The title compound, C9H8FN5·C3H7NO, contains two independent complexes in the asymmetric unit, each consisting of one 3,5-diamino-6-(2-fluorophenyl)-1,2,4-triazine molecule and one dimethylformamide solvent molecule. One triazine molecule is disordered over two conformations within the crystal, the occupancies being 62 (1) and 38 (1)%. The phenyl ring of this molecule resolves into two conformations rotated by almost 180° about the bridging bond between the two rings, while the triazine rings approximately superimpose on each other. The triazine molecules of the asymmetric unit differ in the dihedral angles between their respective phenyl and triazine ring planes, these being 57.6 (2)° for the fully occupied, and 76.9 (6) and 106.8 (8)° for the partially occupied molecules. An extensive network of hydrogen bonds maintains the crystal structure.
Supporting information
CCDC reference: 143260
The crystals were grown by slow evaporation from a dimethylformamide solution at
room temperature. Mounting was in a capillary due to the discovery that the
crystals were sensitive to the bonding agent used initially to make attachment
to a fibre.
The absolute structure was assigned arbitrarily.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CADRAL and CADSHEL (unpublished programs); program(s) used to solve structure: SHELX76 (Sheldrick, 1976); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SNOOPI (Davies, 1983).
3,5-Diamino-6-(2-fluorophenyl)-1,2,4-triazine dimethylformamide
top
Crystal data top
C9H8FN5·C3H7NO | Dx = 1.283 Mg m−3 |
Mr = 278.30 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, Pna21 | Cell parameters from 25 reflections |
a = 17.0016 (10) Å | θ = 7.5–26° |
b = 10.654 (1) Å | µ = 0.81 mm−1 |
c = 15.9038 (10) Å | T = 296 K |
V = 2880.7 (4) Å3 | Block, colourless |
Z = 8 | 0.4 × 0.3 × 0.3 mm |
F(000) = 1168 | |
Data collection top
Enraf-Nonius CAD4 diffractometer | Rint = 0.059 |
Radiation source: fine-focus sealed tube | θmax = 70.1°, θmin = 4.9° |
Graphite monochromator | h = −20→20 |
ω–2θ scans | k = 0→12 |
5092 measured reflections | l = 0→19 |
2750 independent reflections | 3 standard reflections every 200 reflections |
1815 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
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)] = 0.053 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.167 | Calculated w = 1/[σ2(Fo2) + (0.102P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max = 0.026 |
2750 reflections | Δρmax = 0.44 e Å−3 |
498 parameters | Δρmin = −0.19 e Å−3 |
123 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0070 (9) |
Crystal data top
C9H8FN5·C3H7NO | V = 2880.7 (4) Å3 |
Mr = 278.30 | Z = 8 |
Orthorhombic, Pna21 | Cu Kα radiation |
a = 17.0016 (10) Å | µ = 0.81 mm−1 |
b = 10.654 (1) Å | T = 296 K |
c = 15.9038 (10) Å | 0.4 × 0.3 × 0.3 mm |
Data collection top
Enraf-Nonius CAD4 diffractometer | Rint = 0.059 |
5092 measured reflections | 3 standard reflections every 200 reflections |
2750 independent reflections | intensity decay: none |
1815 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 123 restraints |
wR(F2) = 0.167 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | Δρmax = 0.44 e Å−3 |
2750 reflections | Δρmin = −0.19 e Å−3 |
498 parameters | |
Special details top
Experimental. All H atoms were initially located in difference maps, but were then placed
geometrically in riding positions and refined isotropically with Uiso
set to 1.2Ueq of the associated atom. |
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 | Occ. (<1) |
