Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052543/bt2556sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052543/bt2556Isup2.hkl |
CCDC reference: 667454
A hot methanol solution (20 ml) of 2,4-diamino-6-phenyl-1,3,5-triazine (31 mg A ldrich) and sorbic acid (28 mg Loba) was warmed for half an hour over a water bath. The mixture was cooled slowly and kept at room temperature. After a few days colourless plate-like crystals were obtained.
All the H atoms were positioned geometrically and were refined using a riding model. The N—H, O—H and C—H bond lengths are 0.86, 0.82 and 0.93–0.96 Å, repectively [Uiso(H)= 1.2 Ueq(parent atom)].
Hydrogen bonding plays a key role in molecular recognition, crystal engineering and supramolecular chemistry (Desiraju, 1989). Heterocycles play an important role in the study of pharmaceuticals and agrochemicals. Many derivatives of nitrogen heterocyclic rings such as triazine have been synthesized in recent years (Chen et al., 2001). Triazine derivatives show antitumor activity as well as broad range of biological activities like anti-angiogenesis and antimicrobial effects (Bork et al., 2003). The organic and inorganic complexes of triazine form well defined non-covalent supramolecular architectures via multiple hydrogen bonds constituting arrays of hydrogen-bonding sites (MacDonald & Whitesides, 1994). The adducts of carboxylic acids with 2-aminoheterocylic ring system forms a graph-set motif of R22(8) (Lynch & Jones, 2004). The crystal structure of 2,4-diamino-6-phenyl-1,3,5-triazine (Diaz-Ortiz et al., 2004), Melaminium maleate monohydrate (Janczak et al., 2004), 2,4-diamino-6-methyl-1,3,5-triazin-1-ium trifluoroacetate (Perpétuo & Janczak, 2007), 4-(dimethylamino)-benzaldehyde and 6-phenyl-1,3,5-triazine- 2,4-diamine (Habibi et al., 2007) and 2,6-diamino-4-phenyltriazinium chloride monohydrate (Sheshmani et al., 2006) have also been reported in the literature. The crystal structure of sorbic acid (Cox, 1994) is known. Sorbic acid is an antibacterial agent and widely used as a preservative (Martindale, 1996). The sorbic acid moiety lies in the EE configuration. The extended conformation of the sorbic acid can be inferred from the four torsion angles (C13—C14—C15—C16) 179.26 (16)°, (C14—C15—C16—C17) 178.28 (18)°, (C15—C16—C17—C18) -179.48 (18)° and (O1—C13—C14—C15) 177.82 (17)°. This conformation is similar to the trimethoprim sorbate dihydrate (Raj et al., 2003). In the present study, the hydrogen-bonding patterns in the 2,4-diamino-6- phenyl-1,3,5-triazine sorbic acid (1/1) cocrystal, (I), are investigated.
The asymmetric unit (Fig. 1) contains one 2,4-diamino-6-phenyl-1,3,5- triazine molecule and one sorbic acid molecule. The triazine molecules are base paired [with a graph-set of R22(8)] on either sides via N—H···N hydrogen bonds forming a supramolecular ribbon along the c axis (Fig. 2). Each triazine molecule interacts with the carboxyl group of a sorbic acid molecule via N—H···O and O—H···N hydrogen bonds, generating R22(8) motifs (Etter, 1990; Bernstein et al., 1995). The supramolecular ribbons are interlinked by N—H···O hydrogen bonds involving 2-amino group of the triazine molecules and carboxyl oxygen of the sorbic acid molecules.
For related literature, see: Bernstein et al. (1995); Bork et al. (2003); Chen et al. (2001); Cox (1994); Desiraju (1989); Diaz-Ortiz, Elguero, Foces-Foces, de la Hoz, Moreno, del Carmen Mateo, Sanchez-Migallon & Valiente (2004); Etter (1990); Habibi et al. (2007); Janczak & Perpétuo (2004); Lynch & Jones (2004); MacDonald & Whitesides (1994); Martindale (1996); Raj et al. (2003); Sheshmani et al. (2006); Perpétuo & Janczak (2007).
Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).
