research communications
A monoclinic polymorph of 4-(2H-1,3-benzodioxol-5-yl)-1-(4-methylphenyl)-1H-pyrazol-5-amine
aDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, bP. S. Science and H. D. Patel Arts College, S. V. Campus, Kadi, Gujarat 382 715, India, cDepartment of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People's Republic of China, dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and eCentre for Chemical Crystallography and Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: mmjotani@rediffmail.com, edward.tiekink@gmail.com
The title compound, C17H15N3O2, is a monoclinic polymorph (P21/c with Z′ = 1) of the previously reported triclinic (P-1 with Z′ = 2) form [Gajera et al. (2013). Acta Cryst. E69, o736–o737]. The molecule in the monoclinic polymorph features a central pyrazolyl ring with an N-bound p-tolyl group and a C-bound 1,3-benzodioxolyl fused-ring system on either side of the C atom bearing the amino group. The dihedral angles between the central ring and the N- and C-bound rings are 50.06 (5) and 27.27 (5)°, respectively. The angle between the pendent rings is 77.31 (4)°, indicating the molecule has a twisted conformation. The five-membered dioxolyl ring has an with the methylene C atom being the flap. The relative disposition of the amino and dioxolyl substituents is syn. One of the independent molecules in the triclinic form has a similar syn disposition but the other has an anti arrangement of these substituents. In the of the monoclinic form, molecules assemble into supramolecular helical chains via amino–pyrazolyl N—H⋯N hydrogen bonds. These are linked into layers via C—H⋯π interactions, and layers stack along the a axis with no specific interactions between them.
Keywords: crystal structure; amine; polymorph; conformation; Hirshfeld surface.
CCDC reference: 1420783
1. Chemical context
It is the broad range of biological activities, such as anti-depressant, anti-anxiety, anti-fungal, anti-bacterial, anti-diabetic, anti-cancer, etc. (Tanitame et al., 2004; Chimenti et al., 2006; Ding et al.,2009; Shen et al., 2011; Deng et al., 2012), that continues to inspire interest in compounds containing the amino-substituted pyrazole unit. It was in this context that the of 4-(2H-1,3-benzodioxol-5-yl)-1-(4-methylphenyl)-1H-pyrazol-5-amine (I) was originally determined (Gajera et al., 2013). Subsequently, during scale up, crystals of the monoclinic form were isolated from recrystallization of (I) from ethyl acetate, the same solvent system that afforded the original triclinic polymorph. Herein, the crystal and molecular structures of the monoclinic form of (I), hereafter (mI), are described and compared with the triclinic polymorph, (tI).
2. Structural commentary
The molecule in (mI), Fig. 1, comprises a central and almost planar pyrazolyl ring (r.m.s. deviation of the five atoms = 0.0043 Å) flanked by an N-bound p-tolyl group and a C-bound 1,3-benzodioxolyl fused ring system. In the latter, the five-membered dioxolyl ring adopts an with the methylene-C17 atom being the flap; the C17 atom lies 0.318 (2) Å out of the least-squares plane defined by the O1, O2, C14 and C15 atoms (r.m.s. deviation = 0.0005 Å). The dihedral angles between the central ring and the N- and C-bound six-membered rings are 50.06 (5) and 27.27 (5)°, respectively. The dihedral angle between the six-membered rings is 77.31 (4)°, indicating an overall twisted arrangement. In general terms, the relative disposition of the amino and dioxolyl substituents may be described as being syn.
While (mI) crystallizes with Z′ = 1, the triclinic polymorph, (tI), crystallizes with Z′ = 2 (Gajera et al., 2013). In the latter, the molecules have quite different conformations. In one of the independent molecules, the amino and dioxolyl substituents are syn, as for (mI), and in the other these substituents are anti. These differences in molecular conformations are highlighted in Fig. 2. The syn/anti distinction is quite clear from this overlap diagram where the dioxolyl ring obviously occupies a different position in the second independent molecule of (tI, blue image). Also evident from Fig. 2 are variations in the relative dispositions of six-membered rings. These variations are quantified in Table 1.
