Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107015880/gg3088sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107015880/gg3088Isup2.hkl |
CCDC reference: 649089
For related literature, see: Desiraju (1990); Drozd & Marchewka (2005); Gillespie (1963, 1992); Janczak & Kubiak (2005); Janczak & Perpétuo (2002); Krische & Lehn (2000); MacDonald & Whitesides (1994); Marchewka et al. (2003); Matzat (1972); Ng (1992); Pauling (1960); Perpétuo & Janczak (2005, 2006); Row (1999); Sherrington & Taskinen (2001); Zakaria et al. (2002).
A mixture of 2,4,6-triamino-1,3,5-triazine (quality ca 98%) and phthalimide (quality > 99%) in the molar proportion of 1:3 was heated under vaccum in a sealed glass ampoule in a temperature gradient (hot zone 473 K, cold zone 373 K). After several hours, colourless crystals formed in the cold zone, which proved to be suitable for single-crystal X-ray diffraction analysis.
The H atoms were placed in their geometrically defined positions with Uiso(H) values of 1.2Ueq of the N or C atoms directly attached to the H atoms.
Data collection: KM-4 CCD Software (Kuma, 2004); cell refinement: KM-4 CCD Software; data reduction: KM-4 CCD Softwere; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.
C3H6N6·3C8H5NO2 | F(000) = 1176 |
Mr = 567.53 | Dx = 1.443 Mg m−3 Dm = 1.44 Mg m−3 Dm measured by floatation |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 1265 reflections |
a = 26.709 (5) Å | θ = 2.0–25.7° |
b = 25.884 (5) Å | µ = 0.11 mm−1 |
c = 3.779 (1) Å | T = 295 K |
V = 2612.6 (10) Å3 | Paralellepiped, colourless |
Z = 4 | 0.30 × 0.28 × 0.22 mm |
Kuma KM-4 CCD diffractometer | 2555 independent reflections |
Radiation source: fine-focus sealed tube | 1789 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1 | θmax = 25.7°, θmin = 1.5° |
ω scans | h = −32→32 |
Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 1990) | k = −31→31 |
Tmin = 0.962, Tmax = 0.972 | l = −4→4 |
5001 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)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0395P)2 + 0.3044P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
2555 reflections | Δρmax = 0.16 e Å−3 |
211 parameters | Δρmin = −0.13 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0073 (6) |
C3H6N6·3C8H5NO2 | V = 2612.6 (10) Å3 |
Mr = 567.53 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 26.709 (5) Å | µ = 0.11 mm−1 |
b = 25.884 (5) Å | T = 295 K |
c = 3.779 (1) Å | 0.30 × 0.28 × 0.22 mm |
Kuma KM-4 CCD diffractometer | 2555 independent reflections |
Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 1990) | 1789 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.972 | Rint = 0.021 |
5001 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.16 e Å−3 |
2555 reflections | Δρmin = −0.13 e Å−3 |
211 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.43052 (6) | 0.43747 (6) | −0.0560 (5) | 0.0530 (4) | |
C2 | 0.39567 (5) | 0.47711 (6) | −0.1928 (4) | 0.0507 (4) | |
C3 | 0.39960 (7) | 0.53019 (6) | −0.2037 (5) | 0.0637 (5) | |
H3 | 0.4281 | 0.5471 | −0.1221 | 0.076* | |
C4 | 0.35911 (7) | 0.55739 (7) | −0.3421 (5) | 0.0716 (5) | |
H4 | 0.3606 | 0.5932 | −0.3551 | 0.086* | |
C5 | 0.31700 (7) | 0.53216 (7) | −0.4599 (5) | 0.0709 (5) | |
H5 | 0.2905 | 0.5514 | −0.5498 | 0.085* | |
C6 | 0.31305 (6) | 0.47915 (7) | −0.4485 (4) | 0.0620 (4) | |
H6 | 0.2845 | 0.4623 | −0.5294 | 0.074* | |
C7 | 0.35313 (5) | 0.45198 (6) | −0.3120 (4) | 0.0505 (4) | |
