10 | 1.464 (5) | C16—H16B | 0.9600 |
C3—C4 | 1.378 (4) | C16—H16C | 0.9600 |
C3—C8 | 1.384 (4) | C17—C18 | 1.377 (5) |
C3—C9 | 1.514 (4) | C17—C22 | 1.381 (5) |
C4—C5 | 1.392 (5) | C18—C19 | 1.398 (6) |
C5—C6 | 1.344 (5) | C18—H18 | 0.9300 |
C5—H5 | 0.9300 | C19—C20 | 1.381 (6) |
C6—C7 | 1.341 (5) | C19—H19 | 0.9300 |
C6—H6 | 0.9300 | C20—C21 | 1.365 (6) |
C7—C8 | 1.385 (5) | C20—H20 | 0.9300 |
C7—H7 | 0.9300 | C21—C22 | 1.403 (6) |
C9—H9A | 0.9700 | C21—H21 | 0.9300 |
C9—H9B | 0.9700 | C22—H22 | 0.9300 |
C10—C11 | 1.383 (4) | ||
C2—N1—N2 | 106.5 (4) | C15—C10—C2 | 123.1 (3) |
C1—N2—N1 | 109.6 (3) | C12—C11—C10 | 121.2 (4) |
C2—N3—C1 | 106.6 (3) | C12—C11—H11 | 119.4 |
C2—N3—N4 | 128.9 (3) | C10—C11—H11 | 119.4 |
C1—N3—N4 | 124.0 (4) | C11—C12—C13 | 121.1 (4) |
N3—N4—C9 | 114.6 (2) | C11—C12—H12 | 119.4 |
N3—N4—H4 | 122.7 | C13—C12—H12 | 119.4 |
C9—N4—H4 | 122.7 | C14—C13—C12 | 117.5 (4) |
N2—C1—N3 | 107.1 (4) | C14—C13—C16 | 122.7 (4) |
N2—C1—C17 | 126.7 (4) | C12—C13—C16 | 119.8 (5) |
N3—C1—C17 | 126.2 (4) | C15—C14—C13 | 122.2 (4) |
N1—C2—N3 | 110.2 (4) | C15—C14—H14 | 118.9 |
N1—C2—C10 | 122.6 (4) | C13—C14—H14 | 118.9 |
N3—C2—C10 | 127.1 (3) | C14—C15—C10 | 119.2 (3) |
C4—C3—C8 | 115.6 (3) | C14—C15—H15 | 120.4 |
C4—C3—C9 | 121.6 (3) | C10—C15—H15 | 120.4 |
C8—C3—C9 | 122.8 (3) | C13—C16—H16A | 109.5 |
C3—C4—C5 | 122.2 (4) | C13—C16—H16B | 109.5 |
C3—C4—Cl1 | 119.3 (3) | H16A—C16—H16B | 109.5 |
C5—C4—Cl1 | 118.5 (4) | C13—C16—H16C | 109.5 |
C6—C5—C4 | 119.1 (4) | H16A—C16—H16C | 109.5 |
C6—C5—H5 | 120.5 | H16B—C16—H16C | 109.5 |
C4—C5—H5 | 120.5 | C18—C17—C22 | 118.1 (5) |
C7—C6—C5 | 121.5 (5) | C18—C17—C1 | 122.4 (4) |
C7—C6—H6 | 119.3 | C22—C17—C1 | 119.4 (5) |
C5—C6—H6 | 119.3 | C17—C18—C19 | 121.1 (5) |
C6—C7—C8 | 119.2 (4) | C17—C18—H18 | 119.5 |
C6—C7—H7 | 120.4 | C19—C18—H18 | 119.5 |
C8—C7—H7 | 120.4 | C20—C19—C18 | 121.3 (6) |
C3—C8—C7 | 122.4 (4) | C20—C19—H19 | 119.3 |
C3—C8—Cl2 | 119.8 (3) | C18—C19—H19 | 119.3 |
C7—C8—Cl2 | 117.8 (3) | C21—C20—C19 | 116.9 (7) |
N4—C9—C3 | 115.1 (3) | C21—C20—H20 | 121.5 |
