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Acta Cryst. (2008). E64, o1733    [ doi:10.1107/S160053680802518X ]

N-[(3,5-Dimethylpyrazol-1-yl)methyl]phthalimide

S.-Q. Wang, F.-F. Jian and H.-Q. Liu

Abstract top

The title compound {systematic name: 2-[(3,5-dimenthylpyrazol-1-yl)methyl]isoindole-1,3-dione}, C14H13N3O2, was prepared by reaction of N-(bromomethyl)phthalimide and 3,5-dimethylpyrazole in chloroform solution. The molecular structure and packing are stabilized by intramolecular C-H...O hydrogen-bonding and C-H...[pi] interactions.

Comment top

The 3,5-dimethyl pyrazole and its derivatives are of considerable interest as the ligands in many biological systems in which they procvide the potential binding site for metal ions (Barszcz et al., 2004). In our search for new ligands of this type, we have synthesized the title compound (I), and describe its structure here.

In the crystal structure of (I) (Fig. 1), the C═O bond length [1.206 (3) Å), (1.208 (3) Å] and the C—N bond length [1.397 (2) Å), (1.396 (3) Å] (Table 1) are in agreement with those observed before (Jian et al., 2004; Jian et al., 2003). The dihedral angle formed by the ring A (N1/C7/C8/C13/C14) and the ring C (C8–C13) is 1.3 (0)°. The dihedral angles formed by the ring A and ring C with the ring B (N2/N3/C2–C4) are 72.0 (1) and 72.0 (4)°, respectively. There is a C—H···O intramolecular interaction (see table 2). The molecular structure is also stabilized by intermolecular C—H···π interactions (Table 2).

Related literature top

For related literature, see: Jian et al. (2003, 2004); Barszcz et al. (2004).

Experimental top

N-bromomethyl phthalic imidine 7.2 g (0.03 mol) and 3,5-dimethyl pyrazole 2.88 g (0.03 mol) were dissolved in 30 ml chloroform. The solution was cooled to 283 K. Then, 4.4 ml (0.03 mol) triethylamine was added dropwise via cannula into the well stirred solution The reaction mixture was stirred at 283 K for 6 h. Then the solution was continued to stir at room temperature about 17 h. 20 ml water was added into the solution, the organic phase was seperated and dryed with anhydrous potassium carbonate, The colourless organic phase was evaporated. The title compound is afforded in 65% yield. The colourless crystals of suitable for X-ray determination were obtained from anhydrous ethanol at room temperature after two days.

Refinement top

H atoms were fixed geometrically and allowed to ride on their parent atoms, with C—H = 0.93 - 0.97Å, and with Uiso(H)=1.2 or 1.5Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure and atom-labeling scheme for (I), with displacement ellipsoids drawn at the 30% probability level.
2-[(3,5-Dimethylpyrazol-1-yl)methyl]isoindole-1,3-dione top
Crystal data top
C14H13N3O2F000 = 536
Mr = 255.27Dx = 1.318 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1464 reflections
a = 12.285 (2) Åθ = 2.1–28.2º
b = 8.4576 (15) ŵ = 0.09 mm−1
c = 15.6162 (19) ÅT = 293 (2) K
β = 127.566 (8)ºBlock, yellow
V = 1286.1 (3) Å30.20 × 0.15 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		1464 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.060
Monochromator: graphiteθmax = 28.2º
T = 293(2) Kθmin = 2.1º
φ and ω scansh = −16→13
Absorption correction: nonek = −10→11
8080 measured reflectionsl = −19→20
3090 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.056  w = 1/[σ2(Fo2) + (0.0831P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.178(Δ/σ)max < 0.001
S = 0.98Δρmax = 0.33 e Å−3
3090 reflectionsΔρmin = −0.21 e Å−3
173 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.051 (6)
Secondary atom site location: difference Fourier map
Crystal data top
C14H13N3O2V = 1286.1 (3) Å3
Mr = 255.27Z = 4
Monoclinic, P21/cMo Kα
a = 12.285 (2) ŵ = 0.09 mm−1
b = 8.4576 (15) ÅT = 293 (2) K
c = 15.6162 (19) Å0.20 × 0.15 × 0.10 mm
β = 127.566 (8)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3090 independent reflections
Absorption correction: none1464 reflections with I > 2σ(I)
8080 measured reflectionsRint = 0.060
Refinement top
R[F2 > 2σ(F2)] = 0.056173 parameters
wR(F2) = 0.178H-atom parameters constrained
S = 0.98Δρmax = 0.33 e Å−3
3090 reflectionsΔρmin = −0.21 e Å−3
Special details top

