Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106005543/gd1429sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106005543/gd1429Isup2.hkl |
CCDC reference: 605687
Crystals suitable for data collection were obtained by dissolving CI-953 in methanol and subsequently subjected to slow evaporation. Crystals grew in about three weeks. The crystals were small colourless needles. Attempts to grow better crystals in order to avoid disorder proved unsuccessful.
All H atoms, except those of the methyl groups, were initially located on a difference map and well behaving during refinement, however, low data to parameters ratio justified placement of H atoms in calculated positions in a riding model approximation. An overall isotropic temperature displacement parameter was refined for all H atoms except for the methyl groups. The final Uiso=0.08 (3) Å2 and the range of distances 0.86–0.93 Å. The H atoms from methyl groups were refined as idealized disordered groups with two positions rotated from each other by 60° and the methyl groups C atoms and Cl atoms were refined with partial occupancies set to sum to unity. The C—H distances were fixed at 1.0 Å.
Data collection: Picker Operating Manual (Picker, 1967); cell refinement: Picker Operating Manual; data reduction: DATRDN (Stewart, 1976); 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); software used to prepare material for publication: SHELXL97.
C13H13ClN3O+·Cl− | Z = 4 |
Mr = 298.16 | F(000) = 616 |
Triclinic, P1 | Dx = 1.371 Mg m−3 |
a = 8.022 (3) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 13.193 (4) Å | Cell parameters from 32 reflections |
c = 14.893 (4) Å | θ = 19–45° |
α = 69.06 (3)° | µ = 4.01 mm−1 |
β = 81.29 (2)° | T = 294 K |
γ = 80.60 (3)° | Needle, colourless |
V = 1444.9 (9) Å3 | 0.52 × 0.12 × 0.08 mm |
Picker FACS-1 four-circle diffractometer | 3375 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.005 |
Ni-filtered radiation monochromator | θmax = 60.0°, θmin = 3.2° |
θ/2θ scans | h = −4→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −14→14 |
Tmin = 0.586, Tmax = 0.724 | l = −16→16 |
4418 measured reflections | 3 standard reflections every 100 reflections |
4272 independent reflections | intensity decay: 2.7% |
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) = 0.134 | w = 1/[σ2(Fo2) + (0.0837P)2 + 0.3467P] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max = 0.003 |
4272 reflections | Δρmax = 0.27 e Å−3 |
385 parameters | Δρmin = −0.15 e Å−3 |
7 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0062 (6) |
C13H13ClN3O+·Cl− | γ = 80.60 (3)° |
Mr = 298.16 | V = 1444.9 (9) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.022 (3) Å | Cu Kα radiation |
b = 13.193 (4) Å | µ = 4.01 mm−1 |
c = 14.893 (4) Å | T = 294 K |
α = 69.06 (3)° | 0.52 × 0.12 × 0.08 mm |
β = 81.29 (2)° |
Picker FACS-1 four-circle diffractometer | 3375 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.005 |
Tmin = 0.586, Tmax = 0.724 | θmax = 60.0° |
4418 measured reflections | 3 standard reflections every 100 reflections |
4272 independent reflections | intensity decay: 2.7% |