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3. PXRD study
In order to ascertain the nature of the crystalline residue isolated from recrystallization of (I) from ethyl acetate solution, a powder X-ray diffraction (PXRD) experiment was performed on a PANalytical Empyrean XRD system with Cu Kα1 radiation (λ = 1.54056 Å) in the 2θ range of 5 to 50° with a step size of 0.026°. The pattern was analyzed with X'Pert HighScore Plus (PANalytical, 2009). This analysis indicated that the ratio of (mI) to (tI) in the overall sample was 49.1:50.9. This distribution suggests that effectively in the sample there is a 3:1 ratio of molecules with a syn disposition of the amino and dioxolyl substituents to those with a trans arrangement.
4. Supramolecular features
The most notable feature of the crystal packing in (mI) is the formation of supramolecular helical chains aligned along the b axis and mediated by amino–pyrazolyl N—H⋯N hydrogen bonds, Fig. 3 and Table 2. The chains are consolidated into layers in the bc plane by pyrazolyl–tolyl C10—H⋯π and methylene–benzo-C6 C17—H⋯π interactions, Table 2. The layers inter-digitate along the a axis whereby the dioxolyl rings face each other, Fig. 4. The C—H⋯O interactions are at distances beyond the standard criteria (Spek, 2009). In the packing scheme just described, no specific role is found for the second amino-H2N atom. To a first approximation, the mode of association between molecules in (tI) is similar in that supramolecular chains are formed. These comprise alternating independent molecules a and b that are connected by amino–pyrazolyl N—H⋯N hydrogen bonds. The difference is that in (tI), the chains have a zigzag topology. Chains in (tI) are connected by C—H⋯O and C—H⋯π interactions.
5. Analysis of the Hirshfeld surfaces
In order to investigate further the nature of the crystal packing in (mI) and (tI), an analysis of the Hirshfeld surfaces (Spackman & Jayatilaka, 2009) was undertaken employing CrystalExplorer (Wolff et al., 2012). The Hirshfeld surfaces were mapped over dnorm for each of the three molecules, Fig. 5. The points of contact corresponding to the amino–pyrazolyl N—H⋯N hydrogen bonds are recognized easily by deep-red depressions on the Hirshfeld surfaces of all three molecules. The C—H⋯π interactions in (mI) are indicated by both diminutive spots and light-red regions on the surface. These are also apparent in (tI) with additional features arising from the C—H⋯O contacts, Fig. 5. The fingerprint plots (Rohl et al., 2008) were also calculated and enabled a delineation of the relative contribution of the different intermolecular contacts to the respective crystal structures. These contributions are illustrated graphically in Fig. 6. Despite the different modes of association between the respective molecules, to a first approximation the relative contributions to the surfaces are similar.
6. Database survey
A search of the Cambridge Structural Database (Groom & Allen, 2014), revealed there are no direct analogues of (I), i.e. 1,3 N- and C-disubstituted species. There are four examples of 1,3,4 trisubstituted analogues (Abu Thaher et al., 2012; and references therein).
7. Synthesis and crystallization
The title compound was synthesized according to the same synthetic process as described in the original report (Gajera et al., 2013). Single crystals suitable for X-ray measurements in the form of light-brown prisms were obtained from its ethyl acetate solution at room temperature.
8. Refinement
Crystal data, data collection and structure . Carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the in the riding model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The N-bound H atoms were located in a difference Fourier map but were refined with a distance restraint of N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.2Ueq(N).