C9H9N5·C6H8O2 | F(000) = 1264 |
Mr = 299.34 | Dx = 1.299 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 33.867 (2) Å | θ = 3.3–27.5° |
b = 7.4289 (3) Å | µ = 0.09 mm−1 |
c = 12.2015 (8) Å | T = 120 K |
β = 94.241 (2)° | Plate, colourless |
V = 3061.4 (3) Å3 | 0.44 × 0.34 × 0.22 mm |
Z = 8 |
Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer | 2409 reflections with I > 2σ(I) |
Radiation source: Bruker–Nonius FR591 rotating anode | Rint = 0.056 |
Graphite monochromator | θmax = 27.5°, θmin = 3.3° |
Detector resolution: 9.091 pixels mm-1 | h = −42→44 |
φ and ω scans | k = −7→9 |
15418 measured reflections | l = −15→15 |
3490 independent 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)] = 0.059 | H-atom parameters constrained |
wR(F2) = 0.151 | w = 1/[σ2(Fo2) + (0.0729P)2 + 1.012P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
3490 reflections | Δρmax = 0.46 e Å−3 |
202 parameters | Δρmin = −0.47 e Å−3 |
0 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: 0.0114 (10) |
C9H9N5·C6H8O2 | V = 3061.4 (3) Å3 |
Mr = 299.34 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 33.867 (2) Å | µ = 0.09 mm−1 |
b = 7.4289 (3) Å | T = 120 K |
c = 12.2015 (8) Å | 0.44 × 0.34 × 0.22 mm |
β = 94.241 (2)° |
Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer | 2409 reflections with I > 2σ(I) |
15418 measured reflections | Rint = 0.056 |
3490 independent reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.46 e Å−3 |
3490 reflections | Δρmin = −0.47 e Å−3 |
202 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | ||
N1 | 0.33830 (4) | −0.02806 (18) | 0.59344 (11) | 0.0218 (4) | |
N2 | 0.36560 (5) | 0.21597 (18) | 0.51237 (11) | 0.0272 (5) | |
N3 | 0.36902 (4) | 0.20752 (17) | 0.70125 (11) | 0.0215 (4) | |
N4 | 0.36933 (5) | 0.19093 (19) | 0.88889 (11) | 0.0278 (5) | |
N5 | 0.34027 (4) | −0.04358 (18) | 0.78884 (11) | 0.0217 (4) | |
C2 | 0.35752 (5) | 0.1316 (2) | 0.60467 (13) | 0.0211 (5) | |
C4 | 0.35938 (5) | 0.1172 (2) | 0.79131 (13) | 0.0213 (5) | |
C6 | 0.33086 (5) | −0.1085 (2) | 0.68777 (13) | 0.0196 (5) | |
C7 | 0.30998 (5) | −0.2847 (2) | 0.67783 (13) | 0.0218 (5) | |
C8 | 0.30691 (5) | −0.3975 (2) | 0.76805 (14) | 0.0265 (5) | |
C9 | 0.28704 (6) | −0.5603 (2) | 0.75629 (16) | 0.0316 (6) | |
C10 | 0.26997 (6) | −0.6115 (3) | 0.65530 (17) | 0.0412 (7) | |
C11 | 0.27256 (8) | −0.5011 (3) | 0.56587 (18) | 0.0543 (8) | |
C12 | 0.29259 (6) | −0.3383 (3) | 0.57683 (15) | 0.0404 (7) | |
O1 | 0.40728 (4) | 0.53754 (16) | 0.87083 (10) | 0.0306 (4) | |
O2 | 0.40583 (4) | 0.51815 (16) | 0.68782 (10) | 0.0334 (4) | |
