Crystal structure of (E)-1,3-dimethyl-2-[3-(3-nitro­phen­yl)triaz-2-en-1-yl­idene]-2,3-di­hydro-1H-imidazole

Patil, S.; Bugarin, A.

doi:10.1107/S1600536814020698

research communications

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ISSN: 2056-9890

Volume 70| Part 10| October 2014| Pages 224-227

doi:10.1107/S1600536814020698

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Crystal structure of (E)-1,3-dimethyl-2-[3-(3-nitrophenyl)triaz-2-en-1-ylidene]-2,3-dihydro-1H-imidazole

Siddappa Patil ^a and Alejandro Bugarin ^a ^*

^aDepartment of Chemistry & Biochemistry, University of Texas at Arlington, PO Box, 19065, Arlington, TX 76019, USA
^*Correspondence e-mail: bugarin@uta.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 27 August 2014; accepted 15 September 2014; online 20 September 2014)

The title compound, C₁₁H₁₂N₆O₂, a π-conjugated triazene, crystallized with two independent molecules (A and B) in the asymmetric unit. Both molecules have an E conformation about the –N=N– bond and have slightly twisted overall conformations. In molecule A, the imidazole ring is inclined to the benzene ring by 8.12 (4)°, while in molecule B the two rings are inclined to one another by 7.73 (4)°. In the crystal, the independent molecules are linked to each other by C—H⋯O hydrogen bonds, forming –A–A–A– and –B–B–B– chains along [100]. The chains are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming sheets lying parallel to (001). The sheets are linked by further C—H⋯N hydrogen bonds and π–π interactions [centroid–centroid distance = 3.5243 (5) Å; involving the imidazole ring of molecule A and the benzene ring of molecule B], forming a three-dimensional framework structure.

Keywords: crystal structure; azides; π-conjugated triazene; N-heterocyclic carbene; hydrogen bonds; π–π interactions.

CCDC reference: 977732

1. Chemical context

Triazenes are compounds containing three contiguous nitrogen atoms in a linear format with a double bond between the first and second N atoms; i.e., –N=N—N–. The structure of the triazene moiety is influenced by the resonance arising from delocalization of the electron lone-pair on the third N atom, towards the double bond. Triazenes are relatively old compounds from the organic chemist's viewpoint. It was as early as 1862 that Griess described a suitable method for the synthesis of 1,3-diphenyltriazene (Griess, 1862 ). At that time, no applications for triazenes could be found and these compounds were ignored for many decades. Unsubstituted triazenes are unstable under normal conditions; however, substituted triazenes are normally thermally stable. More recently, attention has been paid to substituted triazenes, especially to 1-aryl-3,3-dialkyl-triazenes [which were synthesized for the first time by Baeyer & Jaeger (1875 )] because some of them show activity as insecticides (Giraldi et al., 1990 ). Currently, triazenes have found uses as alkylating agents in tumor therapy (Rouzer et al., 1996 ), as iodo-masking groups in the synthesis of small (Nicolaou et al., 1999 ) and macromolecules (Jones et al., 1997 ), and in the preparation of N-containing heterocycles (Wirshun et al., 1998 ). The first report on a π-conjugated triazenes was by Winberg et al. (1965 ), and more recently, we have reported the syntheses and structures of a variety of such π-conjugated triazenes (Patil et al., 2014 ).

2. Structural commentary

The molecular structures of the two independent molecules (A and B) of the title compound are illustrated in Fig. 1. Both molecules have an E conformation about the –N5=N4– and –N11=N10– bonds and the bond lengths and angles of the π-conjugated triazene unit (Table 1) are very similar to those in related structures (Khramov & Bielawski, 2005 , 2007 ; Jishkariani et al., 2013 ; Tennyson et al., 2010 ). The two molecules have slightly twisted overall conformations, with the imidazole ring (N1/N2/C1–C3) inclined to the benzene ring (C6–C11) by 8.12 (4)° in molecule A, while in molecule B the two rings (N7/N8/C12–C14 and C17–C22) are inclined to one another by 7.73 (4)°.