details are summarized in Table 3Supporting information
CCDC reference: 1420783
10.1107/S2056989015016023/hb7490sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015016023/hb7490Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015016023/hb7490Isup3.cml
It is the broad range of biological activities, such as anti-depressant, anti-anxiety, anti-fungal, anti-bacterial, anti-diabetic, anti-cancer, etc. (Tanitame et al., 2004; Chimenti et al., 2006; Ding et al.,2009; Shen et al., 2011; Deng et al., 2012), that continues to inspire interest in compounds containing the amino-substituted pyrazole unit. It was in this context that the
of 4-(2H-1,3-benzodioxol-5-yl)-1-(4-methylphenyl)-1H-pyrazol-5-amine (I) was originally determined (Gajera et al., 2013). Subsequently, during scale up, crystals of the monoclinic form were isolated from recrystallization of (I) from ethyl acetate, the same solvent system that afforded the original triclinic polymorph. Herein, the crystal and molecular structures of the monoclinic form of (I), hereafter (mI), are described and compared with the triclinic polymorph, (tI).The molecule in (mI), Fig. 1, comprises a central and almost planar pyrazolyl ring (r.m.s. deviation of the five atoms = 0.0043 Å) flanked by an N-bound p-tolyl group and a C-bound 1,3-benzodioxolyl fused ring system. In the latter, the five-membered dioxolyl ring adopts an
with the methylene-C17 atom being the flap; the C17 atom lies 0.318 (2) Å out of the least-squares plane defined by the O1, O2, C14 and C15 atoms (r.m.s. deviation = 0.0005 Å). The dihedral angles between the central ring and the N- and C-bound six-membered rings are 50.06 (5) and 27.27 (5)°, respectively. The dihedral angle between the six-membered rings is 77.31 (4)°, indicating an overall twisted arrangement. In general terms, the relative disposition of the amino and dioxolyl substituents may be described as being syn.While (mI) crystallizes with Z' = 1, the triclinic polymorph, (tI), crystallizes with Z' = 2 (Gajera et al., 2013). In the latter, the molecules have quite different conformations. In one of the independent molecules, the amino and dioxolyl substituents are syn, as for (mI), and in the other these substituents are anti. These differences in molecular conformations are highlighted in Fig. 2. The syn/anti distinction is quite clear from this overlap diagram where the dioxolyl ring obviously occupies a different position in the second independent molecule of (tI, blue image). Also evident from Fig. 2 are variations in the relative dispositions of six-membered rings. These variations are quantified in Table 1.
In order to ascertain the nature of the crystalline residue isolated from recrystallization of (I) from ethyl acetate solution, a powder X-ray diffraction (PXRD) experiment was performed on a PANalytical Empyrean XRD system with Cu Kα1 radiation (λ = 1.54056 Å) in the 2θ range of 5 to 50° with a step size of 0.026°. The pattern was analyzed with X'Pert HighScore Plus (PANalytical, 2009). This analysis indicated that the ratio of (mI) to (tI) in the overall sample was 49.1:50.9. This distribution suggests that effectively in the sample there is a 3:1 ratio of molecules with a syn disposition of the amino and dioxolyl substituents to those with a trans arrangement.
The most notable feature of the crystal packing in (mI) is the formation of supramolecular helical chains aligned along the b axis and mediated by amino–pyrazolyl N—H···N hydrogen bonds, Fig. 3 and Table 2. The chains are consolidated into layers in the bc plane by pyrazolyl–tolyl C10—H···π and methylene–benzo-C6 C17—H···π interactions, Table 2. The layers inter-digitate along the a axis whereby the dioxolyl rings face each other, Fig. 4. The C—H···O interactions are at distances beyond the standard criteria (Spek, 2009). In the packing scheme just described, no specific role is found for the second amino-H2N atom. To a first approximation, the mode of association between molecules in (tI) is similar in that supramolecular chains are formed. These comprise alternating independent molecules a and b that are connected by amino–pyrazolyl N—H···N hydrogen bonds. The difference is that in (tI), the chains have a zigzag topology. Chains in (tI) are connected by C—H···O and C—H···π interactions.
In order to investigate further the nature of the crystal packing in (mI) and (tI), an analysis of the Hirshfeld surfaces (Spackman & Jayatilaka, 2009) was undertaken employing CrystalExplorer (Wolff et al., 2012) . The Hirshfeld surfaces were mapped over dnorm for each of the three molecules, Fig. 5. The points of contact corresponding to the amino–pyrazolyl N—H···N hydrogen bonds are recognized easily by deep-red depressions on the Hirshfeld surfaces of all three molecules. The C—H···π interactions in (mI) are indicated by both diminutive spots and light-red regions on the surface. These are also apparent in (tI) with additional features arising from the C—H···O contacts, Fig. 5. The fingerprint plots (Rohl et al., 2008) were also calculated and enabled a delineation of the relative contribution of the different intermolecular contacts to the respective crystal structures. These contributions are illustrated graphically in Fig. 6. Despite the different modes of association between the respective molecules, to a first approximation the relative contributions to the surfaces are similar.