R[F2 > 2σ(F2)] = 0.043 | 7 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.27 e Å−3 |
4272 reflections | Δρmin = −0.15 e Å−3 |
385 parameters |
Experimental. No observed reflections above 60°. |
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 | Occ. (<1) | |
C1A | −0.1968 (5) | 0.4567 (3) | −0.0898 (3) | 0.0664 (9) | |
H1A | −0.3126 | 0.4760 | −0.0950 | 0.081 (4)* | |
C2A | −0.1406 (5) | 0.3730 (2) | −0.0096 (2) | 0.0564 (8) | |
C3A | 0.0313 (4) | 0.3437 (2) | −0.0020 (2) | 0.0489 (7) | |
C4A | 0.1474 (5) | 0.4004 (2) | −0.0743 (2) | 0.0575 (8) | |
C5A | 0.0879 (6) | 0.4843 (3) | −0.1535 (2) | 0.0696 (10) | |
H5A | 0.1646 | 0.5231 | −0.2019 | 0.081 (4)* | |
C6A | −0.0831 (6) | 0.5110 (3) | −0.1614 (3) | 0.0703 (10) | |
H6A | −0.1215 | 0.5664 | −0.2158 | 0.081 (4)* | |
C7A | 0.344 (2) | 0.3784 (18) | −0.078 (3) | 0.047 (4) | 0.419 (6) |
H7A1 | 0.3770 | 0.3169 | −0.0187 | 0.114 (16)* | 0.209 (3) |
H7A2 | 0.3905 | 0.4456 | −0.0817 | 0.114 (16)* | 0.209 (3) |
H7A3 | 0.3906 | 0.3583 | −0.1365 | 0.114 (16)* | 0.209 (3) |
H7A4 | 0.3951 | 0.4303 | −0.1393 | 0.114 (16)* | 0.209 (3) |
H7A5 | 0.3816 | 0.3016 | −0.0762 | 0.114 (16)* | 0.209 (3) |
H7A6 | 0.3815 | 0.3889 | −0.0214 | 0.114 (16)* | 0.209 (3) |
Cl7A | 0.3601 (7) | 0.3663 (5) | −0.0628 (6) | 0.093 (2) | 0.581 (6) |
N8A | 0.0919 (4) | 0.25512 (19) | 0.07822 (19) | 0.0569 (7) | |
H8A | 0.1330 | 0.2680 | 0.1226 | 0.081 (4)* | |
C9A | 0.0852 (4) | 0.1504 (2) | 0.0853 (2) | 0.0470 (7) | |
O10A | 0.0297 (3) | 0.12564 (17) | 0.02623 (16) | 0.0662 (7) | |
N11A | 0.1474 (3) | 0.07603 (18) | 0.16927 (17) | 0.0486 (6) | |
H11A | 0.1826 | 0.1035 | 0.2063 | 0.081 (4)* | |
C12A | 0.1596 (4) | −0.0351 (2) | 0.2002 (2) | 0.0455 (7) | |
C13A | 0.1199 (5) | −0.0949 (2) | 0.1476 (2) | 0.0581 (8) | |
H13A | 0.0819 | −0.0596 | 0.0868 | 0.081 (4)* | |
C14A | 0.1377 (5) | −0.2058 (3) | 0.1867 (3) | 0.0698 (10) | |
H14A | 0.1094 | −0.2461 | 0.1523 | 0.081 (4)* | |
N15A | 0.1941 (4) | −0.2580 (2) | 0.2723 (2) | 0.0667 (8) | |
H15A | 0.2050 | −0.3282 | 0.2947 | 0.081 (4)* | |
C16A | 0.2343 (5) | −0.2035 (3) | 0.3240 (3) | 0.0647 (9) | |
H16A | 0.2736 | −0.2418 | 0.3841 | 0.081 (4)* | |
C17A | 0.2187 (4) | −0.0931 (2) | 0.2905 (2) | 0.0572 (8) | |
H17A | 0.2472 | −0.0557 | 0.3274 | 0.081 (4)* | |
C18A | −0.274 (3) | 0.3075 (17) | 0.0658 (17) | 0.107 (11) | 0.581 (6) |
H18A | −0.2155 | 0.2510 | 0.1201 | 0.114 (16)* | 0.291 (3) |
H18B | −0.3351 | 0.2708 | 0.0345 | 0.114 (16)* | 0.291 (3) |
H18C | −0.3572 | 0.3583 | 0.0913 | 0.114 (16)* | 0.291 (3) |
H18D | −0.3896 | 0.3357 | 0.0438 | 0.114 (16)* | 0.291 (3) |
H18E | −0.2701 | 0.3160 | 0.1295 | 0.114 (16)* | 0.291 (3) |
H18F | −0.2480 | 0.2285 | 0.0726 | 0.114 (16)* | 0.291 (3) |
Cl1A | −0.2849 (11) | 0.3131 (6) | 0.0812 (7) | 0.0863 (17) | 0.419 (6) |
C1B | 0.7192 (6) | −0.2579 (3) | 0.3600 (3) | 0.0815 (12) | |
H1B | 0.7411 | −0.3191 | 0.4142 | 0.080 (4)* | |
C2B | 0.6887 (4) | −0.1550 (3) | 0.3675 (3) | 0.0580 (8) | |
C3B | 0.6620 (4) | −0.0630 (2) | 0.2857 (2) | 0.0469 (7) | |
C4B | 0.6565 (5) | −0.0767 (3) | 0.1978 (2) | 0.0591 (8) | |
C5B | 0.6860 (6) | −0.1799 (3) | 0.1924 (3) | 0.0827 (12) | |