C13 | 0.41368 (5) | 0.6024 (2) | 0.78110 (14) | 0.0247 (5) | |
C14 | 0.43088 (5) | 0.7830 (2) | 0.77198 (15) | 0.0279 (6) | |
C15 | 0.43979 (5) | 0.8600 (2) | 0.67794 (15) | 0.0259 (5) | |
C16 | 0.45628 (5) | 1.0387 (2) | 0.67058 (16) | 0.0289 (6) | |
C17 | 0.46605 (6) | 1.1137 (2) | 0.57754 (16) | 0.0333 (6) | |
C18 | 0.48345 (7) | 1.2975 (3) | 0.56732 (19) | 0.0429 (7) | |
H2A | 0.37800 | 0.31710 | 0.51570 | 0.0330* | |
H2B | 0.35840 | 0.16920 | 0.44960 | 0.0330* | |
H4A | 0.38150 | 0.29260 | 0.89280 | 0.0330* | |
H4B | 0.36360 | 0.13680 | 0.94800 | 0.0330* | |
H8 | 0.31830 | −0.36340 | 0.83660 | 0.0320* | |
H9 | 0.28520 | −0.63500 | 0.81690 | 0.0380* | |
H10 | 0.25670 | −0.72080 | 0.64760 | 0.0490* | |
H11 | 0.26090 | −0.53560 | 0.49770 | 0.0650* | |
H12 | 0.29430 | −0.26450 | 0.51580 | 0.0480* | |
H2 | 0.39530 | 0.42140 | 0.69930 | 0.0500* | |
H14 | 0.43590 | 0.84850 | 0.83640 | 0.0330* | |
H15 | 0.43510 | 0.79460 | 0.61330 | 0.0310* | |
H16 | 0.46030 | 1.10520 | 0.73500 | 0.0350* | |
H17 | 0.46170 | 1.04640 | 0.51350 | 0.0400* | |
H18A | 0.48580 | 1.35430 | 0.63820 | 0.0640* | |
H18B | 0.46650 | 1.36840 | 0.51760 | 0.0640* | |
H18C | 0.50920 | 1.28770 | 0.53960 | 0.0640* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0282 (8) | 0.0219 (7) | 0.0154 (7) | −0.0008 (6) | 0.0032 (6) | −0.0006 (5) |
N2 | 0.0455 (10) | 0.0219 (8) | 0.0142 (7) | −0.0042 (6) | 0.0027 (7) | 0.0004 (5) |
N3 | 0.0313 (8) | 0.0214 (7) | 0.0121 (7) | −0.0007 (6) | 0.0031 (6) | −0.0007 (5) |
N4 | 0.0466 (10) | 0.0237 (8) | 0.0133 (7) | −0.0073 (6) | 0.0031 (6) | −0.0003 (6) |
N5 | 0.0280 (8) | 0.0231 (8) | 0.0142 (7) | −0.0007 (6) | 0.0022 (6) | −0.0014 (5) |
C2 | 0.0268 (9) | 0.0195 (8) | 0.0172 (8) | 0.0038 (6) | 0.0023 (7) | 0.0007 (6) |
C4 | 0.0257 (9) | 0.0225 (9) | 0.0160 (8) | 0.0021 (7) | 0.0029 (7) | 0.0007 (6) |
C6 | 0.0210 (8) | 0.0226 (9) | 0.0153 (8) | 0.0037 (6) | 0.0027 (7) | −0.0002 (6) |
C7 | 0.0228 (9) | 0.0245 (9) | 0.0188 (8) | 0.0000 (7) | 0.0053 (7) | −0.0028 (7) |
C8 | 0.0301 (10) | 0.0273 (9) | 0.0222 (9) | −0.0009 (7) | 0.0019 (8) | −0.0006 (7) |
C9 | 0.0360 (11) | 0.0267 (10) | 0.0331 (11) | −0.0024 (8) | 0.0096 (8) | 0.0014 (8) |
C10 | 0.0521 (14) | 0.0370 (11) | 0.0366 (12) | −0.0214 (9) | 0.0178 (10) | −0.0122 (9) |
C11 | 0.0776 (17) | 0.0617 (15) | 0.0241 (11) | −0.0389 (13) | 0.0079 (11) | −0.0139 (10) |
C12 | 0.0558 (14) | 0.0462 (12) | 0.0196 (10) | −0.0238 (10) | 0.0059 (9) | −0.0027 (8) |
O1 | 0.0455 (8) | 0.0263 (7) | 0.0203 (7) | −0.0054 (5) | 0.0054 (6) | −0.0022 (5) |