A search of the Cambridge Structural Database (Groom & Allen, 2014), revealed there are no direct analogues of (I), i.e. 1,3 N- and C-disubstituted species. There are four examples of 1,3,4 trisubstituted analogues (Abu Thaher et al., 2012; and references therein).
The title compound was synthesized according to the same synthesis process as described in the original report (Gajera et al., 2013). Single crystals suitable for X-ray measurements in the form of light-brown prisms were obtained from its ethyl acetate solution at room temperature.
Crystal data, data collection and structure
details are summarized in Table 3. Carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the in the riding model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The N-bound H atoms were located in a difference Fourier map but were refined with a distance restraint of N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.2Ueq(N).Data collection: CrysAlis PRO (Agilent, 2014); cell
CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The molecular structure of the molecule found in the monoclinic polymorph showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. | |
Fig. 2. Overlay diagram of the title compound, (mI), red image, with the two independent molecules in (tI), green (molecule a) and blue (b) images. The molecules have been overlapped so that the central pyrazolyl rings are coincident. | |
Fig. 3. A view of a supramolecular helical chain aligned along the b axis and mediated by amino–pyrazolyl N—H···N hydrogen bonds shown as blue dashed lines. | |
Fig. 4. Unit-cell contents shown in projection down the c axis. The N—H···N and C—H···π interactions are shown as blue and purple dashed lines, respectively. | |
Fig. 5. Views of the Hirshfeld surfaces for (a) (mI), (b) (tI) – molecule a, and (c) (tI) – molecule b. | |
Fig. 6. Relative contributions of various intermolecular contacts to the Hirshfeld surface area in (a) mI, and of (tI) molecules (b) a and (c) b. |
C17H15N3O2 | F(000) = 616 |
Mr = 293.32 | Dx = 1.409 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 13.9652 (3) Å | Cell parameters from 2900 reflections |
b = 10.6898 (2) Å | θ = 5.3–75.6° |
c = 9.8459 (2) Å | µ = 0.77 mm−1 |
β = 109.844 (2)° | T = 100 K |
V = 1382.57 (5) Å3 | Prism, light-brown |
Z = 4 | 0.35 × 0.25 × 0.15 mm |
Agilent SuperNova Dual diffractometer with an Atlas detector | 2582 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 2289 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.013 |
ω scans | θmax = 70.0°, θmin = 5.3° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | h = −16→12 |
Tmin = 0.989, Tmax = 1.000 | k = −12→12 |