C8 | 0.36066 (6) | 0.39562 (6) | −0.2544 (4) | 0.0549 (4) | |
N1 | 0.40708 (5) | 0.39059 (5) | −0.1050 (4) | 0.0576 (4) | |
H1 | 0.4202 | 0.3614 | −0.0481 | 0.069* | |
O1 | 0.47194 (4) | 0.44196 (5) | 0.0825 (4) | 0.0771 (4) | |
O8 | 0.33250 (5) | 0.36014 (5) | −0.3216 (4) | 0.0754 (4) | |
N11 | 0.51352 (6) | 0.2500 | 0.4111 (5) | 0.0480 (4) | |
C12 | 0.49062 (5) | 0.29380 (6) | 0.3116 (4) | 0.0469 (3) | |
N13 | 0.44696 (4) | 0.29605 (4) | 0.1344 (3) | 0.0477 (3) | |
C14 | 0.42707 (7) | 0.2500 | 0.0534 (5) | 0.0451 (5) | |
N15 | 0.51282 (5) | 0.33841 (5) | 0.3937 (4) | 0.0591 (4) | |
H151 | 0.5408 | 0.3384 | 0.5064 | 0.071* | |
H152 | 0.4992 | 0.3672 | 0.3338 | 0.071* | |
N16 | 0.38334 (6) | 0.2500 | −0.1209 (5) | 0.0545 (5) | |
H161 | 0.3693 | 0.2788 | −0.1761 | 0.065* | |
N21 | 0.60560 (6) | 0.2500 | 0.7669 (5) | 0.0527 (5) | |
H21 | 0.5762 | 0.2500 | 0.6749 | 0.063* | |
C22 | 0.63169 (6) | 0.29402 (6) | 0.8484 (4) | 0.0515 (4) | |
C23 | 0.68010 (5) | 0.27671 (6) | 0.9981 (4) | 0.0476 (3) | |
C24 | 0.72093 (6) | 0.30425 (6) | 1.1162 (5) | 0.0596 (4) | |
H24 | 0.7210 | 0.3402 | 1.1152 | 0.071* | |
C25 | 0.76186 (6) | 0.27663 (7) | 1.2364 (5) | 0.0637 (5) | |
H25 | 0.7899 | 0.2943 | 1.3187 | 0.076* | |
O22 | 0.61646 (5) | 0.33767 (4) | 0.7962 (4) | 0.0736 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0433 (8) | 0.0552 (9) | 0.0606 (9) | −0.0045 (7) | −0.0040 (7) | 0.0014 (8) |
C2 | 0.0479 (8) | 0.0561 (9) | 0.0480 (9) | −0.0035 (7) | 0.0004 (7) | 0.0029 (7) |
C3 | 0.0661 (11) | 0.0570 (10) | 0.0681 (12) | −0.0078 (8) | 0.0038 (9) | 0.0030 (8) |
C4 | 0.0862 (14) | 0.0553 (9) | 0.0734 (12) | 0.0089 (9) | 0.0081 (11) | 0.0128 (9) |
C5 | 0.0741 (12) | 0.0772 (12) | 0.0613 (11) | 0.0201 (10) | 0.0000 (10) | 0.0139 (9) |
C6 | 0.0528 (9) | 0.0822 (12) | 0.0510 (9) | 0.0053 (9) | −0.0036 (8) | 0.0050 (9) |
C7 | 0.0462 (8) | 0.0607 (9) | 0.0445 (8) | −0.0031 (7) | 0.0009 (7) | 0.0037 (7) |
C8 | 0.0520 (9) | 0.0602 (9) | 0.0525 (9) | −0.0109 (7) | −0.0036 (8) | 0.0008 (8) |
N1 | 0.0533 (8) | 0.0493 (7) | 0.0701 (9) | −0.0042 (6) | −0.0122 (7) | 0.0052 (7) |
O1 | 0.0565 (7) | 0.0729 (8) | 0.1020 (10) | −0.0042 (6) | −0.0204 (7) | 0.0006 (7) |
O8 | 0.0715 (8) | 0.0689 (7) | 0.0857 (9) | −0.0244 (6) | −0.0169 (7) | 0.0016 (7) |
N11 | 0.0431 (9) | 0.0493 (9) | 0.0515 (10) | 0.000 | −0.0024 (8) | 0.000 |
C12 | 0.0432 (8) | 0.0527 (8) | 0.0449 (8) | −0.0026 (7) | 0.0029 (6) | 0.0024 (7) |
N13 | 0.0422 (6) | 0.0500 (7) | 0.0510 (7) | −0.0014 (5) | 0.0001 (6) | 0.0034 (6) |
C14 | 0.0395 (11) | 0.0521 (11) | 0.0437 (11) | 0.000 | 0.0060 (9) | 0.000 |
N15 | 0.0529 (8) | 0.0502 (7) | 0.0742 (10) | −0.0065 (6) | −0.0124 (7) | 0.0054 (7) |
N16 | 0.0432 (9) | 0.0548 (10) | 0.0656 (12) | 0.000 | −0.0060 (9) | 0.000 |
N21 | 0.0434 (9) | 0.0554 (10) | 0.0593 (11) | 0.000 | −0.0062 (9) | 0.000 |
C22 | 0.0520 (8) | 0.0516 (8) | 0.0510 (9) | −0.0009 (7) | −0.0005 (7) | 0.0027 (7) |
C23 | 0.0454 (8) | 0.0556 (8) | 0.0418 (8) | −0.0010 (7) | 0.0024 (6) | 0.0017 (6) |
C24 | 0.0547 (9) | 0.0607 (9) | 0.0634 (10) | −0.0089 (8) | −0.0048 (8) | 0.0011 (8) |
C25 | 0.0465 (8) | 0.0884 (11) | 0.0562 (10) | −0.0086 (8) | −0.0045 (8) | 0.0003 (9) |
O22 | 0.0714 (8) | 0.0531 (6) | 0.0964 (10) | 0.0033 (6) | −0.0185 (7) | 0.0087 (7) |
C1—O1 | 1.229 (2) | C12—N15 | 1.334 (2) |
C1—N1 | 1.378 (2) | C12—N13 | 1.346 (2) |
C1—C2 | 1.479 (2) | N13—C14 | 1.341 (2) |
C2—C3 | 1.379 (2) | C14—N13i | 1.341 (2) |
C2—C7 | 1.385 (2) | C14—N16 | 1.341 (3) |
