Crystal structures and Hirshfeld surface analysis of 5-amino-1-(4-meth-oxy-phen-yl)pyrazole-4-carb-ox-ylic acid and 5-amino-3-(4-meth-oxy-phen-yl)isoxazole.

The title compounds, C11H11N3O3, (I), and C10H10N2O2, (II), are commercially available and were crystallized from ethyl acetate solution. The dihedral angle between the pyrazole and phenyl rings in (I) is 52.34 (7)° and the equivalent angle between the isoxazole and phenyl rings in (II) is 7.30 (13)°. In the crystal of (I), the mol-ecules form carb-oxy-lic acid inversion dimers with an R(8) ring motif via pairwise O-H⋯O hydrogen bonds. In the crystal of (II), the mol-ecules are linked via N-H⋯N hydrogen bonds forming chains propagating along [010] with a C(5) motif. A weak N-H⋯π inter-action also features in the packing of (II). Hirshfeld surface analysis was used to explore the inter-molecular contacts in the crystals of both title compounds: the most important contacts for (I) are H⋯H (41.5%) and O⋯H/H⋯O (22.4%). For (II), the most significant contact percentages are H⋯H (36.1%) followed by C⋯H/H⋯C (31.3%). © Pintro et al. 2022.

Chemical context

This report is one of a series on the structures and hydrogen-bonding motifs in small-mol­ecule aromatic amino carb­oxy­lic acids (I) and small-mol­ecule aromatic amino compounds (II). This study follows other reports including, for example, 3-amino­pyrazine-2-carb­oxy­lic acid (Dobson & Gerkin, 1996 ▸), 5-amino­isophthalic acid hemihydrate (Dobson & Gerkin, 1998 ▸), and 1,4-di­benzyl­piperazine-2,5-dione (Nunez, et al., 2004 ▸). We now describe the structures of 5-amino-1-(4-meth­oxy­phen­yl)-pyrazole-4-carb­oxy­lic acid, (I) and 5-amino-3-(4-meth­oxy­phen­yl)isoxazole, (II).

Structural commentary

The mol­ecular structure of compound (I) is shown in Fig. 1 ▸. The pyrazole ring (r.m.s. deviation = 0.010 Å) is rotated by 52.34 (7)° relative to the phenyl ring (r.m.s. deviation = 0.010 Å), which is the primary contribution to the general non-planarity of the mol­ecule. An intra­molecular N3—H3A⋯O2 hydrogen bond is observed (Table 1 ▸ and Fig. 1 ▸). This bond forms an S(6) ring motif (Fig. 1 ▸ and Table 1 ▸) with an N3⋯O2 distance of 2.941 (3) Å. This is a common feature in analogous compounds (such as those listed in the Database survey). The C3—N3 distance of 1.353 (2) Å is typical for an amino group bound to an aromatic ring. The carb­oxy­lic carbon–oxygen distances are 1.255 (2) and 1.316 (2) for C4—O2 and C4—O1, respectively, indicating that the former bond may be affected by the intra­molecular N—H⋯O hydrogen bond.

Figure 1

The mol­ecular structure of (I) with displacement ellipsoids drawn at the 50% probability level. The intra­molecular hydrogen bond is represented by a red dashed line.

Table 1

Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O2	0.87 (2)	2.32 (2)	2.941 (3)	128.5 (18)
O1—H1⋯O2i	0.90 (2)	1.75 (2)	2.649 (2)	176 (3)

Symmetry code: (i) .

The mol­ecular structure of compound (II) is shown in Fig. 2 ▸. The angle between the phenyl and isoxazole rings is 7.30 (13)°, resulting in the overall mol­ecule being close to planar with the r.m.s. deviation of all non-hydrogen atoms being 0.054 Å. The N1—O1 distance is 1.434 (4) Å and is consistent with other isoxazoles (see Database survey section). The C3—N2 distance is 1.350 (5) Å and is typical of an amino group bound to an aromatic ring.

Figure 2

The mol­ecular structure of (II) with displacement ellipsoids drawn at the 50% probability level.

