organic compounds
4,6-Dimethylpyrimidin-2-amine
aKey Laboratory of Functional Organometallic Materials of General Colleges and Universities in Hunan Province, Department of Chemistry and Materials Science, Hengyang Normal University, Hengyang 421008, People's Republic of China
*Correspondence e-mail: w.w.fu@hotmail.com
The 6H9N3, contains three crystallographically independent molecules of similar geometry. All of the molecules are almost planar, with r.m.s. deviations of 0.003, 0.016 and 0.005 Å. In the crystal, the molecules are linked by N—H⋯N hydrogen bonds into zigzag ribbons parallel to the c axis, generating rings of R22(8) graph-set motif.
of the title compound, CRelated literature
For background to sulfonylurea herbicides, see: Deng (2003). For the properties and crystal structures of metal complexes of the title compound, see: Sun et al. (2010); Yang (2009). For the structure of a hydrate form of the title compound, see: Lin et al. (2008). For the synthesis, see: Fan et al. (2000); Yao & Qu (1997).
Experimental
Crystal data
|
Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536812049458/rz5030sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049458/rz5030Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812049458/rz5030Isup3.cml
In an attempt to synthesize 1,3-bis(4,6-dimethylpyrimidin-2-yl)thiourea according to a literature method (Fan et al., 2000), 4,6-dimethylpyrimidin-2-amine (Yao & Qu, 1997) was used as material as a replacement for pyridin-2-amine. Sodium hydroxide (0.25 g, 6.25 mmol) was dissolved in absolute ethanol (25 ml), then 4,6-dimethylpyrimidin-2-amine (6.15 g, 50 mmol) and carbon disulfide (2.25 g, 30 mmol) were added. After refluxing for 6 h, the mixture was cooled and filtered. The title compound was obtained as colourless crystals suitable for X-ray diffraction instead of the expected thiourea derivative. All reagents and solvents were commercially available and used without further purification.
All non-H atoms were refined anisotropically. Hydrogen atoms were positioned geometrically and treated as riding atoms, with C—H = 0.90–1.00 Å, N—H = 0.88–0.91 Å and with with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(C) for methyl H atoms. The relatively high residual peak of 1.08 e/Å3 is located on a twofold axis.
4,6-Dimethylpyrimidin-2-amine is an important intermediate especially for synthesis of sulfonylurea herbicides (Deng, 2003). It has also been used as an organic ligand in the fluorescence research on Ag(I) coordination complexes (Sun et al., 2010; Yang, 2009). As a continuation of our efforts aimed to the synthesis of new ligands based on this organic compound, the title compound has been unexpectedly obtained and its
is reported herein.The
of the title compound consists of three crystallographically independent molecules of similar geometry (Fig. 1). All molecules are substantially planar, the r.m.s. deviations being 0.003, 0.016 and 0.005 Å for N1–N3/C1–C6, N4–N6/C7–C12 and N7–N9/C13–C18 respectively. In the (Fig. 2), molecules are connected by classical intermolecular N—H···N hydrogen bonds (Table 1) to form zigzag ribbons parallel to the c axis generating rings of R22(8) graph set motif. The structure of a hydrate form of the title compound was reported recently (Lin et al., 2008).For background to sulfonylurea herbicides, see: Deng (2003). For the properties and crystal structures of metal complexes of the title compound, see: Sun et al. (2010); Yang (2009). For the structure of a hydrate form of the title compound, see: Lin et al. (2008). For the synthesis, see: Fan et al. (2000); Yao & Qu (1997).
