1-Anilino-5-methyl-1H-1,2,3-triazole-4-carbaldehyde

The title compound, C₁₀H₁₀N₄O, is twisted about the N_ring—N_amine bond with the dihedral angle between the 1,2,3-triazolyl and N-bound phenyl rings being 79.14 (9)°. The C-bound aldehyde group is coplanar with the triazolyl ring, with the N—C—C—O torsion angle being 3.5 (3)°. While coplanar, the aldehyde O atom is orientated in the opposite direction to the triazolyl-bound methyl group. The most prominent feature of the mol­ecular packing is the formation of zigzag chains (glide symmetry) along the b axis and mediated by amine-N—H...N(triazol­yl) hydrogen bonds. The chains are connected into supra­molecular layers by phenyl- and methyl-C—H...O(aldehyde) inter­actions, with phenyl groups projecting to either side. Layers stack along the c axis with no directional inter­actions between them.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.047
• wR factor = 0.138
• Data-to-parameter ratio = 16.4

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PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1 Note

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          2 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT432_ALERT_2_G Short Inter X...Y Contact  O1     ..  C2      ..       3.01 Ang.
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          1 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          7 Note

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S1. Structural commentary

Inter­est in 1,2,3-triazoles relates, in part, to their biological activity (Dehaen & Bakulev, 2014). For example, compounds related to the title compound have been evaluated previously for activity against Cantagalo virus (Jordão et al., 2009) and for anti-tubercular activity (Jordão et al., 2011).

The title compound, Fig. 1, comprises two effectively co-planar regions. Thus, the aldehyde group connected at C1 is co-planar with the 1,2,3-triazolyl ring (r.m.s. deviation = 0.007 Å), forming a N4—C1—C10—O1 torsion angle of 3.5 (3)°. Indeed, the r.m.s. deviation of the least-squares plane through all non-hydrogen atoms in the molecule excluding those of the phenyl ring is 0.019 Å. The latter sits almost prime to the remainder of the molecule, forming a dihedral angle of 79.14 (9)° with the triazolyl ring. The aldehyde-O1 atom occupies a position anti with respect to the triazolyl-bound methyl group.

Amine-N—H···N(triazoyl) hydrogen bonds feature in the crystal structure, Table 1, and lead to zigzag chains along the b axis. The chains thus formed are linked into a layer in the ab plane, Fig. 2, by phenyl-C—H···O(aldehyde) and methyl-C—H···O(aldehyde) inter­actions, indicating the aldehyde-O atom accepts two inter­actions. The phenyl groups lie to either side of the supra­molecular layers that stack along the c axis. However, there are no directional inter­actions between successive layers.

1,2,3-Triazoles derivatives generated in the biological studies (e.g. Jordão et al., 2009) have provided crystals enabling delineation of the dependency of molecular packing patterns upon the electronegativity of the substituents, i.e. N-aryl­amino-1,2,3-triazole esters (Cunha et al., 2013) and N-(aryl­amino)-1,2,3-triazole-4-carbohydrazides (Seth et al., 2015).

S2. Synthesis and crystallization

To a solution of oxalyl chloride (3.00 mmol) in anhydrous CH₂Cl₂ (3.7 mL), maintained under nitro­gen at -78 ° C, was added drop wise DMSO (0.42 mL, 6.0 mmol). After stirring for 15 mins, a solution of the precursor alcohol (Cunha et al., 2016; 1.00 mmol) in DMSO (2 mL), followed by anhydrous CH₂Cl₂ (6.0 mL), were added drop wise. The reaction mixture was maintained at -78 ° C for 90 mins and Me₃N (1.05 mL,1.0 mmol) was then added drop wise. After stirring for 20 mins, aqueous NaCl was added, and the organic layer was extracted and concentrated under reduced pressure. The resulting residue was column chromatographed using silica gel and ethyl acetate:hexane (3:7) as eluent to give the pure triazole in 80% yield, as a yellow solid; M.pt: 118-120 °C. IR (KBr) ν_max (cm^-1) 3282 (N—H); 1689 (C═O). ¹H NMR (300 MHz, CDCl₃): δ 2.57 (s, 3H, CH₃), 6.52 (dd, 2H, J = 0.9 and 8.5 Hz, H5 & H9), 7.04 (tt, 1H, J = 0.9 and 7.3 Hz), 7.24-7.30 (m, 2H, H6 and H8), 7.66 (bs, 1H, N–H), 10.2 (s, 1H, CHO). ¹³C NMR (75 MHz, CDCl₃): δ 8.3 (CH₃), 113.7 (C5 & C9), 123.1 (C7), 129.5 (C6 & C8), 139.2 (C1 or C2), 142.2 (C1 or C2), 144.7 (C4), 186.0 (CHO). Anal. Calcd. for C₁₀H₁₀N₄O: C, 59.40; H, 4.98; N, 27.71. Found: C, 59.38; H, 4.95; N, 27.88.