Supra­molecular features

In the extended structure of (I), the mol­ecules form centrosymmetric hydrogen-bonded dimers via the O1—H1⋯O2i [symmetry code: (i) −x + 1, −y, −z + 1] link to generate an R(8) loop with O⋯O = 2.649 (2) Å, see Table 1 ▸ and Fig. 3 ▸. These dimers are linked via π–π inter­actions, notably weak stacking inter­actions between the 4-meth­oxy­phenyl rings [Cg1⋯Cg1 (x + 1, y, z) = 3.9608 (4) Å, where Cg1 is the centroid of the C5–C10 ring] along the a-axis direction.

Figure 3

A view along the a-axis direction of the crystal packing of (I) with hydrogen bonds shown as red dashed lines.

In the packing of (II), the mol­ecules form hydrogen-bonded chains running along the b-axis direction via the N2—H2A⋯N1i hydrogen bond [symmetry code: (i) −x + 1, y +  , −z +  ] hydrogen bond forms a C(5) chain motif with an N⋯N distance of 3.003 (5) Å, see Table 2 ▸ and Fig. 4 ▸. No π–π inter­actions are observed.

Table 2

Hydrogen-bond geometry (Å, °) for (II)

Cg2 is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.89 (3)	2.12 (3)	3.003 (5)	174 (6)
N2—H2B⋯Cg2ii	0.85 (2)	2.97 (4)	3.709 (4)	147 (4)

Symmetry codes: (i) ; (ii) .

Figure 4

A view along the a-axis direction of the crystal packing of (II) with hydrogen bonds shown as red dashed lines.

Hirshfeld surface analysis

The inter­molecular inter­actions were further investigated by qu­anti­tative analysis of the Hirshfeld surface, and visualized with Crystal Explorer 17.5 (Turner et al., 2017 ▸; Spackman et al., 2009 ▸) and the two-dimensional fingerprint plots (McKinnon et al., 2007 ▸). The shorter and longer contacts are indicated as red and blue spots, respectively, on the Hirshfeld surfaces, and contacts with distances approximately equal to the sum of the van der Waals radii are colored white. The function d norm is a ratio enclosing the distances of any surface point to the nearest inter­ior (d i) and exterior (d e) atom and the van der Waals (vdW) radii of the atoms. The d norm plots were mapped with a color scale between −0.18 au (blue) and +1.4 au (red).

Fig. 5 ▸. shows the d norm surface of compound (I). The most intense red spots on the d norm surface correspond to the O1—H1⋯O2 inter­actions. The red and blue triangles on the shape-index surface indicate that there are weak π-stacking inter­actions in the crystal structure. Analysis of the two-dimensional fingerprint plots indicate that the H⋯H (41.5%) inter­actions are the major factor in the crystal packing with O⋯H/H⋯O (22.4%) inter­actions making the next highest contribution. The percentage contributions of other significant contacts are: C⋯H/H⋯C (13.1%) and N⋯H/ H⋯N (8.7%).

Figure 5

Hirshfeld surface for (I) mapped over d norm.

Fig. 6 ▸ shows the d norm surface of compound (II). The large red spots represent N2—H2A⋯N1 inter­actions. Some additional inter­actions indicated by very light-red spots correspond to contacts around phenyl ring and isoxazole rings: N2—H2B⋯Cg1ii [2.97 (4) Å], C6—H6⋯Cg1iii (2.86 Å) and C9—H9⋯Cg2ii (2.86 Å) [symmetry codes: (ii) x +  , −y +  , −z + 1; (iii) x −  , −y +  , −z + 1; Cg1 and Cg2 are the centroids of the O1/N1/C1–C3 and C4–C9 rings, respectively]. Analysis of the two-dimensional fingerprint plots indicates that the H⋯H (36.1%) inter­actions are the major factor in the crystal packing with C⋯H/H⋯C (31.3%) contacts making the next highest contribution. The percentage contributions of other weak inter­actions are: O⋯H/H⋯O (17.3%) and N⋯H/ H⋯N (12.1%). Figures showing the shape-index surface for each compound and the overall fingerprint plots are included in the supporting information.

Figure 6

Hirshfeld surface for (II) mapped over d norm.