O2 | 0.0508 (9) | 0.0287 (7) | 0.0217 (7) | −0.0119 (6) | 0.0088 (6) | −0.0052 (5) |
C13 | 0.0291 (10) | 0.0250 (9) | 0.0203 (9) | 0.0011 (7) | 0.0033 (7) | −0.0024 (7) |
C14 | 0.0322 (10) | 0.0269 (9) | 0.0245 (10) | −0.0028 (7) | 0.0013 (8) | −0.0045 (7) |
C15 | 0.0240 (9) | 0.0286 (9) | 0.0249 (9) | 0.0006 (7) | 0.0003 (7) | −0.0009 (7) |
C16 | 0.0262 (10) | 0.0307 (10) | 0.0295 (10) | −0.0018 (7) | −0.0004 (8) | 0.0004 (8) |
C17 | 0.0346 (11) | 0.0332 (10) | 0.0321 (11) | 0.0003 (8) | 0.0018 (8) | 0.0072 (8) |
C18 | 0.0452 (13) | 0.0351 (12) | 0.0489 (13) | −0.0036 (9) | 0.0073 (10) | 0.0109 (10) |
O1—C13 | 1.230 (2) | C10—C11 | 1.373 (3) |
O2—C13 | 1.309 (2) | C11—C12 | 1.388 (3) |
O2—H2 | 0.8190 | C8—H8 | 0.9300 |
N1—C6 | 1.337 (2) | C9—H9 | 0.9304 |
N1—C2 | 1.355 (2) | C10—H10 | 0.9294 |
N2—C2 | 1.335 (2) | C11—H11 | 0.9300 |
N3—C4 | 1.348 (2) | C12—H12 | 0.9300 |
N3—C2 | 1.338 (2) | C13—C14 | 1.470 (2) |
N4—C4 | 1.331 (2) | C14—C15 | 1.336 (2) |
N5—C4 | 1.358 (2) | C15—C16 | 1.446 (2) |
N5—C6 | 1.340 (2) | C16—C17 | 1.328 (3) |
N2—H2A | 0.8602 | C17—C18 | 1.496 (3) |
N2—H2B | 0.8597 | C14—H14 | 0.9294 |
N4—H4A | 0.8601 | C15—H15 | 0.9299 |
N4—H4B | 0.8604 | C16—H16 | 0.9298 |
C6—C7 | 1.488 (2) | C17—H17 | 0.9302 |
C7—C8 | 1.393 (2) | C18—H18A | 0.9603 |
C7—C12 | 1.384 (2) | C18—H18B | 0.9610 |
C8—C9 | 1.386 (2) | C18—H18C | 0.9612 |
C9—C10 | 1.375 (3) | ||
O1···N2i | 2.9477 (19) | C4···H2 | 2.8371 |
O1···N4 | 2.8935 (19) | C4···H2Bvii | 2.8753 |
O2···N3 | 2.6337 (18) | C8···H10viii | 2.7841 |
O1···H4A | 2.0445 | C13···H4A | 2.9260 |
O1···H18Bii | 2.6808 | C16···H16xi | 3.0119 |
O1···H2Ai | 2.3523 | C17···H17xii | 3.0063 |
O2···H2A | 2.6901 | C17···H14xiii | 3.0552 |
O2···H15 | 2.4820 | H2···N2 | 2.8642 |
N1···N4iii | 3.031 (2) | H2···N3 | 1.8222 |
N2···O1iv | 2.9477 (19) | H2···C4 | 2.8371 |
N2···N5iii | 3.0771 (19) | H2···H2A | 2.4017 |
N3···C13 | 3.409 (2) | H2···C2 | 2.7179 |
N3···C16v | 3.257 (2) | H2A···O1iv | 2.3523 |
N3···C9vi | 3.378 (2) | H2A···H2 | 2.4017 |
N3···O2 | 2.6337 (18) | H2A···O2 | 2.6901 |
N4···O1 | 2.8935 (19) | H2B···N4iii | 2.8078 |
N4···N1vii | 3.031 (2) | H2B···N5iii | 2.2175 |
N5···C14v | 3.348 (2) | H2B···C4iii | 2.8753 |
N5···N2vii | 3.0771 (19) | H2B···H4Biii | 2.2803 |
N1···H4Biii | 2.1819 | H2B···H8iii | 2.3558 |
N1···H12 | 2.4484 | H4A···C13 | 2.9260 |
N2···H2 | 2.8642 | H4A···O1 | 2.0445 |
N2···H4Biii | 2.7353 | H4B···N1vii | 2.1819 |
N2···H8iii | 2.8031 | H4B···H2Bvii | 2.2802 |
N3···H2 | 1.8222 | H4B···N2vii | 2.7353 |
N4···H2Bvii | 2.8078 | H4B···C2vii | 2.7804 |