S3. Refinement

The carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_equiv(C). The nitro­gen-bound H-atom was located in a difference Fourier map but were refined with a distance restraint of N—H = 0.88±0.01 Å, and with U_iso(H) set to 1.2U_equiv(N). Owing to poor agreement, a reflection, i.e. (2 1 2), was removed from the final cycles of refinement.

S4. Experimental

To a solution of oxalyl chloride (3.00 mmol) in anhydrous CH₂Cl₂ (3.7 mL), maintained under nitrogen at -78° C, was added dropwise DMSO (0.42 mL, 6.0 mmol). After stirring for 15 mins, a solution of the precursor alcohol (Cunha et al., 2016; 1.00 mmol) in DMSO (2 mL), followed by anhydrous CH₂Cl₂ (6.0 mL), were added drop wise. The reaction mixture was maintained at -78° C for 90 mins and Me₃N (1.05 mL,1.0 mmol) was then added dropwise. After stirring for 20 mins, aqueous NaCl was added, and the organic layer was extracted and concentrated under reduced pressure. The resulting residue was column chromatographed using silica gel and ethyl acetate:hexane (3:7) as eluent to give the pure triazole in 80% yield, as a yellow solid; m.p. 118–120°C. IR (KBr) ν_max (cm^-1) 3282 (N—H); 1689 (C═O). ¹H NMR (300 MHz, CDCl₃): δ 2.57 (s, 3H, CH₃), 6.52 (dd, 2H, J = 0.9 and 8.5 Hz, H5 & H9), 7.04 (tt, 1H, J = 0.9 and 7.3 Hz), 7.24–7.30 (m, 2H, H6 and H8), 7.66 (bs, 1H, N–H), 10.2 (s, 1H, CHO). ¹³C NMR (75 MHz, CDCl₃): δ 8.3 (CH₃), 113.7 (C5 & C9), 123.1 (C7), 129.5 (C6 & C8), 139.2 (C1 or C2), 142.2 (C1 or C2), 144.7 (C4), 186.0 (CHO). Anal. calcd. for C₁₀H₁₀N₄O: C, 59.40; H, 4.98; N, 27.71. Found: C, 59.38; H, 4.95; N, 27.88.

S5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Owing to poor agreement, a reflection, i.e. (2 1 2), was removed from the final cycles of refinement.

Structure description

Interest in 1,2,3-triazoles relates, in part, to their biological activity (Dehaen & Bakulev, 2014). For example, compounds related to the title compound have been evaluated previously for activity against Cantagalo virus (Jordão et al., 2009) and for anti-tubercular activity (Jordão et al., 2011).

The title compound, Fig. 1, comprises two effectively co-planar regions. Thus, the aldehyde group connected at C1 is co-planar with the 1,2,3-triazolyl ring (r.m.s. deviation = 0.007 Å), forming a N4—C1—C10—O1 torsion angle of 3.5 (3)°. Indeed, the r.m.s. deviation of the least-squares plane through all non-hydrogen atoms in the molecule excluding those of the phenyl ring is 0.019 Å. The latter sits almost prime to the remainder of the molecule, forming a dihedral angle of 79.14 (9)° with the triazolyl ring. The aldehyde-O1 atom occupies a position anti with respect to the triazolyl-bound methyl group.

Amine-N—H···N(triazoyl) hydrogen bonds feature in the crystal structure, Table 1, and lead to supramolecular zigzag chains along the b axis. The chains thus formed are linked into a layer in the ab plane, Fig. 2, by phenyl-C—H···O(aldehyde) and methyl-C—H···O(aldehyde) interactions, indicating the aldehyde-O atom accepts two interactions. The phenyl groups lie to either side of the supramolecular layers that stack along the c axis. However, there are no directional interactions between successive layers.

1,2,3-Triazole derivatives generated in the biological studies (e.g. Jordão et al., 2009) have provided crystals enabling delineation of the dependency of molecular packing patterns upon the electronegativity of the substituents, i.e. N-arylamino-1,2,3-triazole esters (Cunha et al., 2013) and N-(arylamino)-1,2,3-triazole-4-carbohydrazides (Seth et al., 2015).

Computing details

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the supramolecular later in the title compound shown in projection down the c axis. The N—H···N and C—H···O interactions are shown as blue and orange dashed lines, respectively.