Database survey

A search of the Cambridge Structural Database (CSD, version 5.42, update of November 2020; Groom et al., 2016 ▸) gave 13 hits for the 3-phenyl­isoxazol-5-amine moiety. The four most closely related compounds are: 5-di­acetyl­amino-3,4-di­phenyl­isoxazole (CSD refcode ACPIXZ; Simon et al., 1974 ▸), 1,5-dimethyl-4-phenyl-3-(3-phenyl-1,2-oxazol-5-yl)imidazol­id­in-2-one (HOGYAE; Li et al., 2007 ▸), N-4-dimethyl-N-[3-{4-(tri­fluoro­meth­yl)phen­yl]-1,2-oxazol-5-yl}benzene-1-sulfonamide (XOSHUL; Chen & Cui, 2019 ▸), 3-phenyl-5-(1H-pyrazol-1-yl)-1,2-oxazole (ZEVGIT; Mikhailov et al., 2018 ▸).

A similar search gave 14 hits for the 5-amino-1-phenyl-1H-pyrazole-4-carb­oxy­lic acid moiety. The seven most closely related compounds are: ethyl 1-(4-chloro-2-nitro­phen­yl)-5-nitro-4,5-di­hydro-1H-pyrazole-4-carboxyl­ate (GOLHEV; Zia-ur-Rehman et al., 2009 ▸), 5-amino-1-phenyl-3-(tri­fluoro­meth­yl)-1H-pyrazole-4-carb­oxy­lic acid (HUDDEQ; Caruso et al., 2009 ▸), 5-amino-1-phenyl-1H-pyrazole-4-carb­oxy­lic acid (KODXIL; Zia-ur-Rehman et al., 2008 ▸), ethyl 5-amino-1-(2,4-di­nitro­phen­yl)-1H-pyrazole-4-carboxyl­ate (QAHJER; Ghorab et al., 2016 ▸), ethyl 5-amino-1-phenyl-1H-pyrazole-4-carboxyl­ate (RUVHUO, Soares et al., 2020 ▸), ethyl 5-amino-1-(4-sulfamoylphen­yl)-1H-pyrazole-4-carboxyl­ate (XUTZIX; Ibrahim et al., 2015 ▸) and 2-eth­oxy­ethyl 5-amino-1-(2,4-di­methyl­phen­yl)-3-(methyl­thio)-1H-pyrazole-4-carboxyl­ate (YOYHOK, Liu et al., 2009 ▸).

Synthesis and crystallization

Compounds (I) and (II) are commercially available and were purchased from Aldrich. Both were dissolved in ethyl acetate until saturated and these solutions were allowed to evaporate slowly at room temperature, which resulted in X-ray quality crystals.

Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 3 ▸. All carbon-bound H atoms were positioned geometrically and refined as riding, with C—H = 0.95 or 0.98 Å and U iso(H) = 1.2U eq(C) or 1.5U eq(methyl C). In order to ensure a chemically meaningful O—H distance in (I), this was restrained to a target value of 0.84 (2) Å and U iso(H) = 1.5U eq(O). In (I), the amino H atoms were located in a difference-Fourier map. In (II), the N—H distances were restrained to a target value of 0.84 (2) Å and U iso(H) = 1.5U eq(N). The absolute structure of (II) was indeterminate based on the present refinement.

Table 3

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C11H11N3O3	C10H10N2O2
M r	233.23	190.20
Crystal system, space group	Monoclinic, P21/n	Orthorhombic, P212121
Temperature (K)	170	170
a, b, c (Å)	3.9608 (4), 24.104 (3), 11.1762 (10)	7.6496 (11), 8.7565 (15), 14.128 (2)
α, β, γ (°)	90, 90.189 (9), 90	90, 90, 90
V (Å3)	1067.0 (2)	946.4 (3)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	0.11	0.10
Crystal size (mm)	0.5 × 0.2 × 0.2	0.4 × 0.2 × 0.2
Data collection
Diffractometer	Rigaku XtaLAB mini	Rigaku XtaLAB mini
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 ▸)	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 ▸)
T min, T max	0.975, 1.000	0.757, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8175, 2937, 1667	6912, 2635, 1344
R int	0.032	0.050
(sin θ/λ)max (Å−1)	0.694	0.694
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.049, 0.155, 1.03	0.052, 0.168, 1.02
No. of reflections	2937	2635
No. of parameters	168	137
No. of restraints	1	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.16, −0.19	0.17, −0.16
Absolute structure	–	Flack x determined using 385 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)
Absolute structure parameter	–	−0.7 (10)

Computer programs: CrysAlis PRO (Rigaku OD, 2018 ▸), SHELXT2014/5 (Sheldrick, 2015a ▸), SHELXL2018/1 (Sheldrick, 2015b ▸), and OLEX2 (Dolomanov et al., 2009 ▸).

Crystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989022001827/hb8013sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022001827/hb8013Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989022001827/hb8013IIsup3.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989022001827/hb8013Isup4.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989022001827/hb8013IIsup5.cml

Shape-index and fingerprint plots for compounds (I) and (II). DOI: 10.1107/S2056989022001827/hb8013sup6.pdf

CCDC references: 2152583, 2152582

Additional supporting information: crystallographic information; 3D view; checkCIF report

C11H11N3O3	F(000) = 488
Mr = 233.23	Dx = 1.452 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 3.9608 (4) Å	Cell parameters from 1271 reflections
b = 24.104 (3) Å	θ = 2.0–23.7°
c = 11.1762 (10) Å	µ = 0.11 mm−1
β = 90.189 (9)°	T = 170 K
V = 1067.0 (2) Å3	Block, clear colourless
Z = 4	0.5 × 0.2 × 0.2 mm

Rigaku XtaLAB mini diffractometer	2937 independent reflections
Radiation source: Sealed Tube, Rigaku (Mo) X-ray Source	1667 reflections with I > 2σ(I)
Graphite Monochromator monochromator	Rint = 0.032
Detector resolution: 13.6612 pixels mm-1	θmax = 29.6°, θmin = 2.0°
profile data from ω–scans	h = −5→5
Absorption correction: multi-scan (CrysalisPro; Rigaku OD, 2018)	k = −33→33
Tmin = 0.975, Tmax = 1.000	l = −15→14
8175 measured reflections

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.049	w = 1/[σ2(Fo2) + (0.060P)2 + 0.1763P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.155	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.16 e Å−3
2937 reflections	Δρmin = −0.19 e Å−3
168 parameters	Extinction correction: SHELXL2018/1 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.017 (3)
Primary atom site location: dual

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
O1	0.3397 (4)	0.03421 (7)	0.62727 (13)	0.0697 (5)
H1	0.370 (8)	0.0005 (8)	0.594 (2)	0.113 (11)*
C1	0.2875 (5)	0.14586 (10)	0.72321 (18)	0.0595 (5)
H1A	0.208584	0.120332	0.781520	0.071*
N1	0.4218 (4)	0.22042 (7)	0.63223 (12)	0.0495 (4)
C2	0.4182 (5)	0.12959 (8)	0.61090 (17)	0.0519 (5)
O2	0.5820 (4)	0.06706 (6)	0.46040 (12)	0.0648 (4)
N2	0.2864 (5)	0.19977 (8)	0.73857 (14)	0.0608 (5)
O3	0.5775 (4)	0.44729 (6)	0.57003 (13)	0.0699 (5)
C3	0.5066 (4)	0.17936 (8)	0.55617 (15)	0.0463 (4)
N3	0.6542 (5)	0.18839 (9)	0.44896 (14)	0.0573 (5)
H3A	0.704 (5)	0.1581 (9)	0.4099 (19)	0.060 (6)*
H3B	0.692 (6)	0.2227 (10)	0.422 (2)	0.070 (7)*
C4	0.4535 (5)	0.07533 (9)	0.56133 (17)	0.0545 (5)
C5	0.4620 (4)	0.27870 (8)	0.61733 (15)	0.0462 (4)
C6	0.3325 (5)	0.30549 (8)	0.51751 (15)	0.0495 (5)
H6	0.215830	0.285018	0.457648	0.059*
C7	0.3738 (5)	0.36188 (9)	0.50557 (16)	0.0522 (5)
H7	0.285859	0.380302	0.437091	0.063*
C8	0.5434 (5)	0.39210 (8)	0.59310 (16)	0.0504 (5)
C9	0.6654 (5)	0.36518 (8)	0.69428 (16)	0.0524 (5)
H9	0.774143	0.385704	0.755892	0.063*
C10	0.6278 (5)	0.30858 (8)	0.70480 (15)	0.0505 (5)
H10	0.716871	0.289972	0.772872	0.061*
C11	0.7499 (6)	0.48080 (10)	0.6567 (2)	0.0770 (7)
H11A	0.979212	0.466515	0.668620	0.115*
H11B	0.627391	0.479613	0.732705	0.115*
H11C	0.761020	0.519180	0.628081	0.115*