C1 | 0.0857 (2) | 0.5336 (3) | 0.3660 (3) | 0.0625 (11) | |
F2 | 0.0122 (2) | 0.4567 (4) | 0.2518 (3) | 0.1128 (13) | |
C2 | 0.0827 (3) | 0.4786 (5) | 0.2874 (4) | 0.0831 (16) | |
C3 | 0.1482 (4) | 0.4436 (6) | 0.2427 (4) | 0.111 (2) | |
H3 | 0.1435 | 0.4048 | 0.1906 | 0.133* | |
C4 | 0.2193 (5) | 0.4668 (7) | 0.2762 (6) | 0.122 (3) | |
H4 | 0.2643 | 0.4455 | 0.2462 | 0.147* | |
C5 | 0.2267 (3) | 0.5215 (7) | 0.3542 (5) | 0.102 (2) | |
H5 | 0.2763 | 0.5349 | 0.3771 | 0.123* | |
C6 | 0.1596 (2) | 0.5567 (5) | 0.3988 (4) | 0.0773 (14) | |
H6 | 0.1646 | 0.5958 | 0.4508 | 0.093* | |
C6t | 0.01337 (19) | 0.5751 (3) | 0.4110 (3) | 0.0566 (10) | |
N1 | 0.00907 (17) | 0.6932 (3) | 0.4315 (3) | 0.0618 (9) | |
N2 | −0.05424 (19) | 0.7379 (3) | 0.4735 (3) | 0.0653 (10) | |
C3t | −0.1123 (2) | 0.6559 (3) | 0.4906 (3) | 0.0609 (11) | |
N3 | −0.1761 (2) | 0.7027 (3) | 0.5286 (3) | 0.0794 (13) | |
H31 | −0.2144 | 0.6539 | 0.5421 | 0.095* | |
H32 | −0.1788 | 0.7816 | 0.5396 | 0.095* | |
N4 | −0.11067 (19) | 0.5325 (3) | 0.4748 (3) | 0.0636 (10) | |
C5t | −0.0474 (2) | 0.4898 (3) | 0.4354 (3) | 0.0596 (11) | |
N5 | −0.0430 (2) | 0.3657 (3) | 0.4198 (3) | 0.0750 (12) | |
H51 | −0.0805 | 0.3169 | 0.4354 | 0.090* | |
H52 | −0.0026 | 0.3354 | 0.3943 | 0.090* | |
C1' | −0.3358 (3) | 0.1814 (9) | 0.6314 (5) | 0.061 (4) | 0.617 (10) |
F2' | −0.2633 (3) | 0.2396 (8) | 0.7512 (4) | 0.125 (3) | 0.617 (10) |
C2' | −0.3333 (4) | 0.2279 (9) | 0.7125 (5) | 0.074 (3) | 0.617 (10) |
C3' | −0.3988 (5) | 0.2641 (14) | 0.7566 (7) | 0.092 (5) | 0.617 (10) |
H3' | −0.3944 | 0.2977 | 0.8104 | 0.110* | 0.617 (10) |
C4' | −0.4696 (6) | 0.250 (2) | 0.7202 (9) | 0.095 (7) | 0.617 (10) |
H4' | −0.5147 | 0.2713 | 0.7499 | 0.114* | 0.617 (10) |
C5' | −0.4765 (4) | 0.203 (2) | 0.6398 (8) | 0.124 (12) | 0.617 (10) |
H5' | −0.5259 | 0.1940 | 0.6155 | 0.149* | 0.617 (10) |
C6' | −0.4092 (3) | 0.1710 (13) | 0.5947 (7) | 0.083 (4) | 0.617 (10) |
H6' | −0.4137 | 0.1422 | 0.5397 | 0.099* | 0.617 (10) |
C6t' | −0.2636 (3) | 0.1392 (6) | 0.5865 (5) | 0.054 (3) | 0.617 (10) |
N1' | −0.2493 (5) | 0.0191 (6) | 0.5858 (9) | 0.055 (3) | 0.617 (10) |
N2' | −0.1852 (5) | −0.0267 (6) | 0.5457 (8) | 0.061 (4) | 0.617 (10) |
C3t' | −0.1344 (6) | 0.0577 (7) | 0.5138 (10) | 0.066 (5) | 0.617 (10) |
N3' | −0.0721 (9) | 0.0108 (10) | 0.4729 (16) | 0.084 (6) | 0.617 (10) |
H31' | −0.0406 | 0.0603 | 0.4467 | 0.100* | 0.617 (10) |
H32' | −0.0637 | −0.0688 | 0.4728 | 0.100* | 0.617 (10) |
N4' | −0.1449 (7) | 0.1823 (7) | 0.5121 (11) | 0.071 (5) | 0.617 (10) |
C5t' | −0.2081 (5) | 0.2254 (5) | 0.5515 (8) | 0.061 (5) | 0.617 (10) |
N5' | −0.2160 (7) | 0.3506 (6) | 0.5596 (12) | 0.077 (5) | 0.617 (10) |
H51' | −0.1807 | 0.3999 | 0.5394 | 0.093* | 0.617 (10) |
H52' | −0.2564 | 0.3811 | 0.5849 | 0.093* | 0.617 (10) |
C1" | −0.3365 (5) | 0.1867 (13) | 0.6467 (7) | 0.062 (6) | 0.383 (10) |
F2" | −0.4125 (5) | 0.0852 (11) | 0.5436 (6) | 0.123 (5) | 0.383 (10) |
C2" | −0.4090 (5) | 0.1590 (12) | 0.6122 (7) | 0.095 (10) | 0.383 (10) |
C3" | −0.4787 (5) | 0.2053 (19) | 0.6425 (12) | 0.115 (19) | 0.383 (10) |
H3" | −0.5260 | 0.1882 | 0.6154 | 0.138* | 0.383 (10) |
C4" | −0.4770 (8) | 0.276 (3) | 0.7125 (17) | 0.105 (14) | 0.383 (10) |
H4" | −0.5238 | 0.3064 | 0.7348 | 0.126* | 0.383 (10) |
C5" | −0.4070 (9) | 0.3044 (18) | 0.7516 (10) | 0.089 (8) | 0.383 (10) |
H5" | −0.4069 | 0.3499 | 0.8015 | 0.107* | 0.383 (10) |
C6" | −0.3362 (7) | 0.2647 (17) | 0.7162 (9) | 0.093 (8) | 0.383 (10) |
H6" | −0.2887 | 0.2908 | 0.7394 | 0.111* | 0.383 (10) |