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).Fig. 1. ORTEP plot of the asymmetric unit of the title compound with displacement ellipsoids drawn at the 30% probability level. | |
Fig. 2. Packing diagram of the title compound viewed along the b axis. Hydrogen bonds are drawn as dashed lines. |
C6H9N3 | F(000) = 1584 |
Mr = 123.16 | Dx = 1.194 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1760 reflections |
a = 11.519 (7) Å | θ = 2.6–23.0° |
b = 11.021 (6) Å | µ = 0.08 mm−1 |
c = 32.386 (18) Å | T = 296 K |
β = 91.112 (10)° | Block, colourless |
V = 4111 (4) Å3 | 0.26 × 0.18 × 0.17 mm |
Z = 24 |
Bruker APEXII CCD diffractometer | 4020 independent reflections |
Radiation source: fine-focus sealed tube | 2252 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
φ and ω scans | θmax = 26.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −14→14 |
Tmin = 0.980, Tmax = 0.987 | k = −13→6 |
11005 measured reflections | l = −39→39 |
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)] = 0.062 | H-atom parameters constrained |
wR(F2) = 0.175 | w = 1/[σ2(Fo2) + (0.0567P)2 + 5.4094P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
4020 reflections | Δρmax = 1.08 e Å−3 |
245 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0011 (2) |
C6H9N3 | V = 4111 (4) Å3 |
Mr = 123.16 | Z = 24 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.519 (7) Å | µ = 0.08 mm−1 |
b = 11.021 (6) Å | T = 296 K |
c = 32.386 (18) Å | 0.26 × 0.18 × 0.17 mm |
β = 91.112 (10)° |
Bruker APEXII CCD diffractometer | 4020 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2252 reflections with I > 2σ(I) |
Tmin = 0.980, Tmax = 0.987 | Rint = 0.032 |
11005 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.01 | Δρmax = 1.08 e Å−3 |
4020 reflections | Δρmin = −0.16 e Å−3 |
245 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 | ||
N1 | 0.47955 (19) | 0.1483 (2) | 0.53927 (8) | 0.0677 (7) | |
H1A | 0.4423 | 0.0961 | 0.5244 | 0.081* | |
H1B | 0.4422 | 0.2003 | 0.5537 | 0.081* | |
N2 | 0.64988 (18) | 0.0645 (2) | 0.51683 (7) | 0.0514 (6) | |
N3 | 0.65035 (18) | 0.2326 (2) | 0.56391 (6) | 0.0497 (6) | |
N4 | −0.0008 (2) | 0.2232 (2) | 0.69589 (8) | 0.0702 (8) | |
H4A | −0.0320 | 0.1741 | 0.6783 | 0.084* | |
H4B | −0.0438 | 0.2682 | 0.7110 | 0.084* | |
N5 | 0.17824 (19) | 0.1573 (2) | 0.67544 (7) | 0.0513 (6) | |
N6 | 0.15897 (19) | 0.3101 (2) | 0.72784 (7) | 0.0528 (6) | |
N7 | 1.03321 (19) | 0.9393 (2) | 0.61966 (8) | 0.0705 (8) | |
H7A | 1.0747 | 0.9889 | 0.6342 | 0.085* | |
H7B | 1.0662 | 0.8868 | 0.6042 | 0.085* | |
N8 | 0.85527 (19) | 0.8637 (2) | 0.59788 (7) | 0.0522 (6) | |
N9 | 0.87060 (18) | 1.0286 (2) | 0.64615 (7) | 0.0507 (6) | |
C1 | 0.5969 (2) | 0.1484 (2) | 0.54006 (8) | 0.0481 (6) | |
C2 | 0.7663 (2) | 0.0667 (2) | 0.51776 (8) | 0.0533 (7) | |