	U11	U22	U33	U12	U13	U23
O1	0.0905 (12)	0.0604 (10)	0.0584 (9)	−0.0021 (9)	0.0143 (8)	0.0150 (7)
C1	0.0614 (12)	0.0677 (14)	0.0495 (11)	−0.0015 (10)	0.0083 (9)	0.0107 (9)
N1	0.0505 (9)	0.0608 (10)	0.0373 (8)	−0.0023 (7)	0.0036 (7)	0.0019 (6)
C2	0.0491 (11)	0.0609 (12)	0.0457 (10)	−0.0016 (9)	−0.0010 (8)	0.0053 (8)
O2	0.0815 (11)	0.0609 (9)	0.0521 (8)	−0.0018 (7)	0.0098 (7)	0.0048 (6)
N2	0.0691 (11)	0.0708 (12)	0.0427 (8)	−0.0016 (9)	0.0140 (8)	0.0069 (7)
O3	0.0846 (11)	0.0573 (9)	0.0678 (9)	−0.0025 (8)	−0.0131 (8)	−0.0037 (7)
C3	0.0403 (9)	0.0623 (12)	0.0362 (8)	−0.0017 (8)	−0.0026 (7)	0.0013 (8)
N3	0.0731 (12)	0.0585 (11)	0.0402 (9)	−0.0022 (9)	0.0104 (8)	0.0009 (8)
C4	0.0528 (11)	0.0610 (13)	0.0495 (11)	0.0002 (9)	−0.0029 (9)	0.0104 (9)
C5	0.0404 (9)	0.0593 (11)	0.0390 (9)	−0.0021 (8)	0.0038 (7)	−0.0005 (7)
C6	0.0468 (10)	0.0638 (12)	0.0379 (9)	−0.0034 (9)	−0.0023 (8)	−0.0026 (8)
C7	0.0511 (11)	0.0647 (13)	0.0409 (9)	0.0033 (9)	−0.0025 (8)	0.0011 (8)
C8	0.0480 (10)	0.0576 (12)	0.0455 (10)	0.0026 (8)	0.0030 (8)	−0.0053 (8)
C9	0.0495 (11)	0.0664 (13)	0.0413 (9)	0.0001 (9)	−0.0026 (8)	−0.0091 (8)
C10	0.0483 (10)	0.0669 (13)	0.0364 (9)	0.0025 (9)	−0.0014 (8)	−0.0024 (8)
C11	0.0820 (16)	0.0637 (14)	0.0852 (16)	−0.0024 (12)	−0.0122 (13)	−0.0173 (12)