4379 measured reflections | l = −11→11 |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0527P)2 + 0.5203P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2582 reflections | Δρmax = 0.19 e Å−3 |
206 parameters | Δρmin = −0.27 e Å−3 |
C17H15N3O2 | V = 1382.57 (5) Å3 |
Mr = 293.32 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 13.9652 (3) Å | µ = 0.77 mm−1 |
b = 10.6898 (2) Å | T = 100 K |
c = 9.8459 (2) Å | 0.35 × 0.25 × 0.15 mm |
β = 109.844 (2)° |
Agilent SuperNova Dual diffractometer with an Atlas detector | 2582 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | 2289 reflections with I > 2σ(I) |
Tmin = 0.989, Tmax = 1.000 | Rint = 0.013 |
4379 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 2 restraints |
wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.19 e Å−3 |
2582 reflections | Δρmin = −0.27 e Å−3 |
206 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. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.01538 (7) | 0.79537 (9) | 0.05812 (10) | 0.0229 (2) | |
O2 | 0.09248 (7) | 0.63677 (9) | 0.17958 (10) | 0.0229 (2) | |
N1 | 0.47346 (8) | 0.93081 (10) | 0.71284 (11) | 0.0146 (2) | |
N2 | 0.46867 (8) | 1.04737 (10) | 0.65038 (11) | 0.0168 (2) | |
N3 | 0.38155 (8) | 0.73744 (11) | 0.67648 (13) | 0.0229 (3) | |
H1N | 0.4302 (10) | 0.6978 (15) | 0.7442 (15) | 0.028* | |
H2N | 0.3203 (8) | 0.7054 (15) | 0.6459 (17) | 0.028* | |
C1 | 0.79815 (10) | 0.85389 (13) | 1.24901 (15) | 0.0226 (3) | |
H1A | 0.7964 | 0.9221 | 1.3147 | 0.034* | |
H1B | 0.8637 | 0.8547 | 1.2330 | 0.034* | |
H1C | 0.7896 | 0.7737 | 1.2917 | 0.034* | |
C2 | 0.71312 (10) | 0.87116 (12) | 1.10672 (14) | 0.0178 (3) | |
C3 | 0.73229 (9) | 0.91569 (12) | 0.98529 (14) | 0.0188 (3) | |
H3 | 0.8002 | 0.9347 | 0.9919 | 0.023* | |
C4 | 0.65366 (9) | 0.93269 (12) | 0.85479 (14) | 0.0173 (3) | |
H4 | 0.6679 | 0.9627 | 0.7728 | 0.021* | |
C5 | 0.55400 (9) | 0.90549 (11) | 0.84473 (13) | 0.0146 (3) | |
C6 | 0.53312 (9) | 0.86113 (11) | 0.96412 (13) | 0.0161 (3) | |
H6 | 0.4651 | 0.8427 | 0.9574 | 0.019* | |
C7 | 0.61276 (10) | 0.84398 (12) | 1.09371 (14) | 0.0174 (3) | |
H7 | 0.5984 | 0.8130 | 1.1752 | 0.021* | |
C8 | 0.39184 (9) | 0.85823 (12) | 0.63961 (13) | 0.0149 (3) | |
C9 | 0.33011 (9) | 0.93033 (12) | 0.52569 (13) | 0.0154 (3) | |
C10 | 0.38242 (10) | 1.04516 (12) | 0.54044 (13) | 0.0170 (3) | |
H10 | 0.3579 | 1.1141 | 0.4773 | 0.020* | |
C11 | 0.23592 (9) | 0.89631 (12) | 0.40828 (13) | 0.0157 (3) | |
C12 | 0.16893 (9) | 0.99103 (12) | 0.33479 (14) | 0.0180 (3) | |
H12 | 0.1828 | 1.0747 | 0.3683 | 0.022* | |
C13 | 0.08223 (10) | 0.96750 (13) | 0.21382 (14) | 0.0199 (3) | |
H13 | 0.0379 | 1.0328 | 0.1646 | 0.024* | |
C14 | 0.06491 (9) | 0.84515 (13) | 0.17031 (13) | 0.0177 (3) | |
C15 | 0.12917 (9) | 0.75009 (12) | 0.24281 (14) | 0.0170 (3) | |