N5···H8 | 2.5695 | H8···H2Bvii | 2.3558 |
N5···H2Bvii | 2.2175 | H8···N5 | 2.5695 |
C2···C16v | 3.451 (2) | H8···N2vii | 2.8031 |
C2···C15v | 3.502 (2) | H9···H12xiv | 2.5360 |
C4···C14v | 3.488 (2) | H10···H11xv | 2.5724 |
C4···C9vi | 3.431 (2) | H10···C8ix | 2.7841 |
C6···C14v | 3.559 (2) | H11···H10xv | 2.5724 |
C8···C10viii | 3.540 (3) | H12···N1 | 2.4484 |
C9···N3v | 3.378 (2) | H12···H9xvi | 2.5360 |
C9···C4v | 3.431 (2) | H14···H16 | 2.4498 |
C10···C8ix | 3.540 (3) | H14···C17ii | 3.0552 |
C12···C12x | 3.572 (3) | H14···H17ii | 2.4007 |
C13···N3 | 3.409 (2) | H15···O2 | 2.4820 |
C14···C4vi | 3.488 (2) | H15···H17 | 2.4404 |
C14···N5vi | 3.348 (2) | H16···H14 | 2.4498 |
C14···C6vi | 3.559 (2) | H16···H18A | 2.3909 |
C15···C2vi | 3.502 (2) | H16···C16xi | 3.0119 |
C16···C16xi | 3.417 (3) | H17···H15 | 2.4404 |
C16···N3vi | 3.257 (2) | H17···C17xii | 3.0063 |
C16···C2vi | 3.451 (2) | H17···H14xiii | 2.4007 |
C17···C17xii | 3.517 (3) | H18A···H16 | 2.3909 |
C2···H4Biii | 2.7804 | H18B···O1xiii | 2.6808 |
C2···H2 | 2.7179 | ||
C13—O2—H2 | 109.51 | C10—C9—H9 | 119.92 |
C2—N1—C6 | 115.08 (13) | C8—C9—H9 | 119.91 |
C2—N3—C4 | 115.84 (13) | C11—C10—H10 | 120.02 |
C4—N5—C6 | 114.67 (13) | C9—C10—H10 | 120.01 |
C2—N2—H2B | 119.97 | C10—C11—H11 | 119.89 |
H2A—N2—H2B | 120.02 | C12—C11—H11 | 119.89 |
C2—N2—H2A | 120.01 | C7—C12—H12 | 119.71 |
C4—N4—H4A | 119.97 | C11—C12—H12 | 119.69 |
H4A—N4—H4B | 120.05 | O1—C13—C14 | 121.45 (15) |
C4—N4—H4B | 119.97 | O2—C13—C14 | 115.26 (15) |
N1—C2—N3 | 124.36 (14) | O1—C13—O2 | 123.29 (14) |
N1—C2—N2 | 116.91 (14) | C13—C14—C15 | 124.85 (16) |
N2—C2—N3 | 118.73 (14) | C14—C15—C16 | 124.00 (16) |
N3—C4—N4 | 117.63 (14) | C15—C16—C17 | 124.06 (17) |
N3—C4—N5 | 124.30 (14) | C16—C17—C18 | 125.36 (17) |
N4—C4—N5 | 118.07 (14) | C13—C14—H14 | 117.55 |
N5—C6—C7 | 118.07 (14) | C15—C14—H14 | 117.60 |
N1—C6—N5 | 125.73 (14) | C14—C15—H15 | 117.99 |
N1—C6—C7 | 116.20 (14) | C16—C15—H15 | 118.01 |
C6—C7—C8 | 121.82 (14) | C15—C16—H16 | 117.94 |
C6—C7—C12 | 119.59 (15) | C17—C16—H16 | 118.00 |
C8—C7—C12 | 118.59 (16) | C16—C17—H17 | 117.29 |
C7—C8—C9 | 120.46 (16) | C18—C17—H17 | 117.35 |
C8—C9—C10 | 120.17 (17) | C17—C18—H18A | 109.45 |
C9—C10—C11 | 120.0 (2) | C17—C18—H18B | 109.41 |
C10—C11—C12 | 120.2 (2) | C17—C18—H18C | 109.48 |
C7—C12—C11 | 120.59 (18) | H18A—C18—H18B | 109.48 |
C7—C8—H8 | 119.77 | H18A—C18—H18C | 109.47 |
C9—C8—H8 | 119.78 | H18B—C18—H18C | 109.54 |
C2—N1—C6—N5 | 0.9 (2) | N5—C6—C7—C8 | −12.5 (2) |
C2—N1—C6—C7 | −179.65 (14) | C6—C7—C12—C11 | −179.24 (19) |
C6—N1—C2—N2 | 179.82 (15) | C12—C7—C8—C9 | 0.4 (3) |