O1—H1	0.901 (17)	N3—H3B	0.90 (2)
O1—C4	1.316 (2)	C5—C6	1.386 (2)
C1—H1A	0.9500	C5—C10	1.379 (2)
C1—C2	1.415 (3)	C6—H6	0.9500
C1—N2	1.311 (3)	C6—C7	1.376 (3)
N1—N2	1.397 (2)	C7—H7	0.9500
N1—C3	1.348 (2)	C7—C8	1.391 (3)
N1—C5	1.424 (2)	C8—C9	1.389 (3)
C2—C3	1.392 (3)	C9—H9	0.9500
C2—C4	1.427 (3)	C9—C10	1.378 (3)
O2—C4	1.255 (2)	C10—H10	0.9500
O3—C8	1.362 (2)	C11—H11A	0.9800
O3—C11	1.433 (3)	C11—H11B	0.9800
C3—N3	1.353 (2)	C11—H11C	0.9800
N3—H3A	0.87 (2)
C4—O1—H1	113.6 (19)	C10—C5—C6	120.09 (19)
C2—C1—H1A	123.4	C5—C6—H6	120.2
N2—C1—H1A	123.4	C7—C6—C5	119.65 (17)
N2—C1—C2	113.11 (18)	C7—C6—H6	120.2
N2—N1—C5	119.63 (15)	C6—C7—H7	119.8
C3—N1—N2	111.84 (16)	C6—C7—C8	120.44 (18)
C3—N1—C5	128.51 (15)	C8—C7—H7	119.8
C1—C2—C4	129.42 (19)	O3—C8—C7	115.24 (17)
C3—C2—C1	104.13 (18)	O3—C8—C9	125.16 (17)
C3—C2—C4	126.45 (18)	C9—C8—C7	119.60 (19)
C1—N2—N1	103.90 (16)	C8—C9—H9	120.2
C8—O3—C11	118.03 (17)	C10—C9—C8	119.65 (17)
N1—C3—C2	106.99 (16)	C10—C9—H9	120.2
N1—C3—N3	123.35 (18)	C5—C10—H10	119.7
N3—C3—C2	129.65 (19)	C9—C10—C5	120.54 (17)
C3—N3—H3A	114.1 (14)	C9—C10—H10	119.7
C3—N3—H3B	121.7 (15)	O3—C11—H11A	109.5
H3A—N3—H3B	124 (2)	O3—C11—H11B	109.5
O1—C4—C2	116.02 (18)	O3—C11—H11C	109.5
O2—C4—O1	121.64 (19)	H11A—C11—H11B	109.5
O2—C4—C2	122.34 (18)	H11A—C11—H11C	109.5
C6—C5—N1	120.85 (16)	H11B—C11—H11C	109.5
C10—C5—N1	119.05 (16)
C1—C2—C3—N1	−1.5 (2)	C3—C2—C4—O1	−177.21 (18)
C1—C2—C3—N3	177.56 (19)	C3—C2—C4—O2	2.1 (3)
C1—C2—C4—O1	2.3 (3)	C4—C2—C3—N1	178.11 (18)
C1—C2—C4—O2	−178.46 (19)	C4—C2—C3—N3	−2.9 (3)
N1—C5—C6—C7	179.75 (16)	C5—N1—N2—C1	−179.45 (17)
N1—C5—C10—C9	−178.75 (16)	C5—N1—C3—C2	179.87 (16)
C2—C1—N2—N1	0.0 (2)	C5—N1—C3—N3	0.8 (3)
N2—C1—C2—C3	0.9 (2)	C5—C6—C7—C8	−0.2 (3)
N2—C1—C2—C4	−178.6 (2)	C6—C5—C10—C9	0.3 (3)
N2—N1—C3—C2	1.6 (2)	C6—C7—C8—O3	178.16 (17)
N2—N1—C3—N3	−177.50 (17)	C6—C7—C8—C9	−1.3 (3)
N2—N1—C5—C6	−127.58 (18)	C7—C8—C9—C10	2.3 (3)
N2—N1—C5—C10	51.4 (2)	C8—C9—C10—C5	−1.8 (3)
O3—C8—C9—C10	−177.11 (18)	C10—C5—C6—C7	0.8 (3)
C3—N1—N2—C1	−1.0 (2)	C11—O3—C8—C7	180.00 (19)
C3—N1—C5—C6	54.3 (3)	C11—O3—C8—C9	−0.5 (3)
C3—N1—C5—C10	−126.71 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2	0.87 (2)	2.32 (2)	2.941 (3)	128.5 (18)
O1—H1···O2i	0.90 (2)	1.75 (2)	2.649 (2)	176 (3)

C10H10N2O2	Dx = 1.335 Mg m−3
Mr = 190.20	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 1405 reflections
a = 7.6496 (11) Å	θ = 2.7–22.5°
b = 8.7565 (15) Å	µ = 0.10 mm−1
c = 14.128 (2) Å	T = 170 K
V = 946.4 (3) Å3	Block, clear colourless
Z = 4	0.4 × 0.2 × 0.2 mm
F(000) = 400

Rigaku XtaLAB mini diffractometer	2635 independent reflections
Radiation source: fine-focus sealed X-ray tube, Rigaku (Mo) X-ray Source	1344 reflections with I > 2σ(I)
Graphite Monochromator monochromator	Rint = 0.050
Detector resolution: 13.6612 pixels mm-1	θmax = 29.6°, θmin = 2.7°
profile data from ω–scans	h = −10→9
Absorption correction: multi-scan (CrysalisPro; Rigaku OD, 2018)	k = −11→11
Tmin = 0.757, Tmax = 1.000	l = −11→19
6912 measured reflections