H5B | 0.6849 | −0.1892 | 0.1335 | 0.080 (4)* | |
C6B | 0.7171 (7) | −0.2696 (3) | 0.2731 (4) | 0.0952 (15) | |
H6B | 0.7369 | −0.3390 | 0.2682 | 0.080 (4)* | |
C7B | 0.638 (3) | 0.0211 (16) | 0.1086 (14) | 0.122 (11) | 0.603 (5) |
H7B1 | 0.6117 | 0.0886 | 0.1266 | 0.114 (16)* | 0.301 (3) |
H7B2 | 0.5436 | 0.0154 | 0.0745 | 0.114 (16)* | 0.301 (3) |
H7B3 | 0.7464 | 0.0249 | 0.0650 | 0.114 (16)* | 0.301 (3) |
H7B4 | 0.6561 | −0.0026 | 0.0508 | 0.114 (16)* | 0.301 (3) |
H7B5 | 0.7242 | 0.0706 | 0.1029 | 0.114 (16)* | 0.301 (3) |
H7B6 | 0.5214 | 0.0610 | 0.1124 | 0.114 (16)* | 0.301 (3) |
Cl7B | 0.6024 (11) | 0.0360 (5) | 0.0992 (4) | 0.0797 (13) | 0.397 (5) |
N8B | 0.6264 (3) | 0.04257 (19) | 0.29224 (18) | 0.0487 (6) | |
H8B | 0.5312 | 0.0801 | 0.2750 | 0.080 (4)* | |
C9B | 0.7349 (4) | 0.0884 (2) | 0.3244 (2) | 0.0462 (7) | |
O10B | 0.8778 (3) | 0.05029 (18) | 0.34184 (19) | 0.0645 (6) | |
N11B | 0.6573 (3) | 0.18678 (19) | 0.33408 (18) | 0.0479 (6) | |
H11B | 0.5549 | 0.2070 | 0.3187 | 0.080 (4)* | |
C12B | 0.7257 (4) | 0.2544 (2) | 0.3652 (2) | 0.0432 (6) | |
C13B | 0.8944 (4) | 0.2432 (3) | 0.3830 (2) | 0.0554 (8) | |
H13B | 0.9699 | 0.1848 | 0.3752 | 0.080 (4)* | |
C14B | 0.9480 (5) | 0.3176 (3) | 0.4116 (3) | 0.0672 (10) | |
H14B | 1.0618 | 0.3111 | 0.4210 | 0.080 (4)* | |
N15B | 0.8428 (4) | 0.3992 (2) | 0.4266 (2) | 0.0659 (8) | |
H15B | 0.8800 | 0.4443 | 0.4464 | 0.080 (4)* | |
C16B | 0.6799 (5) | 0.4130 (3) | 0.4116 (2) | 0.0612 (9) | |
H16B | 0.6080 | 0.4707 | 0.4235 | 0.080 (4)* | |
C17B | 0.6170 (4) | 0.3442 (2) | 0.3791 (2) | 0.0501 (7) | |
H17B | 0.5042 | 0.3561 | 0.3662 | 0.080 (4)* | |
C18B | 0.701 (4) | −0.144 (3) | 0.466 (2) | 0.074 (11) | 0.397 (5) |
H18G | 0.6752 | −0.0655 | 0.4608 | 0.114 (16)* | 0.199 (3) |
H18H | 0.8190 | −0.1719 | 0.4854 | 0.114 (16)* | 0.199 (3) |
H18I | 0.6182 | −0.1878 | 0.5161 | 0.114 (16)* | 0.199 (3) |
H18J | 0.7331 | −0.2179 | 0.5141 | 0.114 (16)* | 0.199 (3) |
H18K | 0.5893 | −0.1116 | 0.4895 | 0.114 (16)* | 0.199 (3) |
H18L | 0.7900 | −0.0956 | 0.4587 | 0.114 (16)* | 0.199 (3) |
Cl1B | 0.6720 (9) | −0.1409 (5) | 0.4801 (5) | 0.0761 (14) | 0.603 (5) |
Cl1 | 0.78591 (10) | 0.49808 (6) | 0.59447 (6) | 0.0552 (3) | |
Cl2 | 0.29829 (10) | 0.21846 (6) | 0.26294 (6) | 0.0625 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.076 (2) | 0.0475 (19) | 0.069 (2) | 0.0088 (17) | −0.0277 (19) | −0.0109 (18) |
C2A | 0.071 (2) | 0.0387 (16) | 0.0548 (19) | −0.0076 (15) | −0.0162 (17) | −0.0057 (14) |
C3A | 0.071 (2) | 0.0302 (14) | 0.0454 (16) | −0.0068 (14) | −0.0215 (15) | −0.0060 (13) |
C4A | 0.076 (2) | 0.0391 (16) | 0.0567 (19) | −0.0111 (15) | −0.0050 (16) | −0.0145 (15) |
C5A | 0.108 (3) | 0.0444 (18) | 0.0493 (19) | −0.020 (2) | 0.0040 (19) | −0.0076 (16) |
C6A | 0.107 (3) | 0.0410 (18) | 0.053 (2) | 0.0070 (19) | −0.026 (2) | −0.0031 (16) |
C7A | 0.050 (8) | 0.026 (5) | 0.075 (10) | −0.005 (5) | −0.009 (7) | −0.027 (6) |
Cl7A | 0.070 (2) | 0.100 (4) | 0.114 (4) | −0.0141 (17) | −0.0103 (19) | −0.039 (2) |
N8A | 0.087 (2) | 0.0320 (13) | 0.0536 (15) | −0.0050 (12) | −0.0352 (14) | −0.0059 (11) |