C3—C4 | 1.393 (2) | N15—H151 | 0.8600 |
C3—H3 | 0.9300 | N15—H152 | 0.8600 |
C4—C5 | 1.375 (3) | N16—H161 | 0.8600 |
C4—H4 | 0.9300 | N21—C22 | 1.371 (2) |
C5—C6 | 1.377 (3) | N21—C22i | 1.371 (2) |
C5—H5 | 0.9300 | N21—H21 | 0.8600 |
C6—C7 | 1.381 (2) | C22—O22 | 1.217 (2) |
C6—H6 | 0.9300 | C22—C23 | 1.481 (2) |
C7—C8 | 1.489 (2) | C23—C24 | 1.377 (2) |
C8—O8 | 1.214 (2) | C23—C23i | 1.383 (3) |
C8—N1 | 1.369 (2) | C24—C25 | 1.383 (2) |
N1—H1 | 0.8600 | C24—H24 | 0.9300 |
N11—C12i | 1.342 (2) | C25—C25i | 1.379 (3) |
N11—C12 | 1.342 (2) | C25—H25 | 0.9300 |
O1—C1—N1 | 123.32 (14) | C12i—N11—C12 | 115.32 (18) |
O1—C1—C2 | 130.53 (15) | N15—C12—N11 | 117.61 (13) |
N1—C1—C2 | 106.14 (13) | N15—C12—N13 | 117.58 (13) |
C3—C2—C7 | 121.40 (15) | N11—C12—N13 | 124.80 (14) |
C3—C2—C1 | 130.84 (15) | C14—N13—C12 | 114.74 (13) |
C7—C2—C1 | 107.73 (14) | N13—C14—N13i | 125.55 (19) |
C2—C3—C4 | 117.12 (17) | N13—C14—N16 | 117.22 (9) |
C2—C3—H3 | 121.4 | N13i—C14—N16 | 117.22 (9) |
C4—C3—H3 | 121.4 | C12—N15—H151 | 120.0 |
C5—C4—C3 | 121.13 (17) | C12—N15—H152 | 120.0 |
C5—C4—H4 | 119.4 | H151—N15—H152 | 120.0 |
C3—C4—H4 | 119.4 | C14—N16—H161 | 120.0 |
C4—C5—C6 | 121.74 (17) | C22—N21—C22i | 112.47 (18) |
C4—C5—H5 | 119.1 | C22—N21—H21 | 123.8 |
C6—C5—H5 | 119.1 | C22i—N21—H21 | 123.8 |
C7—C6—C5 | 117.38 (17) | O22—C22—N21 | 124.44 (15) |
C7—C6—H6 | 121.3 | O22—C22—C23 | 129.39 (14) |
C5—C6—H6 | 121.3 | N21—C22—C23 | 106.16 (13) |
C6—C7—C2 | 121.23 (16) | C24—C23—C23i | 121.17 (9) |
C6—C7—C8 | 131.18 (15) | C24—C23—C22 | 131.20 (14) |
C2—C7—C8 | 107.57 (13) | C23i—C23—C22 | 107.61 (8) |
O8—C8—N1 | 125.15 (16) | C23—C24—C25 | 117.70 (16) |
O8—C8—C7 | 128.84 (15) | C23—C24—H24 | 121.2 |
N1—C8—C7 | 106.01 (13) | C25—C24—H24 | 121.2 |
C8—N1—C1 | 112.54 (13) | C25i—C25—C24 | 121.13 (10) |
C8—N1—H1 | 123.7 | C25i—C25—H25 | 119.4 |
C1—N1—H1 | 123.7 | C24—C25—H25 | 119.4 |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N13 | 0.86 | 1.96 | 2.818 (2) | 174 |
N15—H151···O22 | 0.86 | 2.30 | 3.159 (2) | 179 |
N15—H152···O1 | 0.86 | 2.27 | 3.124 (2) | 169 |
N16—H161···O8 | 0.86 | 2.39 | 3.248 (2) | 178 |
N21—H21···N11 | 0.86 | 1.95 | 2.803 (2) | 173 |
C4—H4···O22ii | 0.93 | 2.51 | 3.278 (2) | 139 |
Symmetry code: (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C3H6N6·3C8H5NO2 |
Mr | 567.53 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 295 |
a, b, c (Å) | 26.709 (5), 25.884 (5), 3.779 (1) |
V (Å3) | 2612.6 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.30 × 0.28 × 0.22 |
Data collection | |
Diffractometer | Kuma KM-4 CCD diffractometer |
Absorption correction | Analytical face-indexed (SHELXTL; Sheldrick, 1990) |
Tmin, Tmax | 0.962, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5001, 2555, 1789 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.092, 1.00 |
No. of reflections | 2555 |
No. of parameters | 211 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.13 |
Computer programs: KM-4 CCD Software (Kuma, 2004), KM-4 CCD Software, KM-4 CCD Softwere, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1990), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N13 | 0.86 | 1.96 | 2.818 (2) | 174 |
N15—H151···O22 | 0.86 | 2.30 | 3.159 (2) | 179 |
N15—H152···O1 | 0.86 | 2.27 | 3.124 (2) | 169 |
N16—H161···O8 | 0.86 | 2.39 | 3.248 (2) | 178 |
N21—H21···N11 | 0.86 | 1.95 | 2.803 (2) | 173 |
C4—H4···O22i | 0.93 | 2.51 | 3.278 (2) | 139 |
Symmetry code: (i) −x+1, −y+1, −z. |