C3 | 0.8282 (2) | 0.1495 (3) | 0.54127 (9) | 0.0572 (7) | |
H3A | 0.9090 | 0.1498 | 0.5416 | 0.069* | |
C4 | 0.7666 (2) | 0.2320 (2) | 0.56421 (8) | 0.0515 (7) | |
C5 | 0.8265 (3) | −0.0260 (3) | 0.49198 (11) | 0.0766 (10) | |
H5A | 0.7697 | −0.0748 | 0.4776 | 0.115* | |
H5B | 0.8739 | −0.0769 | 0.5095 | 0.115* | |
H5C | 0.8745 | 0.0142 | 0.4723 | 0.115* | |
C6 | 0.8267 (3) | 0.3251 (3) | 0.59082 (11) | 0.0743 (9) | |
H6A | 0.7698 | 0.3739 | 0.6043 | 0.111* | |
H6B | 0.8741 | 0.3759 | 0.5740 | 0.111* | |
H6C | 0.8747 | 0.2850 | 0.6112 | 0.111* | |
C7 | 0.1161 (2) | 0.2298 (2) | 0.69984 (8) | 0.0487 (6) | |
C8 | 0.2939 (2) | 0.1687 (2) | 0.67901 (9) | 0.0547 (7) | |
C9 | 0.3449 (2) | 0.2505 (3) | 0.70623 (9) | 0.0597 (8) | |
H9A | 0.4252 | 0.2582 | 0.7081 | 0.072* | |
C10 | 0.2743 (2) | 0.3200 (2) | 0.73041 (8) | 0.0520 (7) | |
C11 | 0.3651 (3) | 0.0882 (3) | 0.65230 (12) | 0.0846 (11) | |
H11A | 0.3146 | 0.0383 | 0.6356 | 0.127* | |
H11B | 0.4139 | 0.0375 | 0.6694 | 0.127* | |
H11C | 0.4125 | 0.1370 | 0.6348 | 0.127* | |
C12 | 0.3216 (3) | 0.4120 (3) | 0.76051 (10) | 0.0744 (9) | |
H12A | 0.2585 | 0.4510 | 0.7742 | 0.112* | |
H12B | 0.3659 | 0.4716 | 0.7460 | 0.112* | |
H12C | 0.3707 | 0.3722 | 0.7806 | 0.112* | |
C13 | 0.9157 (2) | 0.9440 (2) | 0.62120 (8) | 0.0490 (6) | |
C14 | 0.7390 (2) | 0.8696 (3) | 0.60022 (9) | 0.0546 (7) | |
C15 | 0.6851 (2) | 0.9530 (3) | 0.62522 (9) | 0.0582 (7) | |
H15A | 0.6046 | 0.9561 | 0.6267 | 0.070* | |
C16 | 0.7545 (2) | 1.0319 (2) | 0.64800 (8) | 0.0515 (7) | |
C17 | 0.6703 (3) | 0.7818 (3) | 0.57420 (11) | 0.0779 (10) | |
H17A | 0.7223 | 0.7314 | 0.5590 | 0.117* | |
H17B | 0.6208 | 0.8257 | 0.5553 | 0.117* | |
H17C | 0.6237 | 0.7319 | 0.5917 | 0.117* | |
C18 | 0.7026 (3) | 1.1255 (3) | 0.67570 (10) | 0.0759 (10) | |
H18A | 0.7635 | 1.1713 | 0.6890 | 0.114* | |
H18B | 0.6569 | 1.0860 | 0.6962 | 0.114* | |
H18C | 0.6540 | 1.1790 | 0.6596 | 0.114* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0420 (13) | 0.0787 (17) | 0.0825 (18) | −0.0024 (12) | 0.0011 (12) | −0.0227 (14) |
N2 | 0.0469 (13) | 0.0528 (13) | 0.0547 (13) | −0.0021 (11) | 0.0025 (10) | −0.0097 (11) |
N3 | 0.0450 (13) | 0.0505 (13) | 0.0538 (13) | 0.0006 (10) | 0.0035 (10) | −0.0100 (11) |
N4 | 0.0462 (14) | 0.0892 (19) | 0.0751 (17) | −0.0057 (13) | 0.0016 (12) | −0.0298 (15) |
N5 | 0.0496 (14) | 0.0496 (13) | 0.0548 (14) | −0.0051 (11) | 0.0059 (10) | −0.0054 (11) |
N6 | 0.0499 (14) | 0.0566 (14) | 0.0518 (13) | −0.0050 (11) | 0.0025 (10) | −0.0091 (11) |
N7 | 0.0424 (13) | 0.0830 (18) | 0.0862 (18) | 0.0016 (13) | 0.0053 (12) | −0.0293 (15) |
N8 | 0.0469 (13) | 0.0525 (13) | 0.0573 (14) | 0.0002 (11) | 0.0033 (10) | −0.0094 (11) |
N9 | 0.0424 (12) | 0.0534 (13) | 0.0562 (13) | −0.0001 (10) | 0.0025 (10) | −0.0093 (11) |
C1 | 0.0442 (15) | 0.0495 (15) | 0.0504 (15) | −0.0010 (12) | 0.0005 (12) | −0.0031 (13) |