C6t" | −0.2616 (4) | 0.1469 (9) | 0.6061 (8) | 0.046 (4) | 0.383 (10) |
N1" | −0.2444 (9) | 0.0278 (10) | 0.6089 (13) | 0.066 (7) | 0.383 (10) |
N2" | −0.1782 (8) | −0.0161 (10) | 0.5721 (11) | 0.050 (4) | 0.383 (10) |
C3t" | −0.1350 (7) | 0.0666 (12) | 0.5277 (12) | 0.056 (7) | 0.383 (10) |
N3" | −0.0689 (13) | 0.0221 (16) | 0.493 (2) | 0.069 (7) | 0.383 (10) |
H31" | −0.0561 | −0.0554 | 0.4998 | 0.083* | 0.383 (10) |
H32" | −0.0391 | 0.0710 | 0.4640 | 0.083* | 0.383 (10) |
N4" | −0.1488 (9) | 0.1900 (10) | 0.5217 (16) | 0.059 (7) | 0.383 (10) |
C5t" | −0.2143 (8) | 0.2312 (10) | 0.5577 (12) | 0.072 (9) | 0.383 (10) |
N5" | −0.2359 (10) | 0.3509 (10) | 0.5434 (16) | 0.056 (5) | 0.383 (10) |
H51" | −0.2075 | 0.3981 | 0.5117 | 0.068* | 0.383 (10) |
H52" | −0.2780 | 0.3802 | 0.5659 | 0.068* | 0.383 (10) |
O1A | 0.0630 (2) | 0.1600 (4) | 0.4007 (4) | 0.1088 (16) | |
C1A | 0.1326 (4) | 0.1625 (6) | 0.3780 (5) | 0.1027 (19) | |
H1A | 0.1591 | 0.2388 | 0.3795 | 0.123* | |
N1A | 0.1713 (3) | 0.0612 (5) | 0.3515 (4) | 0.0907 (15) | |
C2A | 0.2513 (4) | 0.0774 (10) | 0.3220 (7) | 0.144 (4) | |
H2A1 | 0.2719 | −0.0022 | 0.3042 | 0.173* | |
H2A2 | 0.2832 | 0.1102 | 0.3666 | 0.173* | |
H2A3 | 0.2517 | 0.1348 | 0.2755 | 0.173* | |
C3A | 0.1379 (7) | −0.0588 (9) | 0.3511 (10) | 0.170 (5) | |
H3A1 | 0.1754 | −0.1182 | 0.3299 | 0.204* | |
H3A2 | 0.0921 | −0.0588 | 0.3158 | 0.204* | |
H3A3 | 0.1232 | −0.0817 | 0.4073 | 0.204* | |
O1B | −0.3249 (2) | 0.5582 (4) | 0.5804 (4) | 0.0980 (14) | |
C1B | −0.3907 (3) | 0.5592 (5) | 0.6087 (4) | 0.0766 (14) | |
H1B | −0.4194 | 0.4850 | 0.6052 | 0.092* | |
N1B | −0.4256 (2) | 0.6569 (4) | 0.6443 (3) | 0.0768 (11) | |
C2B | −0.3860 (5) | 0.7758 (7) | 0.6472 (8) | 0.138 (3) | |
H2B1 | −0.4188 | 0.8361 | 0.6753 | 0.166* | |
H2B2 | −0.3753 | 0.8038 | 0.5910 | 0.166* | |
H2B3 | −0.3374 | 0.7669 | 0.6774 | 0.166* | |
C3B | −0.5048 (4) | 0.6498 (9) | 0.6770 (6) | 0.115 (2) | |
H3B1 | −0.5193 | 0.7296 | 0.7005 | 0.138* | |
H3B2 | −0.5073 | 0.5866 | 0.7200 | 0.138* | |
H3B3 | −0.5404 | 0.6287 | 0.6324 | 0.138* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.072 (3) | 0.052 (2) | 0.064 (3) | −0.0006 (18) | 0.009 (2) | 0.0043 (19) |
F2 | 0.143 (3) | 0.104 (2) | 0.091 (3) | −0.027 (2) | −0.014 (2) | −0.018 (2) |
C2 | 0.113 (4) | 0.065 (3) | 0.072 (4) | −0.008 (3) | 0.016 (3) | −0.006 (3) |
C3 | 0.152 (6) | 0.088 (4) | 0.093 (5) | −0.020 (4) | 0.058 (5) | −0.016 (4) |
C4 | 0.147 (7) | 0.087 (5) | 0.132 (8) | 0.001 (4) | 0.079 (6) | 0.010 (4) |
C5 | 0.079 (3) | 0.117 (5) | 0.112 (6) | 0.004 (3) | 0.034 (4) | 0.016 (4) |
C6 | 0.066 (3) | 0.085 (3) | 0.081 (4) | −0.005 (2) | 0.015 (2) | 0.015 (3) |
C6t | 0.058 (2) | 0.0431 (19) | 0.068 (3) | 0.0000 (16) | 0.0017 (19) | 0.0023 (18) |
N1 | 0.066 (2) | 0.0485 (18) | 0.071 (2) | 0.0008 (15) | 0.0055 (18) | −0.0032 (17) |
N2 | 0.067 (2) | 0.0464 (17) | 0.082 (3) | −0.0044 (15) | 0.009 (2) | 0.0014 (19) |
C3t | 0.063 (2) | 0.042 (2) | 0.078 (3) | 0.0024 (17) | 0.002 (2) | 0.0012 (19) |
N3 | 0.067 (2) | 0.050 (2) | 0.122 (4) | −0.0001 (16) | 0.020 (2) | −0.007 (2) |
N4 | 0.0600 (18) | 0.0408 (17) | 0.090 (3) | 0.0013 (13) | 0.0079 (19) | 0.0023 (18) |
C5t | 0.065 (2) | 0.0425 (19) | 0.071 (3) | −0.0029 (17) | −0.002 (2) | 0.002 (2) |
N5 | 0.066 (2) | 0.0427 (17) | 0.116 (4) | −0.0019 (15) | 0.020 (2) | −0.002 (2) |
C1' | 0.079 (11) | 0.050 (7) | 0.053 (5) | −0.001 (6) | 0.008 (5) | 0.008 (4) |
F2' | 0.127 (5) | 0.146 (6) | 0.101 (5) | 0.010 (4) | −0.026 (4) | −0.038 (4) |
C2' | 0.085 (7) | 0.051 (7) | 0.086 (9) | 0.013 (4) | 0.007 (6) | −0.007 (5) |