Refinement on F2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0606P)2] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.052	(Δ/σ)max < 0.001
wR(F2) = 0.168	Δρmax = 0.17 e Å−3
S = 1.02	Δρmin = −0.16 e Å−3
2635 reflections	Extinction correction: SHELXL2018/1 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
137 parameters	Extinction coefficient: 0.037 (7)
2 restraints	Absolute structure: Flack x determined using 385 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: −0.7 (10)
Hydrogen site location: mixed

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
O1	0.5261 (3)	0.8179 (3)	0.69875 (17)	0.0617 (7)
C1	0.5966 (4)	0.6690 (4)	0.5813 (2)	0.0523 (8)
N1	0.4969 (4)	0.6710 (4)	0.6566 (2)	0.0632 (8)
O2	0.6029 (4)	0.1662 (3)	0.33196 (17)	0.0736 (8)
N2	0.6808 (5)	1.0370 (5)	0.6730 (3)	0.0718 (10)
C2	0.6906 (5)	0.8049 (4)	0.5699 (3)	0.0615 (10)
H2	0.770803	0.829616	0.520934	0.074*
C3	0.6421 (5)	0.8938 (4)	0.6445 (2)	0.0578 (9)
C4	0.5977 (4)	0.5345 (4)	0.5186 (2)	0.0516 (8)
C5	0.5115 (5)	0.4010 (4)	0.5422 (2)	0.0588 (9)
H5	0.452653	0.395103	0.601305	0.071*
C6	0.5081 (5)	0.2752 (5)	0.4821 (2)	0.0613 (10)
H6	0.446575	0.185365	0.499673	0.074*
C7	0.5963 (5)	0.2827 (5)	0.3959 (3)	0.0592 (10)
C8	0.6848 (5)	0.4147 (5)	0.3719 (2)	0.0629 (10)
H8	0.746554	0.419948	0.313670	0.076*
C9	0.6843 (5)	0.5390 (5)	0.4321 (2)	0.0606 (10)
H9	0.744260	0.629430	0.414044	0.073*
C10	0.5103 (6)	0.0287 (5)	0.3529 (3)	0.0887 (14)
H10A	0.533820	−0.047211	0.303518	0.133*
H10B	0.384640	0.049924	0.355305	0.133*
H10C	0.549038	−0.011138	0.414254	0.133*
H2A	0.635 (9)	1.074 (6)	0.726 (3)	0.17 (3)*
H2B	0.753 (5)	1.087 (5)	0.640 (3)	0.090 (17)*

	U11	U22	U33	U12	U13	U23
O1	0.0673 (15)	0.0646 (17)	0.0531 (13)	−0.0011 (14)	0.0098 (11)	0.0035 (12)
C1	0.0433 (16)	0.065 (2)	0.0489 (17)	0.0065 (18)	0.0021 (14)	0.0079 (16)
N1	0.071 (2)	0.064 (2)	0.0551 (16)	−0.0038 (18)	0.0105 (15)	−0.0017 (15)
O2	0.0721 (17)	0.089 (2)	0.0600 (15)	−0.0106 (18)	0.0091 (13)	−0.0176 (14)
N2	0.080 (3)	0.065 (2)	0.071 (2)	−0.0054 (19)	0.0106 (19)	−0.0007 (18)
C2	0.056 (2)	0.070 (3)	0.058 (2)	−0.001 (2)	0.0137 (17)	0.0019 (19)
C3	0.056 (2)	0.063 (2)	0.0545 (19)	0.0013 (18)	−0.0014 (16)	0.0057 (18)
C4	0.0453 (17)	0.062 (2)	0.0477 (15)	0.0034 (17)	0.0009 (15)	0.0059 (15)
C5	0.057 (2)	0.070 (2)	0.0493 (18)	0.0015 (19)	0.0071 (16)	0.0024 (17)
C6	0.055 (2)	0.075 (2)	0.0539 (19)	−0.0026 (19)	0.0072 (18)	−0.0003 (18)
C7	0.0492 (18)	0.077 (3)	0.0512 (18)	0.0034 (19)	−0.0005 (17)	−0.0031 (17)
C8	0.055 (2)	0.083 (3)	0.0502 (19)	0.001 (2)	0.0097 (16)	0.0034 (19)
C9	0.056 (2)	0.073 (2)	0.0527 (19)	−0.001 (2)	0.0068 (16)	0.0096 (18)
C10	0.093 (3)	0.092 (3)	0.080 (3)	−0.019 (3)	0.015 (3)	−0.020 (3)