C2 | 0.0503 (16) | 0.0511 (16) | 0.0586 (17) | 0.0019 (13) | 0.0052 (13) | −0.0093 (13) |
C3 | 0.0406 (15) | 0.0619 (17) | 0.0690 (18) | −0.0018 (13) | 0.0024 (13) | −0.0153 (15) |
C4 | 0.0465 (15) | 0.0505 (15) | 0.0575 (16) | −0.0027 (13) | −0.0001 (12) | −0.0095 (13) |
C5 | 0.066 (2) | 0.077 (2) | 0.087 (2) | 0.0056 (17) | 0.0113 (17) | −0.0316 (19) |
C6 | 0.0566 (19) | 0.074 (2) | 0.092 (2) | −0.0037 (16) | −0.0060 (16) | −0.0336 (19) |
C7 | 0.0457 (15) | 0.0527 (16) | 0.0479 (15) | −0.0060 (13) | 0.0017 (12) | 0.0012 (13) |
C8 | 0.0515 (16) | 0.0489 (16) | 0.0639 (18) | −0.0029 (13) | 0.0077 (13) | −0.0053 (14) |
C9 | 0.0430 (15) | 0.0604 (18) | 0.076 (2) | −0.0040 (14) | 0.0040 (14) | −0.0075 (16) |
C10 | 0.0478 (16) | 0.0527 (16) | 0.0555 (16) | −0.0090 (13) | −0.0006 (12) | −0.0022 (13) |
C11 | 0.061 (2) | 0.082 (2) | 0.111 (3) | −0.0008 (18) | 0.0156 (19) | −0.033 (2) |
C12 | 0.068 (2) | 0.073 (2) | 0.081 (2) | −0.0123 (17) | −0.0058 (17) | −0.0222 (18) |
C13 | 0.0434 (15) | 0.0514 (15) | 0.0522 (15) | 0.0018 (12) | 0.0034 (12) | −0.0037 (13) |
C14 | 0.0506 (17) | 0.0541 (16) | 0.0591 (17) | −0.0033 (13) | −0.0001 (13) | −0.0081 (14) |
C15 | 0.0413 (15) | 0.0625 (18) | 0.0709 (19) | 0.0003 (14) | 0.0044 (13) | −0.0128 (15) |
C16 | 0.0449 (15) | 0.0538 (16) | 0.0559 (16) | 0.0023 (13) | 0.0027 (12) | −0.0085 (13) |
C17 | 0.062 (2) | 0.077 (2) | 0.095 (2) | −0.0103 (17) | −0.0020 (17) | −0.032 (2) |
C18 | 0.0580 (19) | 0.083 (2) | 0.087 (2) | 0.0058 (17) | 0.0102 (16) | −0.0310 (19) |
N1—C1 | 1.351 (3) | C5—H5B | 0.9600 |
N1—H1A | 0.8600 | C5—H5C | 0.9600 |
N1—H1B | 0.8600 | C6—H6A | 0.9600 |
N2—C2 | 1.341 (3) | C6—H6B | 0.9600 |
N2—C1 | 1.346 (3) | C6—H6C | 0.9600 |
N3—C4 | 1.339 (3) | C8—C9 | 1.383 (4) |
N3—C1 | 1.349 (3) | C8—C11 | 1.496 (4) |
N4—C7 | 1.351 (3) | C9—C10 | 1.373 (4) |
N4—H4A | 0.8600 | C9—H9A | 0.9300 |
N4—H4B | 0.8600 | C10—C12 | 1.502 (4) |
N5—C8 | 1.341 (3) | C11—H11A | 0.9600 |
N5—C7 | 1.341 (3) | C11—H11B | 0.9600 |
N6—C10 | 1.334 (3) | C11—H11C | 0.9600 |
N6—C7 | 1.354 (3) | C12—H12A | 0.9600 |
N7—C13 | 1.357 (3) | C12—H12B | 0.9600 |
N7—H7A | 0.8600 | C12—H12C | 0.9600 |
N7—H7B | 0.8600 | C14—C15 | 1.380 (4) |
N8—C14 | 1.345 (3) | C14—C17 | 1.499 (4) |
N8—C13 | 1.348 (3) | C15—C16 | 1.384 (4) |
N9—C16 | 1.340 (3) | C15—H15A | 0.9300 |
N9—C13 | 1.344 (3) | C16—C18 | 1.499 (4) |
C2—C3 | 1.379 (4) | C17—H17A | 0.9600 |
C2—C5 | 1.499 (4) | C17—H17B | 0.9600 |
C3—C4 | 1.380 (4) | C17—H17C | 0.9600 |
C3—H3A | 0.9300 | C18—H18A | 0.9600 |
C4—C6 | 1.500 (4) | C18—H18B | 0.9600 |
C5—H5A | 0.9600 | C18—H18C | 0.9600 |
C1—N1—H1A | 120.0 | C9—C8—C11 | 121.6 (3) |
C1—N1—H1B | 120.0 | C10—C9—C8 | 118.5 (3) |
H1A—N1—H1B | 120.0 | C10—C9—H9A | 120.7 |
C2—N2—C1 | 116.1 (2) | C8—C9—H9A | 120.7 |
C4—N3—C1 | 116.5 (2) | N6—C10—C9 | 121.3 (3) |