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The present study is a continuation of our investigations into the characterization of hydrogen-bonding networks formed by triazine derivatives in the solid state (Perpétuo & Janczak, 2005; Janczak & Kubiak, 2005). Triazine and its derivatives, especially 2,4,6-triamino-1,3,5-triazine, i.e. melamine, and its organic and inorganic complexes or salts, can develop well defined noncovalent supramolecular architectures because of their ability to form multiple hydrogen bonds since they contain components of complementary arrays of hydrogen-bonding sites (Desiraju, 1990; MacDonald & Whitesides, 1994; Row, 1999; Krische & Lehn, 2000; Sherrington & Taskinen, 2001). Our interest in these materials arises from the possibility of their displaying nonlinear optical properties (Janczak & Perpétuo, 2002; Marchewka et al., 2003; Perpétuo & Janczak, 2006). We present here the 2,4,6-triamino-1,3,5-triazine–tris(phthalimide) cocrystal, (I), which contains multiple N—H···N and N—H···O hydrogen-bonding interactions.
The asymmetric unit of (I) comprises a half melamine and one and a half phthalimide molecules (Fig. 1). These units through a crystallographic mirror plane form an almost planar C3H6N6·3C8H5NO2 aggregate. The triazine ring in melamine is essentially planar [the deviation of the N and C atoms from the mean plane is less than 0.037 (2) Å], but exhibits significant distortion from the ideal hexagonal form (D3h symmetry). The internal C—N—C angles are smaller than 120°, while the internal N—C—N angles are greater than 120°. This distortion results from the steric effect of the lone-pair electrons, predicted by the valence-shell electron-pair repulsion theory (Gillespie, 1963, 1992). The ab-initio gas-phase geometry calculated for an isolated melamine molecule shows similar correlation between the internal C—N—C and N—C—N angles within the ring (Drozd & Marchewka, 2005). Thus the ring distortions result mainly from the steric effect of the lone pairs of electrons on the ring N atoms and, to a lesser degree, from the hydrogen-bonding arrangement, which diminishes the steric effect of these electron lone pairs by about 2° compared with the ab-initio results (Drozd & Marchewka, 2005). The phthalimide molecule has a similar geometry to that found in the pure phthalimide crystal (Matzat, 1972; Ng, 1992; Zakaria et al., 2002).
An extensive set of almost linear hydrogen bonds (Table 1) link the components of (I) into essentially planar C3H6N6·3C8H5NO2 aggregates with pseudo-threefold symmetry. These aggregates related by a twofold symmetry screw axis interact via C—H···O contacts, forming chains parallel to the b axis, while the plane defined by the atoms of the C3H6N6·3C8H5NO2 aggregates of the chain is inclined by 27.6° to the (001) plane. Each melamine molecule is involved in a maximum of nine hydrogen bonds; in six of these it acts as a donor and in the remaining three as an acceptor (Table 1). The chains related by a translation along the c axis interact via π–π interactions between the π clouds of the aromatic triazine and the phthalimide rings forming a stacked structure. Within the stack the triazine rings are separated by ~3.27 Å and the phthalimide molecules are separated by ~3.40 Å. These values indicate relatively strong π–π interactions within the stack, since they are comparable to the value of 3.4 Å for the interacting π aromatic ring system (Pauling, 1960).