O1—N1	1.434 (4)	C4—C9	1.390 (5)
O1—C3	1.348 (4)	C5—H5	0.9500
C1—N1	1.310 (4)	C5—C6	1.391 (5)
C1—C2	1.399 (5)	C6—H6	0.9500
C1—C4	1.474 (5)	C6—C7	1.394 (5)
O2—C7	1.363 (5)	C7—C8	1.382 (6)
O2—C10	1.429 (5)	C8—H8	0.9500
N2—C3	1.350 (5)	C8—C9	1.381 (5)
N2—H2A	0.89 (3)	C9—H9	0.9500
N2—H2B	0.85 (2)	C10—H10A	0.9800
C2—H2	0.9500	C10—H10B	0.9800
C2—C3	1.362 (5)	C10—H10C	0.9800
C4—C5	1.383 (5)
C3—O1—N1	108.0 (3)	C6—C5—H5	119.0
N1—C1—C2	112.4 (3)	C5—C6—H6	120.4
N1—C1—C4	120.2 (3)	C5—C6—C7	119.2 (4)
C2—C1—C4	127.4 (3)	C7—C6—H6	120.4
C1—N1—O1	105.0 (3)	O2—C7—C6	124.2 (4)
C7—O2—C10	118.4 (3)	O2—C7—C8	116.4 (3)
C3—N2—H2A	120 (4)	C8—C7—C6	119.3 (4)
C3—N2—H2B	117 (3)	C7—C8—H8	119.8
H2A—N2—H2B	122 (5)	C9—C8—C7	120.5 (3)
C1—C2—H2	127.5	C9—C8—H8	119.8
C3—C2—C1	104.9 (3)	C4—C9—H9	119.3
C3—C2—H2	127.5	C8—C9—C4	121.3 (4)
O1—C3—N2	115.7 (3)	C8—C9—H9	119.3
O1—C3—C2	109.7 (3)	O2—C10—H10A	109.5
N2—C3—C2	134.6 (4)	O2—C10—H10B	109.5
C5—C4—C1	121.8 (3)	O2—C10—H10C	109.5
C5—C4—C9	117.6 (3)	H10A—C10—H10B	109.5
C9—C4—C1	120.5 (3)	H10A—C10—H10C	109.5
C4—C5—H5	119.0	H10B—C10—H10C	109.5
C4—C5—C6	122.1 (3)
C1—C2—C3—O1	0.2 (4)	C3—O1—N1—C1	0.2 (4)
C1—C2—C3—N2	−178.0 (4)	C4—C1—N1—O1	−178.9 (3)
C1—C4—C5—C6	178.2 (3)	C4—C1—C2—C3	178.6 (3)
C1—C4—C9—C8	−179.2 (3)	C4—C5—C6—C7	0.9 (6)
N1—O1—C3—N2	178.3 (3)	C5—C4—C9—C8	−0.2 (5)
N1—O1—C3—C2	−0.3 (4)	C5—C6—C7—O2	179.5 (4)
N1—C1—C2—C3	−0.1 (4)	C5—C6—C7—C8	0.0 (5)
N1—C1—C4—C5	−7.7 (5)	C6—C7—C8—C9	−0.9 (6)
N1—C1—C4—C9	171.3 (3)	C7—C8—C9—C4	1.0 (6)
O2—C7—C8—C9	179.5 (3)	C9—C4—C5—C6	−0.8 (5)
C2—C1—N1—O1	−0.1 (4)	C10—O2—C7—C6	1.7 (6)
C2—C1—C4—C5	173.7 (3)	C10—O2—C7—C8	−178.8 (4)
C2—C1—C4—C9	−7.3 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.89 (3)	2.12 (3)	3.003 (5)	174 (6)
N2—H2B···Cg2ii	0.85 (2)	2.97 (4)	3.709 (4)	147 (4)