C16 | 0.21486 (9) | 0.77116 (12) | 0.36133 (14) | 0.0169 (3) | |
H16 | 0.2580 | 0.7044 | 0.4095 | 0.020* | |
C17 | 0.01608 (10) | 0.66946 (14) | 0.04489 (14) | 0.0217 (3) | |
H17A | −0.0427 | 0.6118 | 0.0237 | 0.026* | |
H17B | 0.0442 | 0.6637 | −0.0347 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0172 (4) | 0.0250 (5) | 0.0207 (5) | 0.0016 (4) | −0.0013 (4) | −0.0017 (4) |
O2 | 0.0204 (5) | 0.0185 (5) | 0.0223 (5) | −0.0015 (4) | −0.0023 (4) | −0.0026 (4) |
N1 | 0.0150 (5) | 0.0125 (5) | 0.0151 (5) | −0.0002 (4) | 0.0036 (4) | 0.0007 (4) |
N2 | 0.0198 (5) | 0.0137 (5) | 0.0161 (5) | −0.0013 (4) | 0.0050 (4) | 0.0010 (4) |
N3 | 0.0144 (5) | 0.0165 (6) | 0.0307 (7) | −0.0019 (4) | −0.0017 (5) | 0.0071 (5) |
C1 | 0.0221 (7) | 0.0219 (7) | 0.0195 (7) | −0.0008 (5) | 0.0015 (5) | 0.0003 (5) |
C2 | 0.0197 (6) | 0.0134 (6) | 0.0178 (6) | 0.0013 (5) | 0.0030 (5) | −0.0025 (5) |
C3 | 0.0148 (6) | 0.0188 (6) | 0.0217 (7) | −0.0007 (5) | 0.0046 (5) | −0.0014 (5) |
C4 | 0.0183 (6) | 0.0170 (6) | 0.0171 (6) | 0.0000 (5) | 0.0066 (5) | −0.0001 (5) |
C5 | 0.0158 (6) | 0.0116 (6) | 0.0147 (6) | 0.0013 (4) | 0.0031 (5) | −0.0023 (5) |
C6 | 0.0153 (6) | 0.0142 (6) | 0.0189 (6) | 0.0003 (5) | 0.0061 (5) | −0.0016 (5) |
C7 | 0.0223 (6) | 0.0141 (6) | 0.0162 (6) | 0.0009 (5) | 0.0071 (5) | −0.0008 (5) |
C8 | 0.0127 (6) | 0.0154 (6) | 0.0171 (6) | −0.0001 (4) | 0.0057 (5) | −0.0013 (5) |
C9 | 0.0153 (6) | 0.0147 (6) | 0.0160 (6) | 0.0009 (5) | 0.0052 (5) | 0.0005 (5) |
C10 | 0.0199 (6) | 0.0150 (6) | 0.0149 (6) | 0.0002 (5) | 0.0046 (5) | 0.0014 (5) |
C11 | 0.0141 (6) | 0.0182 (6) | 0.0157 (6) | −0.0001 (5) | 0.0062 (5) | 0.0017 (5) |
C12 | 0.0179 (6) | 0.0157 (6) | 0.0202 (6) | 0.0011 (5) | 0.0063 (5) | 0.0011 (5) |
C13 | 0.0178 (6) | 0.0198 (7) | 0.0204 (7) | 0.0045 (5) | 0.0045 (5) | 0.0046 (5) |
C14 | 0.0132 (6) | 0.0238 (7) | 0.0143 (6) | 0.0002 (5) | 0.0026 (5) | 0.0015 (5) |
C15 | 0.0160 (6) | 0.0166 (6) | 0.0183 (6) | −0.0010 (5) | 0.0057 (5) | −0.0003 (5) |
C16 | 0.0141 (6) | 0.0171 (6) | 0.0181 (6) | 0.0016 (5) | 0.0035 (5) | 0.0025 (5) |
C17 | 0.0180 (6) | 0.0242 (7) | 0.0190 (6) | −0.0007 (5) | 0.0013 (5) | −0.0026 (5) |
O2—C15 | 1.3787 (16) | C4—H4 | 0.9500 |
O2—C17 | 1.4347 (15) | C5—C6 | 1.3872 (18) |
O1—C14 | 1.3856 (15) | C6—C7 | 1.3911 (17) |
O1—C17 | 1.4354 (17) | C6—H6 | 0.9500 |
N1—C8 | 1.3649 (16) | C7—H7 | 0.9500 |
N1—N2 | 1.3810 (15) | C8—C9 | 1.3925 (17) |
N1—C5 | 1.4258 (15) | C9—C10 | 1.4105 (17) |
N2—C10 | 1.3183 (16) | C9—C11 | 1.4719 (17) |
N3—C8 | 1.3621 (17) | C10—H10 | 0.9500 |
N3—H1N | 0.883 (9) | C11—C12 | 1.4016 (18) |
N3—H2N | 0.875 (9) | C11—C16 | 1.4134 (18) |
C1—C2 | 1.5091 (17) | C12—C13 | 1.4032 (17) |
C1—H1A | 0.9800 | C12—H12 | 0.9500 |
C1—H1B | 0.9800 | C13—C14 | 1.372 (2) |
C1—H1C | 0.9800 | C13—H13 | 0.9500 |