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
xyzUiso*/Ueq
O10.66997 (19)−0.2663 (2)−0.13413 (14)0.0613 (6)
O20.38437 (19)−0.1191 (2)−0.05358 (15)0.0610 (6)
N10.50763 (19)−0.1704 (2)−0.11721 (15)0.0443 (5)
N20.3078 (2)−0.1271 (2)−0.30016 (15)0.0481 (6)
N30.3112 (2)−0.2458 (2)−0.35815 (16)0.0508 (6)
C10.1467 (3)0.0376 (4)−0.2904 (2)0.0729 (9)
H1A0.23090.0833−0.22970.109*
H1B0.0965−0.0058−0.26720.109*
H1C0.09250.1178−0.34390.109*
C20.1782 (3)−0.0900 (3)−0.3378 (2)0.0520 (7)
C30.0937 (3)−0.1884 (3)−0.4239 (2)0.0575 (7)
H3B−0.0016−0.1922−0.46690.069*
C40.1783 (3)−0.2813 (3)−0.4344 (2)0.0524 (7)
C50.1404 (3)−0.4075 (4)−0.5153 (2)0.0737 (9)
H5A0.2223−0.4502−0.50130.111*
H5B0.0833−0.3632−0.58670.111*
H5C0.0914−0.4901−0.50990.111*
C60.4354 (2)−0.0637 (3)−0.20848 (18)0.0486 (6)
H6A0.41760.0345−0.18700.058*
H6B0.4937−0.0397−0.22920.058*
C70.6197 (2)−0.2631 (3)−0.0875 (2)0.0442 (6)
C80.6612 (2)−0.3498 (3)0.01092 (18)0.0460 (6)
C90.7624 (3)−0.4605 (3)0.0711 (2)0.0611 (8)
H9A0.8183−0.49370.05310.073*
C100.7773 (3)−0.5210 (4)0.1611 (2)0.0708 (9)
H10A0.8446−0.59660.20380.085*
C110.6954 (3)−0.4717 (4)0.1882 (2)0.0685 (9)
H11A0.7098−0.51210.24980.082*
C120.5915 (3)−0.3625 (3)0.12510 (19)0.0561 (7)
H12A0.5342−0.33060.14200.067*
C130.5765 (2)−0.3033 (3)0.03664 (18)0.0439 (6)
C140.4762 (3)−0.1880 (3)−0.04554 (19)0.0454 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0654 (12)0.0772 (13)0.0586 (11)0.0047 (10)0.0467 (11)−0.0022 (9)
O20.0650 (12)0.0651 (12)0.0718 (12)0.0080 (10)0.0515 (11)0.0043 (10)
N10.0474 (12)0.0503 (12)0.0403 (11)0.0032 (10)0.0294 (10)0.0019 (9)
N20.0492 (12)0.0535 (13)0.0422 (11)0.0021 (10)0.0282 (10)0.0022 (10)
N30.0583 (14)0.0535 (13)0.0446 (12)0.0000 (11)0.0333 (12)−0.0004 (10)
C10.0560 (18)0.082 (2)0.073 (2)0.0076 (16)0.0352 (16)−0.0100 (17)
C20.0488 (15)0.0574 (16)0.0486 (14)0.0033 (13)0.0290 (13)0.0018 (13)
C30.0465 (15)0.0656 (18)0.0539 (16)0.0002 (14)0.0272 (14)−0.0010 (14)
C40.0558 (16)0.0550 (16)0.0448 (14)−0.0043 (13)0.0298 (14)0.0034 (12)
C50.075 (2)0.075 (2)0.0697 (18)−0.0117 (17)0.0434 (17)−0.0163 (17)
C60.0504 (15)0.0524 (15)0.0419 (14)−0.0034 (12)0.0276 (13)−0.0003 (12)
C70.0455 (14)0.0481 (14)0.0425 (13)−0.0036 (11)0.0287 (12)−0.0064 (11)
C80.0428 (14)0.0493 (15)0.0407 (13)−0.0045 (12)0.0227 (12)−0.0046 (12)
C90.0532 (17)0.0645 (18)0.0576 (17)0.0062 (14)0.0297 (14)0.0038 (15)
C100.0634 (19)0.064 (2)0.0615 (19)0.0063 (15)0.0261 (16)0.0135 (15)
C110.078 (2)0.072 (2)0.0461 (16)−0.0097 (17)0.0329 (16)0.0050 (15)