C7—N4—H4A | 120.0 | N6—C10—C12 | 116.4 (3) |
C7—N4—H4B | 120.0 | C9—C10—C12 | 122.4 (3) |
H4A—N4—H4B | 120.0 | C8—C11—H11A | 109.5 |
C8—N5—C7 | 115.7 (2) | C8—C11—H11B | 109.5 |
C10—N6—C7 | 116.5 (2) | H11A—C11—H11B | 109.5 |
C13—N7—H7A | 120.0 | C8—C11—H11C | 109.5 |
C13—N7—H7B | 120.0 | H11A—C11—H11C | 109.5 |
H7A—N7—H7B | 120.0 | H11B—C11—H11C | 109.5 |
C14—N8—C13 | 116.1 (2) | C10—C12—H12A | 109.5 |
C16—N9—C13 | 116.3 (2) | C10—C12—H12B | 109.5 |
N2—C1—N3 | 125.8 (2) | H12A—C12—H12B | 109.5 |
N2—C1—N1 | 116.9 (2) | C10—C12—H12C | 109.5 |
N3—C1—N1 | 117.2 (2) | H12A—C12—H12C | 109.5 |
N2—C2—C3 | 122.1 (2) | H12B—C12—H12C | 109.5 |
N2—C2—C5 | 116.7 (3) | N9—C13—N8 | 126.2 (2) |
C3—C2—C5 | 121.2 (3) | N9—C13—N7 | 116.5 (2) |
C2—C3—C4 | 117.8 (3) | N8—C13—N7 | 117.3 (2) |
C2—C3—H3A | 121.1 | N8—C14—C15 | 121.7 (3) |
C4—C3—H3A | 121.1 | N8—C14—C17 | 116.9 (3) |
N3—C4—C3 | 121.6 (2) | C15—C14—C17 | 121.4 (3) |
N3—C4—C6 | 116.8 (2) | C14—C15—C16 | 118.0 (3) |
C3—C4—C6 | 121.5 (3) | C14—C15—H15A | 121.0 |
C2—C5—H5A | 109.5 | C16—C15—H15A | 121.0 |
C2—C5—H5B | 109.5 | N9—C16—C15 | 121.7 (2) |
H5A—C5—H5B | 109.5 | N9—C16—C18 | 117.1 (2) |
C2—C5—H5C | 109.5 | C15—C16—C18 | 121.2 (2) |
H5A—C5—H5C | 109.5 | C14—C17—H17A | 109.5 |
H5B—C5—H5C | 109.5 | C14—C17—H17B | 109.5 |
C4—C6—H6A | 109.5 | H17A—C17—H17B | 109.5 |
C4—C6—H6B | 109.5 | C14—C17—H17C | 109.5 |
H6A—C6—H6B | 109.5 | H17A—C17—H17C | 109.5 |
C4—C6—H6C | 109.5 | H17B—C17—H17C | 109.5 |
H6A—C6—H6C | 109.5 | C16—C18—H18A | 109.5 |
H6B—C6—H6C | 109.5 | C16—C18—H18B | 109.5 |
N5—C7—N4 | 117.0 (2) | H18A—C18—H18B | 109.5 |
N5—C7—N6 | 126.3 (2) | C16—C18—H18C | 109.5 |
N4—C7—N6 | 116.6 (2) | H18A—C18—H18C | 109.5 |
N5—C8—C9 | 121.7 (3) | H18B—C18—H18C | 109.5 |
N5—C8—C11 | 116.7 (3) | ||
C2—N2—C1—N3 | −0.3 (4) | N5—C8—C9—C10 | 0.8 (4) |
C2—N2—C1—N1 | 179.5 (3) | C11—C8—C9—C10 | −178.7 (3) |
C4—N3—C1—N2 | 0.2 (4) | C7—N6—C10—C9 | −1.0 (4) |
C4—N3—C1—N1 | −179.7 (3) | C7—N6—C10—C12 | 178.1 (2) |
C1—N2—C2—C3 | 0.3 (4) | C8—C9—C10—N6 | −0.3 (4) |
C1—N2—C2—C5 | −179.9 (3) | C8—C9—C10—C12 | −179.3 (3) |
N2—C2—C3—C4 | −0.2 (4) | C16—N9—C13—N8 | 0.6 (4) |
C5—C2—C3—C4 | −179.9 (3) | C16—N9—C13—N7 | −179.2 (3) |
C1—N3—C4—C3 | 0.0 (4) | C14—N8—C13—N9 | −0.2 (4) |
C1—N3—C4—C6 | −179.7 (3) | C14—N8—C13—N7 | 179.5 (3) |
C2—C3—C4—N3 | 0.0 (4) | C13—N8—C14—C15 | −0.2 (4) |
C2—C3—C4—C6 | 179.7 (3) | C13—N8—C14—C17 | 179.5 (3) |
C8—N5—C7—N4 | 177.8 (3) | N8—C14—C15—C16 | 0.3 (4) |
C8—N5—C7—N6 | −1.5 (4) | C17—C14—C15—C16 | −179.4 (3) |
C10—N6—C7—N5 | 2.0 (4) | C13—N9—C16—C15 | −0.4 (4) |
C10—N6—C7—N4 | −177.3 (2) | C13—N9—C16—C18 | 179.9 (3) |
C7—N5—C8—C9 | 0.0 (4) | C14—C15—C16—N9 | 0.1 (4) |
C7—N5—C8—C11 | 179.6 (3) | C14—C15—C16—C18 | 179.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.45 | 3.304 (4) | 175 |