C3' | 0.140 (12) | 0.054 (9) | 0.080 (8) | 0.016 (7) | 0.029 (8) | −0.004 (5) |
C4' | 0.098 (12) | 0.082 (11) | 0.104 (12) | 0.023 (7) | 0.050 (10) | 0.010 (8) |
C5' | 0.098 (15) | 0.16 (2) | 0.112 (16) | 0.052 (12) | −0.015 (11) | −0.022 (14) |
C6' | 0.051 (7) | 0.105 (10) | 0.093 (8) | 0.015 (6) | 0.013 (5) | −0.025 (7) |
C6t' | 0.056 (6) | 0.051 (6) | 0.055 (6) | 0.000 (4) | −0.003 (4) | −0.007 (4) |
N1' | 0.070 (5) | 0.037 (4) | 0.057 (8) | −0.002 (3) | 0.008 (4) | −0.007 (3) |
N2' | 0.069 (5) | 0.047 (4) | 0.067 (8) | −0.003 (3) | 0.009 (5) | −0.008 (4) |
C3t' | 0.084 (10) | 0.025 (5) | 0.089 (9) | −0.003 (5) | 0.021 (6) | 0.004 (4) |
N3' | 0.081 (9) | 0.055 (7) | 0.115 (12) | 0.003 (5) | 0.042 (9) | −0.010 (6) |
N4' | 0.057 (8) | 0.062 (10) | 0.094 (10) | 0.009 (6) | 0.019 (7) | 0.007 (8) |
C5t' | 0.074 (9) | 0.027 (6) | 0.082 (10) | −0.005 (6) | −0.010 (7) | 0.009 (5) |
N5' | 0.061 (7) | 0.046 (5) | 0.125 (11) | 0.008 (3) | 0.014 (7) | 0.000 (4) |
C1" | 0.049 (12) | 0.065 (13) | 0.071 (11) | 0.004 (9) | 0.016 (8) | −0.013 (10) |
F2" | 0.089 (6) | 0.161 (11) | 0.118 (8) | 0.015 (6) | −0.026 (5) | −0.065 (8) |
C2" | 0.10 (2) | 0.11 (2) | 0.068 (11) | −0.013 (15) | 0.009 (11) | 0.020 (12) |
C3" | 0.062 (15) | 0.09 (2) | 0.19 (4) | −0.007 (13) | 0.08 (2) | 0.00 (2) |
C4" | 0.086 (16) | 0.066 (14) | 0.16 (3) | 0.024 (11) | 0.056 (17) | 0.014 (14) |
C5" | 0.120 (17) | 0.048 (13) | 0.100 (15) | 0.015 (9) | 0.048 (12) | −0.004 (9) |
C6" | 0.154 (19) | 0.048 (11) | 0.076 (13) | 0.012 (8) | 0.053 (13) | −0.014 (7) |
C6t" | 0.077 (11) | 0.032 (7) | 0.029 (6) | −0.004 (6) | 0.002 (5) | −0.003 (4) |
N1" | 0.089 (11) | 0.065 (10) | 0.044 (11) | 0.002 (7) | 0.001 (6) | −0.009 (6) |
N2" | 0.061 (7) | 0.040 (6) | 0.048 (10) | −0.001 (4) | 0.001 (6) | −0.011 (5) |
C3t" | 0.035 (8) | 0.069 (15) | 0.064 (10) | 0.013 (8) | −0.005 (7) | −0.012 (9) |
N3" | 0.064 (10) | 0.022 (6) | 0.12 (2) | 0.011 (5) | 0.012 (8) | −0.010 (7) |
N4" | 0.061 (13) | 0.012 (8) | 0.104 (17) | 0.000 (7) | 0.014 (11) | −0.012 (8) |
C5t" | 0.049 (12) | 0.077 (18) | 0.091 (18) | 0.019 (11) | 0.031 (12) | −0.020 (12) |
N5" | 0.035 (6) | 0.036 (6) | 0.098 (12) | 0.003 (4) | 0.011 (8) | 0.014 (5) |
O1A | 0.078 (2) | 0.091 (3) | 0.157 (5) | 0.014 (2) | 0.037 (3) | −0.002 (3) |
C1A | 0.115 (5) | 0.081 (4) | 0.112 (5) | 0.006 (3) | 0.014 (4) | −0.003 (4) |
N1A | 0.079 (3) | 0.107 (4) | 0.086 (3) | 0.028 (3) | 0.004 (2) | −0.006 (3) |
C2A | 0.096 (5) | 0.194 (10) | 0.142 (8) | −0.012 (6) | 0.016 (5) | −0.022 (7) |
C3A | 0.194 (9) | 0.105 (7) | 0.211 (13) | −0.015 (6) | 0.019 (9) | −0.038 (8) |
O1B | 0.073 (2) | 0.079 (2) | 0.142 (4) | 0.0139 (16) | 0.026 (2) | −0.002 (2) |
C1B | 0.073 (3) | 0.064 (3) | 0.093 (4) | 0.000 (2) | 0.005 (3) | −0.002 (3) |
N1B | 0.074 (2) | 0.077 (3) | 0.079 (3) | 0.0065 (19) | 0.005 (2) | 0.001 (2) |
C2B | 0.119 (5) | 0.085 (4) | 0.211 (10) | 0.003 (4) | 0.026 (6) | −0.030 (6) |
C3B | 0.091 (4) | 0.143 (6) | 0.111 (6) | 0.008 (4) | 0.031 (4) | −0.012 (5) |
Geometric parameters (Å, º) top
C1—C2 | 1.382 (7) | C3t'—N3' | 1.339 (5) |
C1—C6t | 1.490 (5) | N4'—C5t' | 1.326 (5) |
F2—C2 | 1.346 (6) | C5t'—N5' | 1.347 (5) |
C2—C3 | 1.371 (7) | C1"—C2" | 1.382 (7) |
C3—C4 | 1.344 (11) | C1"—C6" | 1.383 (6) |
C4—C5 | 1.376 (11) | C1"—C6t" | 1.490 (5) |
C5—C6 | 1.394 (7) | F2"—C2" | 1.346 (6) |
C6t—N1 | 1.303 (4) | C2"—C3" | 1.371 (7) |
C6t—C5t | 1.429 (5) | C3"—C4" | 1.344 (11) |
N1—N2 | 1.353 (4) | C4"—C5" | 1.376 (11) |
N2—C3t | 1.346 (4) | C5"—C6" | 1.394 (7) |
C3t—N3 | 1.338 (5) | C6t"—N1" | 1.303 (4) |