C6—N1—C2—N3 | 0.5 (2) | C6—C7—C8—C9 | 179.57 (16) |
C2—N3—C4—N4 | −178.16 (15) | C8—C7—C12—C11 | 0.0 (3) |
C4—N3—C2—N1 | −1.8 (2) | C7—C8—C9—C10 | −0.3 (3) |
C4—N3—C2—N2 | 178.90 (15) | C8—C9—C10—C11 | −0.1 (3) |
C2—N3—C4—N5 | 1.9 (2) | C9—C10—C11—C12 | 0.4 (3) |
C4—N5—C6—N1 | −0.8 (2) | C10—C11—C12—C7 | −0.4 (3) |
C4—N5—C6—C7 | 179.76 (14) | O2—C13—C14—C15 | −2.3 (3) |
C6—N5—C4—N4 | 179.35 (15) | O1—C13—C14—C15 | 177.82 (17) |
C6—N5—C4—N3 | −0.7 (2) | C13—C14—C15—C16 | 179.26 (16) |
N1—C6—C7—C12 | −12.8 (2) | C14—C15—C16—C17 | 178.28 (18) |
N1—C6—C7—C8 | 167.99 (15) | C15—C16—C17—C18 | −179.48 (18) |
N5—C6—C7—C12 | 166.65 (16) |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+2, z+1/2; (iii) x, −y, z−1/2; (iv) x, −y+1, z−1/2; (v) x, y−1, z; (vi) x, y+1, z; (vii) x, −y, z+1/2; (viii) −x+1/2, y+1/2, −z+3/2; (ix) −x+1/2, y−1/2, −z+3/2; (x) −x+1/2, −y−1/2, −z+1; (xi) −x+1, y, −z+3/2; (xii) −x+1, −y+2, −z+1; (xiii) x, −y+2, z−1/2; (xiv) x, −y−1, z+1/2; (xv) −x+1/2, −y−3/2, −z+1; (xvi) x, −y−1, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N3 | 0.82 | 1.82 | 2.6337 (18) | 171 |
N2—H2A···O1iv | 0.86 | 2.35 | 2.9477 (19) | 127 |
N2—H2B···N5iii | 0.86 | 2.22 | 3.0771 (19) | 179 |
N4—H4A···O1 | 0.86 | 2.04 | 2.8935 (19) | 169 |
N4—H4B···N1vii | 0.86 | 2.18 | 3.031 (2) | 169 |
C12—H12···N1 | 0.93 | 2.45 | 2.775 (3) | 101 |
Symmetry codes: (iii) x, −y, z−1/2; (iv) x, −y+1, z−1/2; (vii) x, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H9N5·C6H8O2 |
Mr | 299.34 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 120 |
a, b, c (Å) | 33.867 (2), 7.4289 (3), 12.2015 (8) |
β (°) | 94.241 (2) |
V (Å3) | 3061.4 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.44 × 0.34 × 0.22 |
Data collection | |
Diffractometer | Bruker–Nonius 95mm CCD camera on κ-goniostat |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15418, 3490, 2409 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.151, 1.10 |
No. of reflections | 3490 |
No. of parameters | 202 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.47 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N3 | 0.8200 | 1.8200 | 2.6337 (18) | 171.00 |
N2—H2A···O1i | 0.8600 | 2.3500 | 2.9477 (19) | 127.00 |
N2—H2B···N5ii | 0.8600 | 2.2200 | 3.0771 (19) | 179.00 |
N4—H4A···O1 | 0.8600 | 2.0400 | 2.8935 (19) | 169.00 |
N4—H4B···N1iii | 0.8600 | 2.1800 | 3.031 (2) | 169.00 |
C12—H12···N1 | 0.9300 | 2.4500 | 2.775 (3) | 101.00 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, −y, z−1/2; (iii) x, −y, z+1/2. |