C9A | 0.0598 (18) | 0.0332 (15) | 0.0455 (16) | −0.0043 (13) | −0.0117 (14) | −0.0085 (13) |
O10A | 0.109 (2) | 0.0392 (11) | 0.0547 (13) | −0.0073 (12) | −0.0369 (13) | −0.0099 (10) |
N11A | 0.0670 (16) | 0.0341 (13) | 0.0424 (13) | −0.0040 (11) | −0.0207 (12) | −0.0053 (11) |
C12A | 0.0493 (17) | 0.0355 (15) | 0.0440 (16) | −0.0013 (12) | −0.0051 (13) | −0.0059 (12) |
C13A | 0.079 (2) | 0.0371 (16) | 0.0561 (19) | −0.0065 (15) | −0.0182 (17) | −0.0091 (14) |
C14A | 0.094 (3) | 0.0395 (17) | 0.076 (2) | −0.0062 (17) | −0.023 (2) | −0.0149 (17) |
N15A | 0.080 (2) | 0.0331 (14) | 0.075 (2) | −0.0024 (13) | −0.0101 (16) | −0.0037 (14) |
C16A | 0.079 (2) | 0.0450 (18) | 0.0520 (19) | 0.0008 (16) | −0.0153 (17) | 0.0053 (15) |
C17A | 0.073 (2) | 0.0398 (17) | 0.0489 (18) | −0.0022 (15) | −0.0163 (16) | −0.0016 (14) |
C18A | 0.063 (9) | 0.113 (15) | 0.121 (18) | 0.011 (8) | −0.033 (10) | −0.013 (10) |
Cl1A | 0.095 (4) | 0.072 (3) | 0.077 (2) | −0.031 (2) | 0.004 (2) | −0.003 (2) |
C1B | 0.103 (3) | 0.0385 (19) | 0.092 (3) | −0.0078 (19) | −0.003 (2) | −0.0125 (19) |
C2B | 0.064 (2) | 0.0428 (17) | 0.065 (2) | −0.0061 (15) | −0.0063 (16) | −0.0158 (16) |
C3B | 0.0503 (17) | 0.0332 (15) | 0.0563 (18) | −0.0079 (12) | 0.0013 (13) | −0.0156 (14) |
C4B | 0.074 (2) | 0.0481 (18) | 0.0564 (19) | −0.0160 (16) | 0.0026 (16) | −0.0193 (16) |
C5B | 0.115 (3) | 0.066 (2) | 0.082 (3) | −0.028 (2) | 0.017 (2) | −0.046 (2) |
C6B | 0.140 (4) | 0.043 (2) | 0.104 (4) | −0.016 (2) | 0.012 (3) | −0.034 (2) |
C7B | 0.143 (14) | 0.123 (13) | 0.113 (13) | −0.006 (7) | −0.009 (7) | −0.065 (9) |
Cl7B | 0.118 (3) | 0.075 (2) | 0.0488 (17) | −0.034 (2) | −0.0102 (18) | −0.0130 (15) |
N8B | 0.0533 (15) | 0.0362 (13) | 0.0603 (15) | −0.0011 (11) | −0.0142 (12) | −0.0193 (11) |
C9B | 0.0492 (18) | 0.0393 (15) | 0.0480 (17) | −0.0058 (13) | −0.0012 (13) | −0.0134 (13) |
O10B | 0.0449 (13) | 0.0576 (14) | 0.0969 (18) | 0.0020 (11) | −0.0106 (12) | −0.0358 (13) |
N11B | 0.0440 (13) | 0.0425 (13) | 0.0625 (16) | −0.0035 (11) | −0.0072 (11) | −0.0243 (12) |
C12B | 0.0477 (16) | 0.0366 (15) | 0.0442 (15) | −0.0122 (12) | −0.0030 (12) | −0.0102 (12) |
C13B | 0.0522 (18) | 0.0456 (17) | 0.072 (2) | −0.0072 (14) | −0.0110 (15) | −0.0214 (16) |
C14B | 0.068 (2) | 0.056 (2) | 0.080 (2) | −0.0149 (18) | −0.0260 (19) | −0.0154 (18) |
N15B | 0.093 (2) | 0.0441 (15) | 0.0686 (18) | −0.0205 (15) | −0.0270 (16) | −0.0161 (14) |
C16B | 0.084 (3) | 0.0380 (17) | 0.060 (2) | −0.0058 (16) | −0.0060 (18) | −0.0154 (15) |
C17B | 0.0573 (19) | 0.0385 (16) | 0.0538 (17) | −0.0082 (13) | −0.0029 (14) | −0.0148 (14) |
C18B | 0.060 (10) | 0.051 (10) | 0.09 (2) | 0.009 (7) | −0.029 (14) | 0.009 (11) |
Cl1B | 0.107 (3) | 0.0648 (19) | 0.0493 (12) | −0.0180 (18) | −0.0004 (16) | −0.0107 (11) |
Cl1 | 0.0700 (5) | 0.0341 (4) | 0.0603 (5) | −0.0074 (3) | −0.0128 (4) | −0.0115 (3) |
Cl2 | 0.0624 (5) | 0.0558 (5) | 0.0780 (6) | 0.0086 (4) | −0.0341 (4) | −0.0292 (4) |
C1A—C6A | 1.362 (6) | C1B—C6B | 1.360 (6) |
C1A—C2A | 1.381 (5) | C1B—C2B | 1.381 (5) |
C1A—H1A | 0.9300 | C1B—H1B | 0.9300 |
C2A—C3A | 1.381 (5) | C2B—C3B | 1.393 (5) |
C2A—C18A | 1.55 (2) | C2B—C18B | 1.55 (3) |