C2—C7 | 1.3940 (19) | C14—C15 | 1.3830 (18) |
C2—C3 | 1.3946 (19) | C15—C16 | 1.3771 (17) |
C3—C4 | 1.3898 (17) | C16—H16 | 0.9500 |
C3—H3 | 0.9500 | C17—H17A | 0.9900 |
C4—C5 | 1.3921 (18) | C17—H17B | 0.9900 |
C15—O2—C17 | 104.43 (10) | N3—C8—N1 | 122.88 (11) |
C14—O1—C17 | 104.05 (9) | N3—C8—C9 | 130.31 (12) |
C8—N1—N2 | 111.85 (10) | N1—C8—C9 | 106.77 (11) |
C8—N1—C5 | 129.22 (11) | C8—C9—C10 | 103.96 (11) |
N2—N1—C5 | 118.74 (10) | C8—C9—C11 | 129.77 (12) |
C10—N2—N1 | 104.01 (10) | C10—C9—C11 | 126.12 (11) |
C8—N3—H1N | 122.2 (11) | N2—C10—C9 | 113.40 (11) |
C8—N3—H2N | 117.3 (11) | N2—C10—H10 | 123.3 |
H1N—N3—H2N | 119.0 (16) | C9—C10—H10 | 123.3 |
C2—C1—H1A | 109.5 | C12—C11—C16 | 119.12 (12) |
C2—C1—H1B | 109.5 | C12—C11—C9 | 119.26 (12) |
H1A—C1—H1B | 109.5 | C16—C11—C9 | 121.47 (11) |
C2—C1—H1C | 109.5 | C11—C12—C13 | 122.76 (12) |
H1A—C1—H1C | 109.5 | C11—C12—H12 | 118.6 |
H1B—C1—H1C | 109.5 | C13—C12—H12 | 118.6 |
C7—C2—C3 | 118.16 (12) | C14—C13—C12 | 116.48 (12) |
C7—C2—C1 | 120.64 (12) | C14—C13—H13 | 121.8 |
C3—C2—C1 | 121.20 (12) | C12—C13—H13 | 121.8 |
C4—C3—C2 | 121.06 (12) | C13—C14—C15 | 121.64 (12) |
C4—C3—H3 | 119.5 | C13—C14—O1 | 128.63 (12) |
C2—C3—H3 | 119.5 | C15—C14—O1 | 109.69 (12) |
C3—C4—C5 | 119.71 (12) | C16—C15—O2 | 127.53 (12) |
C3—C4—H4 | 120.1 | C16—C15—C14 | 122.83 (12) |
C5—C4—H4 | 120.1 | O2—C15—C14 | 109.63 (11) |
C6—C5—C4 | 120.25 (11) | C15—C16—C11 | 117.16 (11) |
C6—C5—N1 | 120.59 (11) | C15—C16—H16 | 121.4 |
C4—C5—N1 | 119.06 (11) | C11—C16—H16 | 121.4 |
C5—C6—C7 | 119.32 (11) | O2—C17—O1 | 107.40 (10) |
C5—C6—H6 | 120.3 | O2—C17—H17A | 110.2 |
C7—C6—H6 | 120.3 | O1—C17—H17A | 110.2 |
C6—C7—C2 | 121.51 (12) | O2—C17—H17B | 110.2 |
C6—C7—H7 | 119.2 | O1—C17—H17B | 110.2 |
C2—C7—H7 | 119.2 | H17A—C17—H17B | 108.5 |
C8—N1—N2—C10 | 1.15 (13) | C8—C9—C10—N2 | 0.51 (14) |
C5—N1—N2—C10 | −174.21 (10) | C11—C9—C10—N2 | −175.48 (11) |
C7—C2—C3—C4 | 0.04 (19) | C8—C9—C11—C12 | 158.82 (13) |
C1—C2—C3—C4 | −179.34 (12) | C10—C9—C11—C12 | −26.24 (19) |
C2—C3—C4—C5 | 0.3 (2) | C8—C9—C11—C16 | −25.6 (2) |
C3—C4—C5—C6 | −0.26 (19) | C10—C9—C11—C16 | 149.34 (13) |
C3—C4—C5—N1 | 176.08 (11) | C16—C11—C12—C13 | −1.36 (19) |
C8—N1—C5—C6 | −47.97 (18) | C9—C11—C12—C13 | 174.33 (11) |
N2—N1—C5—C6 | 126.47 (12) | C11—C12—C13—C14 | 0.57 (19) |
C8—N1—C5—C4 | 135.70 (13) | C12—C13—C14—C15 | 0.53 (19) |
N2—N1—C5—C4 | −49.86 (16) | C12—C13—C14—O1 | 178.07 (12) |
C4—C5—C6—C7 | −0.10 (18) | C17—O1—C14—C13 | 168.94 (14) |
N1—C5—C6—C7 | −176.39 (11) | C17—O1—C14—C15 | −13.28 (14) |
C5—C6—C7—C2 | 0.44 (19) | C17—O2—C15—C16 | −168.01 (13) |
C3—C2—C7—C6 | −0.41 (19) | C17—O2—C15—C14 | 13.12 (14) |
C1—C2—C7—C6 | 178.98 (12) | C13—C14—C15—C16 | −0.8 (2) |