C3t—N4 | 1.338 (4) | C6t"—C5t" | 1.430 (5) |
N4—C5t | 1.326 (5) | N1"—N2" | 1.353 (4) |
C5t—N5 | 1.347 (4) | N2"—C3t" | 1.347 (4) |
C1'—C6' | 1.382 (6) | C3t"—N4" | 1.339 (4) |
C1'—C2' | 1.382 (7) | C3t"—N3" | 1.339 (5) |
C1'—C6t' | 1.490 (5) | N4"—C5t" | 1.326 (5) |
F2'—C2' | 1.346 (6) | C5t"—N5" | 1.347 (5) |
C2'—C3' | 1.372 (7) | O1A—C1A | 1.238 (8) |
C3'—C4' | 1.344 (11) | C1A—N1A | 1.333 (8) |
C4'—C5' | 1.376 (11) | N1A—C3A | 1.399 (11) |
C5'—C6' | 1.394 (7) | N1A—C2A | 1.448 (9) |
C6t'—N1' | 1.303 (4) | O1B—C1B | 1.206 (6) |
C6t'—C5t' | 1.430 (5) | C1B—N1B | 1.326 (7) |
N1'—N2' | 1.353 (4) | N1B—C2B | 1.435 (9) |
N2'—C3t' | 1.347 (4) | N1B—C3B | 1.446 (8) |
C3t'—N4' | 1.339 (4) | | |
| | | |
C6—C1—C2 | 116.8 (4) | N4'—C3t'—N2' | 125.7 (3) |
C6—C1—C6t | 121.1 (4) | N4'—C3t'—N3' | 117.7 (3) |
C2—C1—C6t | 122.0 (4) | N2'—C3t'—N3' | 116.2 (3) |
F2—C2—C3 | 117.2 (5) | C5t'—N4'—C3t' | 116.2 (3) |
F2—C2—C1 | 119.1 (5) | N4'—C5t'—N5' | 118.0 (3) |
C3—C2—C1 | 123.6 (5) | N4'—C5t'—C6t' | 119.8 (3) |
C4—C3—C2 | 118.3 (6) | N5'—C5t'—C6t' | 122.2 (4) |
C3—C4—C5 | 121.1 (5) | C2"—C1"—C6" | 116.7 (4) |
C4—C5—C6 | 119.9 (6) | C2"—C1"—C6t" | 122.0 (4) |
C1—C6—C5 | 120.2 (6) | C6"—C1"—C6t" | 121.0 (4) |
N1—C6t—C5t | 120.4 (3) | F2"—C2"—C3" | 117.2 (6) |
N1—C6t—C1 | 117.0 (3) | F2"—C2"—C1" | 119.1 (5) |
C5t—C6t—C1 | 122.5 (3) | C3"—C2"—C1" | 123.6 (5) |
C6t—N1—N2 | 120.6 (3) | C4"—C3"—C2" | 118.3 (6) |
N1—N2—C3t | 117.0 (3) | C3"—C4"—C5" | 121.1 (5) |
N3—C3t—N4 | 117.9 (3) | C4"—C5"—C6" | 119.8 (6) |
N3—C3t—N2 | 116.3 (3) | C1"—C6"—C5" | 120.2 (6) |
N4—C3t—N2 | 125.8 (3) | N1"—C6t"—C5t" | 120.3 (3) |
C5t—N4—C3t | 116.3 (3) | N1"—C6t"—C1" | 117.0 (3) |
N4—C5t—N5 | 117.9 (3) | C5t"—C6t"—C1" | 122.4 (3) |
N4—C5t—C6t | 119.8 (3) | C6t"—N1"—N2" | 120.5 (3) |
N5—C5t—C6t | 122.3 (4) | C3t"—N2"—N1" | 117.0 (3) |
C6'—C1'—C2' | 116.8 (4) | N2"—C3t"—N4" | 125.7 (4) |
C6'—C1'—C6t' | 121.1 (4) | N2"—C3t"—N3" | 116.2 (3) |
C2'—C1'—C6t' | 122.1 (4) | N4"—C3t"—N3" | 117.8 (3) |
F2'—C2'—C3' | 117.2 (5) | C5t"—N4"—C3t" | 116.2 (3) |
F2'—C2'—C1' | 119.2 (5) | N4"—C5t"—N5" | 118.0 (3) |
C3'—C2'—C1' | 123.6 (5) | N4"—C5t"—C6t" | 119.7 (3) |
C4'—C3'—C2' | 118.3 (6) | N5"—C5t"—C6t" | 122.2 (4) |
C3'—C4'—C5' | 121.1 (5) | O1A—C1A—N1A | 123.2 (6) |
C4'—C5'—C6' | 119.9 (6) | C1A—N1A—C3A | 122.7 (7) |
C1'—C6'—C5' | 120.2 (6) | C1A—N1A—C2A | 118.0 (7) |
N1'—C6t'—C5t' | 120.3 (3) | C3A—N1A—C2A | 119.3 (7) |
N1'—C6t'—C1' | 117.0 (3) | O1B—C1B—N1B | 125.5 (5) |
C5t'—C6t'—C1' | 122.5 (3) | C1B—N1B—C2B | 119.8 (5) |
C6t'—N1'—N2' | 120.5 (3) | C1B—N1B—C3B | 122.0 (5) |
C3t'—N2'—N1' | 117.0 (3) | C2B—N1B—C3B | 118.1 (5) |
| | | |
C6—C1—C2—F2 | −178.5 (5) | C1'—C6t'—N1'—N2' | 179.4 (10) |
C6t—C1—C2—F2 | −3.1 (7) | C6t'—N1'—N2'—C3t' | 5.8 (19) |
C6—C1—C2—C3 | 1.9 (8) | N1'—N2'—C3t'—N4' | −6 (2) |
C6t—C1—C2—C3 | 177.4 (5) | N1'—N2'—C3t'—N3' | −178.7 (15) |
F2—C2—C3—C4 | 178.7 (6) | N2'—C3t'—N4'—C5t' | 6 (2) |
C1—C2—C3—C4 | −1.7 (10) | N3'—C3t'—N4'—C5t' | 178.5 (16) |
C2—C3—C4—C5 | 1.5 (11) | C3t'—N4'—C5t'—N5' | 172.5 (16) |
C3—C4—C5—C6 | −1.6 (11) | C3t'—N4'—C5t'—C6t' | −5.3 (17) |
C2—C1—C6—C5 | −1.9 (7) | N1'—C6t'—C5t'—N4' | 5.6 (14) |
C6t—C1—C6—C5 | −177.5 (5) | C1'—C6t'—C5t'—N4' | −179.9 (10) |
C4—C5—C6—C1 | 1.9 (9) | N1'—C6t'—C5t'—N5' | −172.1 (14) |
C6—C1—C6t—N1 | 53.9 (6) | C1'—C6t'—C5t'—N5' | 2.4 (15) |
C2—C1—C6t—N1 | −121.4 (5) | C6"—C1"—C2"—F2" | 178.9 (13) |
C6—C1—C6t—C5t | −122.7 (5) | C6t"—C1"—C2"—F2" | 5.6 (13) |
C2—C1—C6t—C5t | 62.0 (6) | C6"—C1"—C2"—C3" | 0.7 (18) |
C5t—C6t—N1—N2 | −2.5 (6) | C6t"—C1"—C2"—C3" | −172.7 (14) |