Hydrogen bonding plays a key role in molecular recognition, crystal engineering and supramolecular chemistry (Desiraju, 1989). Heterocycles play an important role in the study of pharmaceuticals and agrochemicals. Many derivatives of nitrogen heterocyclic rings such as triazine have been synthesized in recent years (Chen et al., 2001). Triazine derivatives show antitumor activity as well as broad range of biological activities like anti-angiogenesis and antimicrobial effects (Bork et al., 2003). The organic and inorganic complexes of triazine form well defined non-covalent supramolecular architectures via multiple hydrogen bonds constituting arrays of hydrogen-bonding sites (MacDonald & Whitesides, 1994). The adducts of carboxylic acids with 2-aminoheterocylic ring system forms a graph-set motif of R22(8) (Lynch & Jones, 2004). The crystal structure of 2,4-diamino-6-phenyl-1,3,5-triazine (Diaz-Ortiz et al., 2004), Melaminium maleate monohydrate (Janczak et al., 2004), 2,4-diamino-6-methyl-1,3,5-triazin-1-ium trifluoroacetate (Perpétuo & Janczak, 2007), 4-(dimethylamino)-benzaldehyde and 6-phenyl-1,3,5-triazine- 2,4-diamine (Habibi et al., 2007) and 2,6-diamino-4-phenyltriazinium chloride monohydrate (Sheshmani et al., 2006) have also been reported in the literature. The crystal structure of sorbic acid (Cox, 1994) is known. Sorbic acid is an antibacterial agent and widely used as a preservative (Martindale, 1996). The sorbic acid moiety lies in the EE configuration. The extended conformation of the sorbic acid can be inferred from the four torsion angles (C13—C14—C15—C16) 179.26 (16)°, (C14—C15—C16—C17) 178.28 (18)°, (C15—C16—C17—C18) -179.48 (18)° and (O1—C13—C14—C15) 177.82 (17)°. This conformation is similar to the trimethoprim sorbate dihydrate (Raj et al., 2003). In the present study, the hydrogen-bonding patterns in the 2,4-diamino-6- phenyl-1,3,5-triazine sorbic acid (1/1) cocrystal, (I), are investigated.
The asymmetric unit (Fig. 1) contains one 2,4-diamino-6-phenyl-1,3,5- triazine molecule and one sorbic acid molecule. The triazine molecules are base paired [with a graph-set of R22(8)] on either sides via N—H···N hydrogen bonds forming a supramolecular ribbon along the c axis (Fig. 2). Each triazine molecule interacts with the carboxyl group of a sorbic acid molecule via N—H···O and O—H···N hydrogen bonds, generating R22(8) motifs (Etter, 1990; Bernstein et al., 1995). The supramolecular ribbons are interlinked by N—H···O hydrogen bonds involving 2-amino group of the triazine molecules and carboxyl oxygen of the sorbic acid molecules.