C2A—Cl1A | 1.689 (8) | C2B—Cl1B | 1.735 (6) |
C3A—C4A | 1.391 (5) | C3B—C4B | 1.393 (4) |
C3A—N8A | 1.422 (4) | C3B—N8B | 1.410 (3) |
C4A—C5A | 1.381 (5) | C4B—C5B | 1.372 (5) |
C4A—C7A | 1.551 (18) | C4B—C7B | 1.491 (19) |
C4A—Cl7A | 1.711 (7) | C4B—Cl7B | 1.726 (7) |
C5A—C6A | 1.372 (6) | C5B—C6B | 1.372 (6) |
C5A—H5A | 0.9300 | C5B—H5B | 0.9300 |
C6A—H6A | 0.9300 | C6B—H6B | 0.9300 |
C7A—H7A1 | 1.0000 | C7B—H7B1 | 1.0000 |
C7A—H7A2 | 1.0000 | C7B—H7B2 | 1.0000 |
C7A—H7A3 | 1.0000 | C7B—H7B3 | 1.0000 |
C7A—H7A4 | 1.0000 | C7B—H7B4 | 1.0000 |
C7A—H7A5 | 1.0000 | C7B—H7B5 | 1.0000 |
C7A—H7A6 | 1.0000 | C7B—H7B6 | 1.0000 |
N8A—C9A | 1.356 (4) | N8B—C9B | 1.362 (4) |
N8A—H8A | 0.8600 | N8B—H8B | 0.8600 |
C9A—O10A | 1.204 (3) | C9B—O10B | 1.201 (4) |
C9A—O10A | 1.204 (3) | C9B—O10B | 1.201 (4) |
C9A—N11A | 1.389 (4) | C9B—N11B | 1.392 (4) |
N11A—C12A | 1.362 (4) | N11B—C12B | 1.357 (4) |
N11A—H11A | 0.8600 | N11B—H11B | 0.8600 |
C12A—C13A | 1.392 (4) | C12B—C13B | 1.393 (4) |
C12A—C17A | 1.400 (4) | C12B—C17B | 1.411 (4) |
C13A—C14A | 1.360 (5) | C13B—C14B | 1.349 (4) |
C13A—H13A | 0.9300 | C13B—H13B | 0.9300 |
C14A—N15A | 1.323 (5) | C14B—N15B | 1.319 (5) |
C14A—H14A | 0.9300 | C14B—H14B | 0.9300 |
N15A—C16A | 1.327 (5) | N15B—C16B | 1.331 (5) |
N15A—H15A | 0.8600 | N15B—H15B | 0.8600 |
C16A—C17A | 1.352 (4) | C16B—C17B | 1.361 (4) |
C16A—H16A | 0.9300 | C16B—H16B | 0.9300 |
C17A—H17A | 0.9300 | C17B—H17B | 0.9300 |
C18A—H18A | 1.0000 | C18B—H18G | 1.0000 |
C18A—H18B | 1.0000 | C18B—H18H | 1.0000 |
C18A—H18C | 1.0000 | C18B—H18I | 1.0000 |
C18A—H18D | 1.0000 | C18B—H18J | 1.0000 |
C18A—H18E | 1.0000 | C18B—H18K | 1.0000 |
C18A—H18F | 1.0000 | C18B—H18L | 1.0000 |
C6A—C1A—C2A | 120.2 (4) | C6B—C1B—C2B | 119.9 (4) |
C6A—C1A—H1A | 119.9 | C6B—C1B—H1B | 120.1 |
C2A—C1A—H1A | 119.9 | C2B—C1B—H1B | 120.1 |
C1A—C2A—C3A | 120.0 (3) | C1B—C2B—C3B | 120.2 (3) |
C1A—C2A—C18A | 118.3 (8) | C1B—C2B—C18B | 118.5 (12) |
C3A—C2A—C18A | 121.4 (8) | C3B—C2B—C18B | 121.1 (12) |
C1A—C2A—Cl1A | 118.9 (4) | C1B—C2B—Cl1B | 119.9 (4) |
C3A—C2A—Cl1A | 120.9 (4) | C3B—C2B—Cl1B | 119.9 (3) |
C2A—C3A—C4A | 119.8 (3) | C2B—C3B—C4B | 119.1 (3) |
C2A—C3A—N8A | 120.9 (3) | C2B—C3B—N8B | 121.1 (3) |
C4A—C3A—N8A | 119.3 (3) | C4B—C3B—N8B | 119.6 (3) |
C5A—C4A—C3A | 119.1 (3) | C5B—C4B—C3B | 119.5 (3) |
C5A—C4A—C7A | 114.1 (13) | C5B—C4B—C7B | 120.6 (9) |
C3A—C4A—C7A | 126.8 (13) | C3B—C4B—C7B | 119.6 (9) |
C5A—C4A—Cl7A | 121.4 (4) | C5B—C4B—Cl7B | 121.3 (4) |
C3A—C4A—Cl7A | 119.5 (4) | C3B—C4B—Cl7B | 119.1 (3) |
C6A—C5A—C4A | 120.7 (3) | C6B—C5B—C4B | 120.7 (4) |
C6A—C5A—H5A | 119.7 | C6B—C5B—H5B | 119.6 |
C4A—C5A—H5A | 119.7 | C4B—C5B—H5B | 119.6 |
C1A—C6A—C5A | 120.3 (3) | C1B—C6B—C5B | 120.6 (3) |
C1A—C6A—H6A | 119.9 | C1B—C6B—H6B | 119.7 |
C5A—C6A—H6A | 119.9 | C5B—C6B—H6B | 119.7 |
C4A—C7A—H7A1 | 109.5 | C4B—C7B—H7B1 | 109.5 |
C4A—C7A—H7A2 | 109.5 | C4B—C7B—H7B2 | 109.5 |
H7A1—C7A—H7A2 | 109.5 | H7B1—C7B—H7B2 | 109.5 |
C4A—C7A—H7A3 | 109.5 | C4B—C7B—H7B3 | 109.5 |
H7A1—C7A—H7A3 | 109.5 | H7B1—C7B—H7B3 | 109.5 |
H7A2—C7A—H7A3 | 109.5 | H7B2—C7B—H7B3 | 109.5 |
C4A—C7A—H7A4 | 109.5 | C4B—C7B—H7B4 | 109.5 |