C1—C6t—N1—N2 | −179.1 (4) | F2"—C2"—C3"—C4" | 178.0 (18) |
C6t—N1—N2—C3t | −1.6 (7) | C1"—C2"—C3"—C4" | −4 (3) |
N1—N2—C3t—N3 | −177.0 (5) | C2"—C3"—C4"—C5" | 2 (4) |
N1—N2—C3t—N4 | 4.8 (7) | C3"—C4"—C5"—C6" | 3 (3) |
N3—C3t—N4—C5t | 178.5 (4) | C2"—C1"—C6"—C5" | 4 (2) |
N2—C3t—N4—C5t | −3.3 (8) | C6t"—C1"—C6"—C5" | 177.8 (13) |
C3t—N4—C5t—N5 | 178.8 (5) | C4"—C5"—C6"—C1" | −6 (3) |
C3t—N4—C5t—C6t | −1.1 (7) | C2"—C1"—C6t"—N1" | −71.9 (15) |
N1—C6t—C5t—N4 | 4.0 (6) | C6"—C1"—C6t"—N1" | 115.0 (17) |
C1—C6t—C5t—N4 | −179.6 (4) | C2"—C1"—C6t"—C5t" | 101.2 (14) |
N1—C6t—C5t—N5 | −175.9 (5) | C6"—C1"—C6t"—C5t" | −71.9 (15) |
C1—C6t—C5t—N5 | 0.5 (7) | C5t"—C6t"—N1"—N2" | 5 (2) |
C6'—C1'—C2'—F2' | 179.8 (10) | C1"—C6t"—N1"—N2" | 178.7 (15) |
C6t'—C1'—C2'—F2' | 2.3 (11) | C6t"—N1"—N2"—C3t" | −5 (3) |
C6'—C1'—C2'—C3' | −0.5 (15) | N1"—N2"—C3t"—N4" | 5 (3) |
C6t'—C1'—C2'—C3' | −177.9 (10) | N1"—N2"—C3t"—N3" | 179 (2) |
F2'—C2'—C3'—C4' | −178.0 (14) | N2"—C3t"—N4"—C5t" | −5 (3) |
C1'—C2'—C3'—C4' | 2 (2) | N3"—C3t"—N4"—C5t" | −179 (2) |
C2'—C3'—C4'—C5' | −2 (3) | C3t"—N4"—C5t"—N5" | −171 (2) |
C3'—C4'—C5'—C6' | 0 (3) | C3t"—N4"—C5t"—C6t" | 6 (2) |
C2'—C1'—C6'—C5' | −1.7 (18) | N1"—C6t"—C5t"—N4" | −5.9 (19) |
C6t'—C1'—C6'—C5' | 175.8 (13) | C1"—C6t"—C5t"—N4" | −178.8 (12) |
C4'—C5'—C6'—C1' | 2 (3) | N1"—C6t"—C5t"—N5" | 170 (2) |
C6'—C1'—C6t'—N1' | −78.8 (12) | C1"—C6t"—C5t"—N5" | −2 (2) |
C2'—C1'—C6t'—N1' | 98.6 (11) | O1A—C1A—N1A—C3A | −3.4 (13) |
C6'—C1'—C6t'—C5t' | 106.6 (11) | O1A—C1A—N1A—C2A | 176.5 (8) |
C2'—C1'—C6t'—C5t' | −76.0 (10) | O1B—C1B—N1B—C2B | 3.5 (11) |
C5t'—C6t'—N1'—N2' | −5.8 (17) | O1B—C1B—N1B—C3B | −179.8 (7) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H31···O1B | 0.86 | 2.22 | 3.073 (5) | 170 |
N5—H52···O1A | 0.86 | 2.18 | 2.854 (5) | 135 |
N3—H32···N2′i | 0.86 | 2.05 | 2.900 (7) | 171 |
N5—H51···N4′ | 0.86 | 2.18 | 2.996 (8) | 159 |
N3′—H31′···O1A | 0.86 | 2.18 | 3.019 (11) | 165 |
N3′—H32′···N2ii | 0.86 | 2.07 | 2.923 (11) | 175 |
N5′—H52′···O1B | 0.86 | 2.22 | 2.903 (8) | 137 |
N5′—H51′···N4 | 0.86 | 2.11 | 2.964 (10) | 169 |
N3—H32···N2"i | 0.86 | 2.22 | 3.074 (11) | 176 |
N5—H51···N4" | 0.86 | 2.25 | 3.061 (10) | 157 |
N3"—H32"···O1A | 0.86 | 2.22 | 3.055 (14) | 164 |
N3"—H31"···N2ii | 0.86 | 2.24 | 3.053 (17) | 157 |
N5"—H52"···O1B | 0.86 | 2.07 | 2.742 (11) | 134 |
N5"—H51"···N4 | 0.86 | 2.26 | 3.076 (13) | 159 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z. |
Experimental details
Crystal data |
Chemical formula | C9H8FN5·C3H7NO |
Mr | 278.30 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 296 |
a, b, c (Å) | 17.0016 (10), 10.654 (1), 15.9038 (10) |
V (Å3) | 2880.7 (4) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 0.81 |
Crystal size (mm) | 0.4 × 0.3 × 0.3 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5092, 2750, 1815 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.610 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.167, 1.13 |
No. of reflections | 2750 |
No. of parameters | 498 |
No. of restraints | 123 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.44, −0.19 |
Selected geometric parameters (Å, º) topC1—C6t | 1.490 (5) | N2—C3t | 1.346 (4) |
F2—C2 | 1.346 (6) | C3t—N3 | 1.338 (5) |
C6t—N1 | 1.303 (4) | C3t—N4 | 1.338 (4) |
C6t—C5t | 1.429 (5) | N4—C5t | 1.326 (5) |
N1—N2 | 1.353 (4) | C5t—N5 | 1.347 (4) |
| | | |
N1—C6t—C5t | 120.4 (3) | N3—C3t—N2 | 116.3 (3) |
N1—C6t—C1 | 117.0 (3) | N4—C3t—N2 | 125.8 (3) |
C5t—C6t—C1 | 122.5 (3) | C5t—N4—C3t | 116.3 (3) |
C6t—N1—N2 | 120.6 (3) | N4—C5t—N5 | 117.9 (3) |