1-Anilino-5-methyl-1H-1,2,3-triazole-4-carbaldehyde

Crystal data

C10H10N4O	Dx = 1.336 Mg m^−3
Mr = 202.22	Mo Kα radiation, λ = 0.71069 Å
Orthorhombic, Pbca	Cell parameters from 2601 reflections
a = 10.2208 (5) Å	θ = 2.9–27.5°
b = 10.8693 (6) Å	µ = 0.09 mm^−1
c = 18.1059 (6) Å	T = 120 K
V = 2011.44 (16) Å^3	Block, colourless
Z = 8	0.42 × 0.36 × 0.14 mm
F(000) = 848

Data collection

Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer	2310 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1639 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
φ & ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→12
Tmin = 0.713, Tmax = 1.000	l = −16→23
15215 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.047	w = 1/[σ^2(Fo^2) + (0.0767P)^2 + 0.2474P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.138	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.26 e Å^−3
2310 reflections	Δρmin = −0.25 e Å^−3
141 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2014), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.008 (2)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.79842 (12)	0.40421 (12)	0.54426 (7)	0.0402 (4)
N1	0.91541 (13)	0.88492 (13)	0.41939 (7)	0.0247 (3)
H1N	0.8472 (13)	0.9349 (14)	0.4211 (10)	0.030*
N2	0.88217 (12)	0.76712 (12)	0.44112 (7)	0.0219 (3)
N3	0.81206 (12)	0.69078 (13)	0.39631 (7)	0.0248 (3)
N4	0.79436 (12)	0.58967 (13)	0.43324 (7)	0.0238 (3)
C1	0.85041 (15)	0.60189 (15)	0.50173 (8)	0.0229 (4)
C2	0.90728 (15)	0.71584 (15)	0.50683 (8)	0.0233 (4)
C3	0.98009 (17)	0.77895 (18)	0.56623 (9)	0.0348 (5)
H3A	1.0446	0.8348	0.5444	0.052*
H3B	1.0250	0.7178	0.5969	0.052*
H3C	0.9189	0.8261	0.5968	0.052*
C4	0.99103 (15)	0.89324 (15)	0.35369 (8)	0.0227 (4)
C5	1.08721 (16)	0.80734 (16)	0.33814 (9)	0.0287 (4)
H5	1.1020	0.7401	0.3706	0.034*
C6	1.16142 (17)	0.82057 (18)	0.27480 (10)	0.0344 (5)
H6	1.2264	0.7611	0.2633	0.041*
C7	1.14220 (17)	0.91920 (18)	0.22815 (10)	0.0347 (5)
H7	1.1929	0.9271	0.1844	0.042*
C8	1.04906 (16)	1.00614 (17)	0.24536 (9)	0.0311 (4)
H8	1.0377	1.0756	0.2142	0.037*
C9	0.97184 (15)	0.99312 (15)	0.30771 (9)	0.0259 (4)
H9	0.9063	1.0523	0.3188	0.031*
C10	0.84565 (17)	0.50441 (17)	0.55572 (10)	0.0315 (4)
H10	0.8818	0.5199	0.6032	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0422 (8)	0.0268 (8)	0.0518 (9)	−0.0059 (6)	−0.0096 (6)	0.0107 (6)
N1	0.0283 (7)	0.0169 (7)	0.0289 (7)	0.0013 (6)	0.0038 (6)	0.0016 (6)
N2	0.0249 (7)	0.0178 (7)	0.0231 (7)	−0.0021 (6)	0.0009 (5)	−0.0018 (5)
N3	0.0271 (7)	0.0229 (8)	0.0246 (7)	−0.0037 (6)	−0.0002 (5)	−0.0033 (6)
N4	0.0253 (7)	0.0211 (8)	0.0250 (7)	−0.0009 (6)	0.0003 (5)	−0.0014 (6)
C1	0.0209 (8)	0.0225 (9)	0.0251 (9)	0.0000 (6)	−0.0016 (6)	0.0001 (6)
C2	0.0230 (8)	0.0226 (9)	0.0242 (8)	0.0014 (7)	−0.0019 (6)	0.0013 (6)
C3	0.0390 (10)	0.0330 (11)	0.0325 (10)	−0.0082 (8)	−0.0130 (7)	0.0001 (8)
C4	0.0246 (8)	0.0210 (9)	0.0224 (8)	−0.0042 (7)	−0.0014 (6)	−0.0011 (6)
C5	0.0274 (8)	0.0259 (10)	0.0328 (9)	0.0004 (7)	0.0014 (7)	0.0034 (7)
C6	0.0273 (9)	0.0358 (12)	0.0401 (11)	0.0027 (8)	0.0073 (7)	−0.0010 (8)
C7	0.0325 (10)	0.0409 (12)	0.0306 (10)	−0.0068 (8)	0.0076 (7)	0.0025 (8)
C8	0.0351 (9)	0.0292 (10)	0.0289 (9)	−0.0075 (7)	−0.0009 (7)	0.0061 (7)
C9	0.0274 (8)	0.0223 (9)	0.0282 (9)	−0.0019 (7)	−0.0018 (7)	−0.0009 (7)
C10	0.0310 (9)	0.0273 (10)	0.0363 (10)	−0.0017 (8)	−0.0078 (7)	0.0044 (8)