C120.0666 (18)0.0576 (17)0.0447 (14)−0.0142 (14)0.0343 (14)−0.0067 (13)
C130.0479 (14)0.0455 (14)0.0375 (13)−0.0073 (11)0.0256 (12)−0.0054 (11)
C140.0471 (14)0.0521 (15)0.0413 (13)−0.0039 (12)0.0292 (12)−0.0051 (12)
Geometric parameters (Å, °) top
O1—O10.000 (5)C5—H5A0.9600
O1—C71.208 (3)C5—H5B0.9600
O2—C141.206 (3)C5—H5C0.9600
N1—C71.396 (3)C6—H6A0.9700
N1—C141.397 (3)C6—H6B0.9700
N1—C61.446 (3)C7—O11.208 (3)
N2—C21.355 (3)C7—C81.485 (3)
N2—N31.369 (3)C8—C91.372 (3)
N2—C61.435 (3)C8—C131.382 (3)
N3—C41.343 (3)C9—C101.399 (4)
C1—C21.487 (4)C9—H9A0.9300
C1—H1A0.9600C10—C111.373 (4)
C1—H1B0.9600C10—H10A0.9300
C1—H1C0.9600C11—C121.385 (4)
C2—C31.370 (4)C11—H11A0.9300
C3—C41.390 (4)C12—C131.372 (3)
C3—H3B0.9300C12—H12A0.9300
C4—C51.495 (4)C13—C141.479 (4)
O1—O1—C70(10)N1—C6—H6A109.0
C7—N1—C14111.9 (2)N2—C6—H6B109.0
C7—N1—C6124.48 (19)N1—C6—H6B109.0
C14—N1—C6123.6 (2)H6A—C6—H6B107.8
C2—N2—N3112.6 (2)O1—C7—O10.00 (8)
C2—N2—C6128.8 (2)O1—C7—N1125.1 (2)
N3—N2—C6118.6 (2)O1—C7—N1125.1 (2)
C4—N3—N2103.8 (2)O1—C7—C8129.3 (2)
C2—C1—H1A109.5O1—C7—C8129.3 (2)
C2—C1—H1B109.5N1—C7—C8105.5 (2)
H1A—C1—H1B109.5C9—C8—C13121.6 (2)
C2—C1—H1C109.5C9—C8—C7129.9 (2)
H1A—C1—H1C109.5C13—C8—C7108.5 (2)
H1B—C1—H1C109.5C8—C9—C10116.5 (3)
N2—C2—C3105.8 (2)C8—C9—H9A121.7
N2—C2—C1123.1 (2)C10—C9—H9A121.7
C3—C2—C1131.1 (2)C11—C10—C9121.8 (3)
C2—C3—C4106.6 (2)C11—C10—H10A119.1
C2—C3—H3B126.7C9—C10—H10A119.1
C4—C3—H3B126.7C10—C11—C12120.9 (3)
N3—C4—C3111.2 (2)C10—C11—H11A119.5
N3—C4—C5119.5 (2)C12—C11—H11A119.5
C3—C4—C5129.3 (2)C13—C12—C11117.4 (3)
C4—C5—H5A109.5C13—C12—H12A121.3
C4—C5—H5B109.5C11—C12—H12A121.3
H5A—C5—H5B109.5C12—C13—C8121.7 (3)
C4—C5—H5C109.5C12—C13—C14130.1 (2)
H5A—C5—H5C109.5C8—C13—C14108.2 (2)
H5B—C5—H5C109.5O2—C14—N1124.3 (2)
N2—C6—N1112.99 (19)O2—C14—C13129.8 (2)
N2—C6—H6A109.0N1—C14—C13105.9 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6B···O10.972.582.917 (3)101
C11—H11A···Cg2i0.932.963.723 (3)140
Symmetry codes: (i) −x+1, −y−1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6B···O10.972.582.917 (3)101
C11—H11A···Cg2i0.932.963.723 (3)140
Symmetry codes: (i) −x+1, −y−1, −z.
references
References top

Barszcz, B., Glowiak, T., Jezierska, J. & Tomkiewicz, A. (2004). Polyhedron, 23, 1309–1316.

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Jian, F. F., Li, Y., Xiao, H. L. & Sun, P. P. (2003). Struct. Chem. 22, 687–690.

Jian, F.-F., Xiao, H.-L., Qin, Y.-Q. & Xu, L.-Z. (2004). Acta Cryst. C60, o492–o493.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.