N1—N2—C3t | 117.0 (3) | N4—C5t—C6t | 119.8 (3) |
N3—C3t—N4 | 117.9 (3) | N5—C5t—C6t | 122.3 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H31···O1B | 0.86 | 2.22 | 3.073 (5) | 170 |
N5—H52···O1A | 0.86 | 2.18 | 2.854 (5) | 135 |
N3—H32···N2'i | 0.86 | 2.05 | 2.900 (7) | 171 |
N5—H51···N4' | 0.86 | 2.18 | 2.996 (8) | 159 |
N3'—H31'···O1A | 0.86 | 2.18 | 3.019 (11) | 165 |
N3'—H32'···N2ii | 0.86 | 2.07 | 2.923 (11) | 175 |
N5'—H52'···O1B | 0.86 | 2.22 | 2.903 (8) | 137 |
N5'—H51'···N4 | 0.86 | 2.11 | 2.964 (10) | 169 |
N3—H32···N2"i | 0.86 | 2.22 | 3.074 (11) | 176 |
N5—H51···N4" | 0.86 | 2.25 | 3.061 (10) | 157 |
N3"—H32"···O1A | 0.86 | 2.22 | 3.055 (14) | 164 |
N3"—H31"···N2ii | 0.86 | 2.24 | 3.053 (17) | 157 |
N5"—H52"···O1B | 0.86 | 2.07 | 2.742 (11) | 134 |
N5"—H51"···N4 | 0.86 | 2.26 | 3.076 (13) | 159 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z. |
The work presented on the title compound, (I), forms part of an on-going investigation into structure-activity studies on analogues of the anticonvulsant lamotrigine. The structure of lamotrigine (Janes et al., 1989), and a number of these analogues (Janes & Palmer, 1995a,b, 1996; Janes 1999) have been reported, and investigations of these structures have been undertaken (Janes & Palmer, 1995c). The material for this study was provided by Wellcome Pharmaceuticals (UK), now GlaxoWellcome. The asymmetric unit comprises two analogue molecules and two dimethylformamide solvent molecules. Fig. 1 presents a displacement ellipsoid plot with the asymmetric unit labelled, and shows a hydrogen-bonded layer of molecules within the unit cell. One of the analogue molecules exhibits disorder having two positions for its phenyl ring orientated almost 180° apart in rotation about the bridging bond between the rings, the attached fluorine being located on opposite sides of the ring as shown in Fig. 2, and the triazine ring placed such that the atoms almost superimpose one another. The analogue structures reported here will be referred to as the `fully occupied' and as the `percentage occupied' structures for ease of distinction. In Fig. 2, the top view is that of the fully occupied molecule, while the middle and lower views are those of the partial occupancy molecules. The structure with the fluorine labelled F2' in Fig. 1 is 62 (1)% occupied, while that for F2'' (omitted for clarity) is 38 (1)%. The principal moieties of the disordered structures, being almost superimposable upon one another, were resolved using the similarity restraints in SHELXL (Sheldrick, 1997). \sch
The phenyl and triazine rings of the fully occupied analogue molecule are both planar, the overall root mean square deviations (rmsd) for these atoms being 0.006 Å for the phenyl ring and 0.018 Å for the triazine ring. The fluorine attached to the phenyl ring deviates by only 0.023 (8) Å from its ring plane. The N atoms of the amino groups also deviate from their triazine ring plane by -0.071 (8) Å for N3, and 0.074 (8) Å for N5. For the 62% occupied molecule the rmsd for the ring atoms are 0.010 Å and 0.019 Å for the phenyl and triazine rings, respectively. The fluorine F2' does not deviate significantly from its phenyl ring plane. The N atoms of the amino groups of the triazine ring barely deviate from their ring plane [by -0.05 (3) Å for N3' and 0.14 (3) Å for N5']. The 38% occupied molecule has rmsd values of 0.022 Å and 0.018 Å for its phenyl and triazine rings, respectively. The fluorine F2" is 0.04 (2) Å from its phenyl ring, while atoms N3" and N5" are 0.04 (4) Å and -0.17 (4) Å, respectively, from their ring plane.