Table 1
Selected geometric parameters (Å, °)

N3—C3	1.3532 (9)	N9—C14	1.3501 (9)
N3—N4	1.3318 (8)	N9—N10	1.3299 (8)
N4—N5	1.2856 (8)	N10—N11	1.2866 (8)

N4—N3—C3	112.23 (6)	N10—N9—C14	112.44 (6)
N5—N4—N3	111.84 (6)	N11—N10—N9	111.74 (6)
N4—N5—C6	111.86 (6)	N10—N11—C17	111.77 (6)

Figure 1
A view of the molecular structure of the two independent molecules (A and B) of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal, the independent molecules are linked by C—H⋯O hydrogen bonds forming –A–A–A– and –B–B–B– chains along [100]. The chains are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming sheets lying parallel to (001); see Fig. 2 and Table 2. The sheets are linked by further C—H⋯N hydrogen bonds and C—H⋯π and π–π interactions [Cg1⋯Cg4ⁱ = 3.5243 (5) Å; Cg1 and Cg4 are the centroids of the imidazole ring of molecule A and the benzene ring of molecule B; symmetry code: (i) x, y, z − 1], forming a three-dimensional framework structure (Fig. 3 and Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

Cg2 and Cg3 are the centroids of the benzene ring (C6–C11) of molecule A and the imidazole ring (N7/N8/C12–C14) ring of molecule B, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O3ⁱ	0.95	2.55	3.3223 (11)	139
C16—H00B⋯N5ⁱⁱ	0.98	2.50	3.4757 (11)	172
C16—H00C⋯N3ⁱⁱⁱ	0.98	2.61	3.5557 (11)	163
C8—H8⋯N9^iv	0.95	2.44	3.3882 (10)	178
C13—H13⋯N3ⁱⁱ	0.95	2.60	3.5441 (10)	174
C15—H15B⋯O4^v	0.98	2.48	3.3692 (11)	151
C4—H4C⋯Cg3^vi	0.98	2.96	3.8391 (9)	150
C15—H15A⋯Cg2ⁱⁱⁱ	0.98	2.80	3.5398 (9)	132
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+2, -y+1, -z+1; (iii) x, y, z+1; (iv) -x+2, -y, -z+1; (v) x+1, y, z; (vi) $[x, -y-{\script{1\over 2}}, z-{\script{3\over 2}}]$ .

Figure 2
A view along the c axis of the crystal packing of title compound, with hydrogen bonds shown as dashed lines (see Table 2

for details).

Figure 3
A view along the a axis of the crystal packing of the title compound, with hydrogen bonds shown as dashed lines (see Table 2

for details; H atoms not involved in hydrogen bonds have been omitted for clarity).

4. Database survey

The first synthesis of a π-conjugated triazene was reported on in 1965 (Winberg & Coffman, 1965). The first X-ray structure analysis of a π-conjugated triazene appeared many years later (Khramov et al., 2005). A search of the WebCSD database, gave 15 hits for π-conjugated triazenes. Two of these structures (Patil et al., 2014) employed 1,3-dimethylimidazolium iodide as the carbene precursor. Although, there is a compound that closely resembles the title compound in the literature (Patil et al., 2014), it differs in the position of the nitro-substituent in the aromatic moiety. In the title compound, the nitro substituent is in the meta position, while the parallel report has the nitro substituent in the para position.

5. Synthesis and crystallization

1-Azido-3-nitrobenzene was prepared according to the literature procedure (Siddiki et al., 2013 ). The synthesis of 1,3-dimethylimidazolium iodide was carried out accordingly to literature procedure (Oertel et al., 2011 ). For the synthesis of the title compound, 1-azido-3-nitrobenzene (196 mg, 1.2 mmol) was added in one portion to a suspension of 1,3-dimethylimidazolium iodide (134 mg, 0.6 mmol) in dry THF (5 mL) and stirred at room temperature for 5 min. In one portion, NaH (24 mg, 0.6 mmol, 60% in mineral oil) was added to the reaction vessel and the resulting mixture was stirred at room temperature for 6 h. The yellowish-orange precipitate that formed was collected by filtration and dried under reduced pressure, giving the title compound as an orange crystalline solid (yield 140 mg, 90%). Crystals were prepared by slow infusion of hexanes into a saturated THF solution of the title compound. IR (neat) ν 3439, 1601, 1398, 1357, 1191 cm^{−1. 1}H NMR (500 MHz, DMSO-d₆): δ 7.99 (s, 1H, Ph-H), 7.85–7.83 (m, 1H, Ph-H), 7.70–7.69 (m, 1 H, Ph-H), 7.55–7.52 (m, 1H, Ph-H), 7.06 (s, 2H, NCH) 3.60 (s, 6H, N-CH₃). ¹³C NMR (125 MHz, DMSO-d₆): δ 154.4, 151.1, 149.0, 130.6, 126.9, 118.8, 118.3, 114.4, 35.7. UV/Vis (0.1 µM, CH₂Cl₂): λ (∊) = 455 nm. HRMS (ESI, N₂): m/z calculated for C₁₁H₁₃N₆O₂ [M + H]⁺ 261.1095, found 261.1094.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The C-bound H atoms were included in calculated positions and treated as riding atoms: C-H = 0.95 and 0.98 Å for CH and CH₃ H atoms, respectively, with U_iso(H) = 1.5U_eq(C) for methyl H atoms and = 1.2U_eq(C) for other H atoms.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₆O₂
M_r	260.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	103
a, b, c (Å)	14.0377 (5), 12.9071 (5), 14.2995 (5)
β (°)	113.6050 (8)
V (Å³)	2374.08 (15)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.43 × 0.33 × 0.25