H7A1—C7A—H7A4 | 141.1 | H7B1—C7B—H7B4 | 141.1 |
H7A2—C7A—H7A4 | 56.3 | H7B2—C7B—H7B4 | 56.3 |
H7A3—C7A—H7A4 | 56.3 | H7B3—C7B—H7B4 | 56.3 |
C4A—C7A—H7A5 | 109.5 | C4B—C7B—H7B5 | 109.5 |
H7A1—C7A—H7A5 | 56.3 | H7B1—C7B—H7B5 | 56.3 |
H7A2—C7A—H7A5 | 141.1 | H7B2—C7B—H7B5 | 141.1 |
H7A3—C7A—H7A5 | 56.3 | H7B3—C7B—H7B5 | 56.3 |
H7A4—C7A—H7A5 | 109.5 | H7B4—C7B—H7B5 | 109.5 |
C4A—C7A—H7A6 | 109.5 | C4B—C7B—H7B6 | 109.5 |
H7A1—C7A—H7A6 | 56.3 | H7B1—C7B—H7B6 | 56.3 |
H7A2—C7A—H7A6 | 56.3 | H7B2—C7B—H7B6 | 56.3 |
H7A3—C7A—H7A6 | 141.1 | H7B3—C7B—H7B6 | 141.1 |
H7A4—C7A—H7A6 | 109.5 | H7B4—C7B—H7B6 | 109.5 |
H7A5—C7A—H7A6 | 109.5 | H7B5—C7B—H7B6 | 109.5 |
C9A—N8A—C3A | 120.5 (2) | C9B—N8B—C3B | 123.5 (3) |
C9A—N8A—H8A | 119.8 | C9B—N8B—H8B | 118.3 |
C3A—N8A—H8A | 119.8 | C3B—N8B—H8B | 118.3 |
O10A—C9A—N8A | 123.8 (3) | O10B—C9B—N8B | 125.4 (3) |
O10A—C9A—N8A | 123.8 (3) | O10B—C9B—N8B | 125.4 (3) |
O10A—C9A—N11A | 124.4 (3) | O10B—C9B—N11B | 124.2 (3) |
O10A—C9A—N11A | 124.4 (3) | O10B—C9B—N11B | 124.2 (3) |
N8A—C9A—N11A | 111.8 (2) | N8B—C9B—N11B | 110.4 (3) |
C12A—N11A—C9A | 128.0 (2) | C12B—N11B—C9B | 127.0 (3) |
C12A—N11A—H11A | 116.0 | C12B—N11B—H11B | 116.5 |
C9A—N11A—H11A | 116.0 | C9B—N11B—H11B | 116.5 |
N11A—C12A—C13A | 124.6 (3) | N11B—C12B—C13B | 125.4 (3) |
N11A—C12A—C17A | 117.6 (3) | N11B—C12B—C17B | 117.0 (3) |
C13A—C12A—C17A | 117.8 (3) | C13B—C12B—C17B | 117.5 (3) |
C14A—C13A—C12A | 118.8 (3) | C14B—C13B—C12B | 119.7 (3) |
C14A—C13A—H13A | 120.6 | C14B—C13B—H13B | 120.1 |
C12A—C13A—H13A | 120.6 | C12B—C13B—H13B | 120.1 |
N15A—C14A—C13A | 121.7 (3) | N15B—C14B—C13B | 121.6 (3) |
N15A—C14A—H14A | 119.1 | N15B—C14B—H14B | 119.2 |
C13A—C14A—H14A | 119.1 | C13B—C14B—H14B | 119.2 |
C14A—N15A—C16A | 121.0 (3) | C14B—N15B—C16B | 121.1 (3) |
C14A—N15A—H15A | 119.5 | C14B—N15B—H15B | 119.4 |
C16A—N15A—H15A | 119.5 | C16B—N15B—H15B | 119.4 |
N15A—C16A—C17A | 120.8 (3) | N15B—C16B—C17B | 121.1 (3) |
N15A—C16A—H16A | 119.6 | N15B—C16B—H16B | 119.5 |
C17A—C16A—H16A | 119.6 | C17B—C16B—H16B | 119.5 |
C16A—C17A—C12A | 119.8 (3) | C16B—C17B—C12B | 118.9 (3) |
C16A—C17A—H17A | 120.1 | C16B—C17B—H17B | 120.5 |
C12A—C17A—H17A | 120.1 | C12B—C17B—H17B | 120.5 |
C2A—C18A—H18A | 109.5 | C2B—C18B—H18G | 109.5 |
C2A—C18A—H18B | 109.5 | C2B—C18B—H18H | 109.5 |
H18A—C18A—H18B | 109.5 | H18G—C18B—H18H | 109.5 |
C2A—C18A—H18C | 109.5 | C2B—C18B—H18I | 109.5 |
H18A—C18A—H18C | 109.5 | H18G—C18B—H18I | 109.5 |
H18B—C18A—H18C | 109.5 | H18H—C18B—H18I | 109.5 |
C2A—C18A—H18D | 109.5 | C2B—C18B—H18J | 109.5 |
H18A—C18A—H18D | 141.1 | H18G—C18B—H18J | 141.1 |
H18B—C18A—H18D | 56.3 | H18H—C18B—H18J | 56.3 |
H18C—C18A—H18D | 56.3 | H18I—C18B—H18J | 56.3 |
C2A—C18A—H18E | 109.5 | C2B—C18B—H18K | 109.5 |
H18A—C18A—H18E | 56.3 | H18G—C18B—H18K | 56.3 |
H18B—C18A—H18E | 141.1 | H18H—C18B—H18K | 141.1 |
H18C—C18A—H18E | 56.3 | H18I—C18B—H18K | 56.3 |
H18D—C18A—H18E | 109.5 | H18J—C18B—H18K | 109.5 |
C2A—C18A—H18F | 109.5 | C2B—C18B—H18L | 109.5 |
H18A—C18A—H18F | 56.3 | H18G—C18B—H18L | 56.3 |
H18B—C18A—H18F | 56.3 | H18H—C18B—H18L | 56.3 |
H18C—C18A—H18F | 141.1 | H18I—C18B—H18L | 141.1 |