The dihedral angles between the phenyl and triazine rings of the analogue molecules within the asymmetric unit show significant differences. That for the fully occupied is 57.6 (2)°, while for the partially occupied molecule the dihedral angles are 76.9 (6)° for the 62% occupied, and 106.8 (8)° for the 38% occupied structures. The 2-fluorophenyl analogue has been solved as a methanolate (Janes & Palmer, 1995a), and this structure also comprises two analogue and two solvent molecules as the asymmetric unit, although in this case, no disorder is present. Here, the dihedral angles are 50.8 (1)° and 125.0 (1)° between the phenyl and triazine ring planes. The diversity of dihedral angles observed for this analogue reveals that there must exist a high degree of flexibility for rotation about the bridging bond between the rings, at least between the extreme values of the dihedral angles, without any significant penalty to the internal energetics of the molecule.
The two rings of the analogue molecules for the fully and partially occupied structures exhibit some degree of distortion away from being coaxial, as seen in Fig. 2. This distortion can be further illustrated by focusing on the distances of the specific coaxial atoms, namely C4, C1, C6t and C3t, from their opposing ring planes. For the fully occupied structure, carbon C1 of the phenyl ring is nominally coplanar with the opposing triazine ring atoms, lying only -0.019 (7) Å from its least-squares mean plane, but C4 is -0.13 (2) Å from the same plane. Likewise, C6t of the triazine ring is 0.062 (8) Å from the phenyl ring plane, while C3t deviates by 0.26 (1) Å from the same ring. Similarly, for the 62% occupied structure, carbon C1' is only 0.02 (2) Å from the corresponding triazine ring plane, while C4' is 0.15 (4) Å from this same plane. Also, C6t' is 0.08 (2) Å while C3t' is 0.30 (4) Å from their related phenyl ring. For the 38% occupied structure, C1" and C4" are -0.05 (2) Å and -0.29 (5) Å from their triazine ring plane, respectively. Additionally, C6t" and C3t" are -0.11 (3) Å and -0.27 (6) Å, respectively, from their phenyl ring.
There is extensive hydrogen bonding within the structure that maintains the framework of the molecules within the unit cell (Fig. 1 and Table 2). The molecules of the asymmetric unit are arranged as a nearly centrosymmetric dimer via hydrogen bonding. These dimeric pairs are further bonded to the solvent molecules and to neighbouring analogue molecules to produce a chain of hydrogen bonds throughout the crystal. Whilst the phenyl ring moieties of the partially occupied analogue molecules exhibit a near 180° rotation about the bridging bond between them and their respective triazine rings, the latter rings maintain a near comparable juxtaposition to the adjacent fully occupied analogue molecule. This results in maintaining the triazine rings of the partially occupied moieties in a suitable orientation for hydrogen bonding. A similar pattern of hydrogen bonding is found in the 2-fluorophenyl methanolate structure (Janes & Palmer, 1995a) which also has two analogue and two solvent molecules comprising the asymmetric unit. However, a difference between these two structures in respect of their hydrogen bonding, is that of the seven possible hydrogen-bonding atoms of the triazine rings, atoms N1 and N1' (and N1") are not utilized in this structure while they are in the comparable methanolate, bonding to the solvent molecule hydrogen atoms of the hydroxyl group.