N4—C9—H9A | 108.5 | C19—C20—H20 | 121.5 |
C3—C9—H9A | 108.5 | C20—C21—C22 | 122.7 (6) |
N4—C9—H9B | 108.5 | C20—C21—H21 | 118.6 |
C3—C9—H9B | 108.5 | C22—C21—H21 | 118.6 |
H9A—C9—H9B | 107.5 | C17—C22—C21 | 119.7 (5) |
C11—C10—C15 | 118.8 (4) | C17—C22—H22 | 120.1 |
C11—C10—C2 | 118.1 (4) | C21—C22—H22 | 120.1 |
C2—N1—N2—C1 | −1.1 (4) | N3—N4—C9—C3 | −59.6 (4) |
C2—N3—N4—C9 | 89.7 (4) | C4—C3—C9—N4 | −77.1 (4) |
C1—N3—N4—C9 | −80.4 (4) | C8—C3—C9—N4 | 102.1 (4) |
N1—N2—C1—N3 | 0.4 (4) | N1—C2—C10—C11 | 40.8 (5) |
N1—N2—C1—C17 | 179.4 (4) | N3—C2—C10—C11 | −141.0 (4) |
C2—N3—C1—N2 | 0.5 (4) | N1—C2—C10—C15 | −139.3 (3) |
N4—N3—C1—N2 | 172.4 (3) | N3—C2—C10—C15 | 39.0 (5) |
C2—N3—C1—C17 | −178.5 (4) | C15—C10—C11—C12 | −1.0 (6) |
N4—N3—C1—C17 | −6.6 (5) | C2—C10—C11—C12 | 178.9 (4) |
N2—N1—C2—N3 | 1.4 (4) | C10—C11—C12—C13 | 1.2 (6) |
N2—N1—C2—C10 | 179.9 (3) | C11—C12—C13—C14 | −0.3 (6) |
C1—N3—C2—N1 | −1.2 (4) | C11—C12—C13—C16 | 178.6 (4) |
N4—N3—C2—N1 | −172.6 (3) | C12—C13—C14—C15 | −0.7 (6) |
C1—N3—C2—C10 | −179.6 (3) | C16—C13—C14—C15 | −179.5 (3) |
N4—N3—C2—C10 | 8.9 (6) | C13—C14—C15—C10 | 0.8 (5) |
C8—C3—C4—C5 | −3.4 (5) | C11—C10—C15—C14 | 0.1 (5) |
C9—C3—C4—C5 | 176.0 (3) | C2—C10—C15—C14 | −179.9 (3) |
C8—C3—C4—Cl1 | 177.6 (3) | N2—C1—C17—C18 | 137.4 (4) |
C9—C3—C4—Cl1 | −3.1 (5) | N3—C1—C17—C18 | −43.7 (6) |
C3—C4—C5—C6 | 1.8 (6) | N2—C1—C17—C22 | −40.4 (6) |
Cl1—C4—C5—C6 | −179.1 (3) | N3—C1—C17—C22 | 138.5 (4) |
C4—C5—C6—C7 | 0.7 (7) | C22—C17—C18—C19 | −0.9 (6) |
C5—C6—C7—C8 | −1.4 (7) | C1—C17—C18—C19 | −178.7 (4) |
C4—C3—C8—C7 | 2.6 (5) | C17—C18—C19—C20 | 1.4 (7) |
C9—C3—C8—C7 | −176.7 (3) | C18—C19—C20—C21 | −2.7 (8) |
C4—C3—C8—Cl2 | −177.7 (3) | C19—C20—C21—C22 | 3.8 (9) |
C9—C3—C8—Cl2 | 3.0 (5) | C18—C17—C22—C21 | 1.9 (6) |
C6—C7—C8—C3 | −0.3 (6) | C1—C17—C22—C21 | 179.8 (4) |
C6—C7—C8—Cl2 | −180.0 (3) | C20—C21—C22—C17 | −3.5 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N2i | 0.86 | 2.20 | 3.030 (4) | 162 |
C9—H9B···Cl2 | 0.97 | 2.57 | 3.082 (3) | 113 |
Symmetry code: (i) x−1/2, y, −z−1/2. |