N1—H1B···N8ii | 0.86 | 2.52 | 3.376 (4) | 173 |
N4—H4A···N9iii | 0.86 | 2.21 | 3.050 (3) | 167 |
N4—H4B···N6iv | 0.86 | 2.45 | 3.243 (4) | 154 |
N7—H7A···N5v | 0.86 | 2.57 | 3.421 (4) | 173 |
N7—H7B···N3vi | 0.86 | 2.36 | 3.219 (3) | 176 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1/2, y−1/2, z; (iii) x−1, y−1, z; (iv) −x, y, −z+3/2; (v) x+1, y+1, z; (vi) x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C6H9N3 |
Mr | 123.16 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 11.519 (7), 11.021 (6), 32.386 (18) |
β (°) | 91.112 (10) |
V (Å3) | 4111 (4) |
Z | 24 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.26 × 0.18 × 0.17 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.980, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11005, 4020, 2252 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.175, 1.01 |
No. of reflections | 4020 |
No. of parameters | 245 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.08, −0.16 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2008), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.45 | 3.304 (4) | 175.0 |
N1—H1B···N8ii | 0.86 | 2.52 | 3.376 (4) | 173.3 |
N4—H4A···N9iii | 0.86 | 2.21 | 3.050 (3) | 166.6 |
N4—H4B···N6iv | 0.86 | 2.45 | 3.243 (4) | 153.5 |
N7—H7A···N5v | 0.86 | 2.57 | 3.421 (4) | 172.6 |
N7—H7B···N3vi | 0.86 | 2.36 | 3.219 (3) | 176.3 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1/2, y−1/2, z; (iii) x−1, y−1, z; (iv) −x, y, −z+3/2; (v) x+1, y+1, z; (vi) x+1/2, y+1/2, z. |
Acknowledgements
Financial support by the Doctoral Startup Foundation of Hengyang Normal University (09B02) and the Foundation of Hengyang Bureau of Science and Technology (2011 K J21) are gratefully acknowledged.
References
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4,6-Dimethylpyrimidin-2-amine is an important intermediate especially for synthesis of sulfonylurea herbicides (Deng, 2003). It has also been used as an organic ligand in the fluorescence research on Ag(I) coordination complexes (Sun et al., 2010; Yang, 2009). As a continuation of our efforts aimed to the synthesis of new ligands based on this organic compound, the title compound has been unexpectedly obtained and its crystal structure is reported herein.
The asymmetric unit of the title compound consists of three crystallographically independent molecules of similar geometry (Fig. 1). All molecules are substantially planar, the r.m.s. deviations being 0.003, 0.016 and 0.005 Å for N1–N3/C1–C6, N4–N6/C7–C12 and N7–N9/C13–C18 respectively. In the crystal structure (Fig. 2), molecules are connected by classical intermolecular N—H···N hydrogen bonds (Table 1) to form zigzag ribbons parallel to the c axis generating rings of R22(8) graph set motif. The structure of a hydrate form of the title compound was reported recently (Lin et al., 2008).