Geometric parameters (Å, º)

O1—C10	1.209 (2)	C3—H3C	0.9800
N1—N2	1.3818 (18)	C4—C9	1.382 (2)
N1—C4	1.421 (2)	C4—C5	1.385 (2)
N1—H1N	0.885 (9)	C5—C6	1.383 (2)
N2—C2	1.3387 (19)	C5—H5	0.9500
N2—N3	1.3639 (17)	C6—C7	1.379 (3)
N3—N4	1.2990 (18)	C6—H6	0.9500
N4—C1	1.372 (2)	C7—C8	1.377 (3)
C1—C2	1.371 (2)	C7—H7	0.9500
C1—C10	1.442 (2)	C8—C9	1.385 (2)
C2—C3	1.477 (2)	C8—H8	0.9500
C3—H3A	0.9800	C9—H9	0.9500
C3—H3B	0.9800	C10—H10	0.9500
N2—N1—C4	115.52 (13)	C9—C4—N1	118.49 (14)
N2—N1—H1N	111.4 (12)	C5—C4—N1	120.88 (14)
C4—N1—H1N	114.8 (12)	C6—C5—C4	119.21 (16)
C2—N2—N3	112.09 (13)	C6—C5—H5	120.4
C2—N2—N1	126.28 (13)	C4—C5—H5	120.4
N3—N2—N1	121.57 (12)	C7—C6—C5	120.72 (17)
N4—N3—N2	106.36 (12)	C7—C6—H6	119.6
N3—N4—C1	108.97 (13)	C5—C6—H6	119.6
C2—C1—N4	108.98 (14)	C8—C7—C6	119.56 (16)
C2—C1—C10	129.21 (15)	C8—C7—H7	120.2
N4—C1—C10	121.81 (15)	C6—C7—H7	120.2
N2—C2—C1	103.59 (13)	C7—C8—C9	120.55 (16)
N2—C2—C3	123.40 (15)	C7—C8—H8	119.7
C1—C2—C3	133.01 (15)	C9—C8—H8	119.7
C2—C3—H3A	109.5	C4—C9—C8	119.38 (16)
C2—C3—H3B	109.5	C4—C9—H9	120.3
H3A—C3—H3B	109.5	C8—C9—H9	120.3
C2—C3—H3C	109.5	O1—C10—C1	123.98 (16)
H3A—C3—H3C	109.5	O1—C10—H10	118.0
H3B—C3—H3C	109.5	C1—C10—H10	118.0
C9—C4—C5	120.52 (15)
C4—N1—N2—C2	124.41 (16)	C10—C1—C2—C3	−0.6 (3)
C4—N1—N2—N3	−58.74 (18)	N2—N1—C4—C9	146.17 (14)
C2—N2—N3—N4	−1.04 (17)	N2—N1—C4—C5	−37.6 (2)
N1—N2—N3—N4	−178.30 (12)	C9—C4—C5—C6	−1.9 (2)
N2—N3—N4—C1	1.16 (16)	N1—C4—C5—C6	−178.06 (15)
N3—N4—C1—C2	−0.93 (17)	C4—C5—C6—C7	1.3 (3)
N3—N4—C1—C10	179.48 (15)	C5—C6—C7—C8	0.8 (3)
N3—N2—C2—C1	0.45 (17)	C6—C7—C8—C9	−2.1 (3)
N1—N2—C2—C1	177.56 (14)	C5—C4—C9—C8	0.6 (2)
N3—N2—C2—C3	−179.19 (15)	N1—C4—C9—C8	176.79 (14)
N1—N2—C2—C3	−2.1 (2)	C7—C8—C9—C4	1.5 (3)
N4—C1—C2—N2	0.27 (17)	C2—C1—C10—O1	−176.00 (18)
C10—C1—C2—N2	179.83 (16)	N4—C1—C10—O1	3.5 (3)
N4—C1—C2—C3	179.87 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N4^i	0.89 (2)	2.23 (2)	3.101 (2)	168 (1)
C3—H3C···O1^i	0.98	2.56	3.181 (2)	121
C5—H5···O1^ii	0.95	2.42	3.345 (2)	163

Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) −x+2, −y+1, −z+1.