H18D—C18A—H18F | 109.5 | H18J—C18B—H18L | 109.5 |
H18E—C18A—H18F | 109.5 | H18K—C18B—H18L | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N8A—H8A···Cl2 | 0.86 | 2.48 | 3.273 (3) | 154 |
N8B—H8B···Cl2 | 0.86 | 2.37 | 3.183 (3) | 158 |
N11A—H11A···Cl2 | 0.86 | 2.34 | 3.173 (3) | 163 |
N11B—H11B···Cl2 | 0.86 | 2.30 | 3.131 (3) | 164 |
N15A—H15A···Cl1i | 0.86 | 2.26 | 3.072 (3) | 158 |
N15B—H15B···Cl1 | 0.86 | 2.53 | 3.155 (3) | 131 |
N15B—H15B···Cl1ii | 0.86 | 2.82 | 3.397 (3) | 126 |
C13A—H13A···O10A | 0.93 | 2.27 | 2.864 (4) | 121 |
C13A—H13A···O10Aiii | 0.93 | 2.48 | 3.186 (4) | 133 |
C13B—H13B···O10B | 0.93 | 2.26 | 2.850 (4) | 121 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C13H13ClN3O+·Cl− |
Mr | 298.16 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 8.022 (3), 13.193 (4), 14.893 (4) |
α, β, γ (°) | 69.06 (3), 81.29 (2), 80.60 (3) |
V (Å3) | 1444.9 (9) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 4.01 |
Crystal size (mm) | 0.52 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Picker FACS-1 four-circle diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.586, 0.724 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4418, 4272, 3375 |
Rint | 0.005 |
θmax (°) | 60.0 |
(sin θ/λ)max (Å−1) | 0.562 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.134, 0.94 |
No. of reflections | 4272 |
No. of parameters | 385 |
No. of restraints | 7 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.15 |
Computer programs: Picker Operating Manual (Picker, 1967), Picker Operating Manual, DATRDN (Stewart, 1976), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N8A—H8A···Cl2 | 0.86 | 2.48 | 3.273 (3) | 154 |
N8B—H8B···Cl2 | 0.86 | 2.37 | 3.183 (3) | 158 |
N11A—H11A···Cl2 | 0.86 | 2.34 | 3.173 (3) | 163 |
N11B—H11B···Cl2 | 0.86 | 2.30 | 3.131 (3) | 164 |
N15A—H15A···Cl1i | 0.86 | 2.26 | 3.072 (3) | 158 |
N15B—H15B···Cl1 | 0.86 | 2.53 | 3.155 (3) | 131 |
N15B—H15B···Cl1ii | 0.86 | 2.82 | 3.397 (3) | 126 |
C13A—H13A···O10A | 0.93 | 2.27 | 2.864 (4) | 121 |
C13A—H13A···O10Aiii | 0.93 | 2.48 | 3.186 (4) | 133 |
C13B—H13B···O10B | 0.93 | 2.26 | 2.850 (4) | 121 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x, −y, −z. |
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N-Phenyl-N'-pyridinylureas were shown (Lobbestael et al., 1986) to possess anticonvulsant activity in the NIH–NINCDS Antiepileptic Drug Discovery Program. Subsequently, synthesis and testing of a series of over 50 substituted derivatives (Pavia et al., 1990) led to identification of N-(2-chloro-6-methylphenyl)-N'-pyridin-4-ylurea (CI-953) as having the most desirable in vivo profile for a potential anticonvulsant drug. The overall pharmaceutical effects of CI-953 in animal models were similar qualitatively and quantitatively to those of the well known antiepileptic drug phenytoin. These pharmacological similarities led us to determine the crystal and conformational structures of CI-953 in order to ascertain if it possessed stereochemical features in common with the chemically different drug phenytoin, which might be responsible for their similar anticonvulsant properties.