N2—N1—C8—N3 | 177.01 (11) | O1—C14—C15—C16 | −178.81 (11) |
C5—N1—C8—N3 | −8.2 (2) | C13—C14—C15—O2 | 178.09 (12) |
N2—N1—C8—C9 | −0.87 (14) | O1—C14—C15—O2 | 0.12 (15) |
C5—N1—C8—C9 | 173.88 (11) | O2—C15—C16—C11 | −178.70 (12) |
N3—C8—C9—C10 | −177.44 (13) | C14—C15—C16—C11 | 0.03 (19) |
N1—C8—C9—C10 | 0.23 (13) | C12—C11—C16—C15 | 1.02 (18) |
N3—C8—C9—C11 | −1.7 (2) | C9—C11—C16—C15 | −174.57 (11) |
N1—C8—C9—C11 | 176.01 (12) | C15—O2—C17—O1 | −21.31 (13) |
N1—N2—C10—C9 | −1.00 (14) | C14—O1—C17—O2 | 21.29 (13) |
Cg1 and Cg2 are the centroids of the C2–C7 and C11–C16 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N···N2i | 0.88 (2) | 2.16 (2) | 2.9981 (16) | 159 (1) |
C10—H10···Cg1ii | 0.95 | 2.97 | 3.6753 (14) | 133 |
C17—H17B···Cg2iii | 0.99 | 2.66 | 3.6334 (15) | 169 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y+1/2, z−3/2. |
Structure | pyrazolyl/p-tolyl | pyrazolyl/benzo-C6 | p-tolyl/benzo-C6 |
(mI) | 50.06 (5) | 27.27 (5) | 77.31 (4) |
(tI), molecule a | 49.08 (9) | 47.18 (7) | 85.22 (8) |
(tI), molecule b | 68.22 (9) | 31.67 (8) | 80.63 (8) |
Cg1 and Cg2 are the centroids of the C2–C7 and C11–C16 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N···N2i | 0.882 (15) | 2.159 (15) | 2.9981 (16) | 158.6 (14) |
C10—H10···Cg1ii | 0.95 | 2.97 | 3.6753 (14) | 133 |
C17—H17B···Cg2iii | 0.99 | 2.66 | 3.6334 (15) | 169 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y+1/2, z−3/2. |
Experimental details
Crystal data | |
Chemical formula | C17H15N3O2 |
Mr | 293.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 13.9652 (3), 10.6898 (2), 9.8459 (2) |
β (°) | 109.844 (2) |
V (Å3) | 1382.57 (5) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.77 |
Crystal size (mm) | 0.35 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Agilent SuperNova Dual diffractometer with an Atlas detector |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2014) |
Tmin, Tmax | 0.989, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4379, 2582, 2289 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.096, 1.03 |
No. of reflections | 2582 |
No. of parameters | 206 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.27 |
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXL97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
Acknowledgements
The authors are thankful to the Department of Chemistry, The Hong Kong University of Science and Technology (HKUST), Hong Kong (People's Republic of China), for access to the X-ray diffraction facility during the IYCr2014 OpenLab. One of the authors, MMJ, is also thankful to Professor Ian D. Williams (HKUST) for useful discussions. We thank Mr Y. S. Tan (University of Malaya) for performing the PXRD analysis.
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