CI-953 hydrochloride crystallizes with Z' = 2 (Fig. 1). The two independent molecules have similar conformations with approximately planar pyridinylurea fragments intersecting the 2,6-disubstituted phenyl ring planes at angles of 69 and 78°. The phenyl rings in both molecules exist in two possible conformations differing by 180° rotation about the C3—N8 bond, resulting in positional disorder of the ortho Cl atoms and methyl groups, with each occupying 50% of each position in the crystal structure. This disorder is further augmented by rotational disorder of the methyl group's H atoms in both positions. Protonation occurs at the pyridinyl atom N15 in both independent molecules. As shown in Fig. 1, the two CI-953 molecules are indirectly linked through hydrogen bonds (Table 1) from the two urea imine groups in each to a chloride anion, a strong intermolecular interaction made possible by/resulting in the cis conformation of the imine H atoms (Fig.2). In addition, a C—H···O hydrogen bond links the type A molecules (Table 1). Van der Waals interactions also contribute to the crystal packing. Intramolecular bond distances and angles are consistent with normal values.
Stereochemical features common to several chemically different types of anticonvulsant drugs, and which are likely determinants of their antiepileptic activity, have been established (Camerman & Camerman, 1980). They consist of two electronegative atoms (hydrogen-bond acceptors) approximately 4.5–5.5 Å apart and at least one hydrophobic group (phenyl ring or equivalent) at a particular location and orientation relative to those atoms. These findings are further supported by a recent study (Thenmozhiyal et al., 2004) of the anticonvulsant properties of a series of phenylmethylenehydantoins, which found that the most important structure–activity descriptor, in essence, was the molecular electronegativity or electron donor capabilities. Although CI-953 is chemically very different from the other drugs studied, we have investigated through molecular superpositions whether similar stereochemical features could exist in CI-953.
Superpositions of CI-953 with phenytoin (Camerman & Camerman, 1971), the best known and conformationally most rigid of the anticonvulsants, maximizing the fit of the two most electronegative atoms, the carbonyl atom O10 and the pyridinal atom N15, with the carbonyl O atoms of phenytoin did not result in a fit of the substituted phenyl group of CI-953 with a phenyl ring of phenytoin even if allowable phenyl ring rotations were invoked. However, as noted above, the observed CI-953 molecular conformation has cis imine H atoms, a conformation favored because of intermolecular hydrogen bonding to the chloride ions. In the absence of this crystallographically imposed feature, a molecular conformation featuring a trans relation of the urea imine H atoms would also be plausible. Accordingly, we produced that conformation by a rotation of 180° about the N8—C9 bond. We then superposed this CI-953 structure with phenytoin by a least-squares maximization of the fit of three atoms in each molecule: O10 and N15 in CI-953 with the carbonyl O atoms in phenytoin, and a phenyl C atom in each (C5 in CI-953 and C11 in phenytoin). The results are shown stereoscopically in Fig. 3. Despite their differences in chemical structure, the two electronegative atoms in each molecule occupy similar positions in space and the disubstituted phenyl ring of CI-953 has a similar position and orientation to a phenyl ring of phenytoin. Since these features are the mediators of anticonvulsant activity in phenytoin, the stereochemical results presented here are persuasive evidence that these features are responsible for the similar anticonvulsant effects of CI-953, and that the two drugs likely involve very similar mechanisms.
It is also noteworthy that in the series of N-phenyl-N'-pyridinylureas synthesized and tested for anticonvulsant activity the most promising analogues, in addition to CI-953, were the 2,6-bismethylphenyl and 2,6-bischlorophenyl compounds. This suggest that the primary function of these groups is to ensure, through steric interactions, that the phenyl plane is roughly perpendicular to the plane of the rest of the molecule, thus maintaining an orientation similar to that of a phenyl ring in phenytoin. The small size of the substituents is also necessary to limit the overall size of the hydrophobic entity in this position.
The efficacy of many antiepileptic drugs is attributed to interactions with ion channels or neurotransmitter systems (Malawska, 2005) but their therapeutic mechanisms at the molecular level are not well understood. Although broad classification of drugs into categories based on a particular mechanistic system is possible, this has limited value because most anticonvulsants possess more than one mechanism of action. The identification of common stereochemical features in chemically different anticonvulsant molecules facilitates new drug design independent of the mechanism(s) of action.