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.952, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	60704, 14895, 10565
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.916

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.128, 1.03
No. of reflections	14895
No. of parameters	347
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.30
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 and SHELXL2013 (Sheldrick 2008 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 977732

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814020698/su2778sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814020698/su2778Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814020698/su2778Isup3.cml

checkCIF report

Chemical context top

Triazenes are compounds containing three contiguous nitrogen atoms in a linear format with a double bond between the first and second N atoms; i.e., –N=N—N–. The structure of the triazene moiety is influenced by the resonance arising from delocalization of the electron lone-pair on the third N atom, towards the double bond. Triazenes are relatively old compounds from the organic chemist's viewpoint. It was as early as 1862 that Griess described a suitable method for the synthesis of 1,3-diphenyltriazene (Griess, 1862). At that time, no applications for triazenes could be found and these compounds were ignored for many decades. Unsubstituted triazenes are unstable under normal conditions; however, substituted triazenes are normally thermally stable. More recently, attention has been paid to substituted triazenes, especially to 1-aryl-3,3-dialkyl-triazenes [which were synthesized for the first time by Baeyer & Jaeger (1875)] because some of them show activity as insecticides (Giraldi et al., 1990). Currently, triazenes have found uses as alkylating agents in tumor therapy (Rouzer et al., 1996), as iodo-masking groups in the synthesis of small (Nicolaou et al., 1999) and macromolecules (Jones et al., 1997), and in the preparation of N-containing heterocycles (Wirshun et al., 1998). The first report on a π-conjugated triazenes was by Winberg et al. (1965), and more recently, we have reported the syntheses and structures of a variety of such π-conjugated triazenes (Patil et al., 2014).

Structural commentary top

The molecular structures of the two independent molecules (A and B) of the title compound are illustrated in Fig. 1. Both molecules have an E conformation about the –N5═N4– and –N11═N10– bonds and the bond lengths and angles of the π-conjugated triazene unit (Table 1) are very similar to those in related structures (Khramov & Bielawski, 2005, 2007; Jishkariani et al., 2013; Tennyson et al., 2010). The two molecules have slightly twisted overall conformations, with the imidazole ring (N1/N2/C1–C3) inclined to the benzene ring (C6–C11) by 8.12 (4)° in molecule A, while in molecule B the two rings (N7/N8/C12–C14 and C17–C22) are inclined to one another by 7.73 (4)°.

Supramolecular features top

In the crystal, the independent molecules are linked by C—H···O hydrogen bonds forming –A–A–A– and –B–B–B– chains along [100]. The chains are linked by C—H···O and C—H···N hydrogen bonds, forming sheets lying parallel to (001); see Fig. 2 and Table 2. The sheets are linked by further C—H···N hydrogen bonds and C—H···π and π–π interactions [Cg1···Cg4ⁱ = 3.5243 (5) Å; Cg1 and Cg4 are the centroids of the imidazole ring of molecule A and the benzene ring of molecule B; symmetry code: (i) x, y, z-1], forming a three-dimensional framework structure (Fig. 3 and Table 2).

Database survey top

Synthesis and crystallization top

1-Azido-3-nitrobenzene was prepared according to the literature procedure (Siddiki et al., 2013). The synthesis of 1,3-dimethylimidazolium iodide was carried out accordingly to literature procedure (Oertel et al., 2011). For the synthesis of the title compound, 1-azido-3-nitrobenzene (196 mg, 1.2 mmol) was added in one portion to a suspension of 1,3-dimethylimidazolium iodide (134 mg, 0.6 mmol) in dry THF (5 mL) and stirred at room temperature for 5 min. In one portion, NaH (24 mg, 0.6 mmol, 60% in mineral oil) was added to the reaction vessel and the resulting mixture was stirred at room temperature for 6 h. The yellowish-orange precipitate that formed was collected by filtration and dried under reduced pressure, giving the title compound as an orange crystalline solid (yield 140 mg, 90%). Crystals were prepared by slow infusion of hexanes into a saturated THF solution of the title compound. IR (neat) ν 3439, 1601, 1398, 1357, 1191 cm^-1. ¹H NMR (500 MHz, DMSO-d₆): δ 7.99 (s, 1H, Ph—H), 7.85–7.83 (m, 1H, Ph—H), 7.70–7.69 (m, 1 H, Ph—H), 7.55–7.52 (m, 1H, Ph—H), 7.06 (s, 2H, NCH) 3.60 (s, 6H, N—CH₃). ¹³C NMR (125 MHz, DMSO-d₆): δ 154.4, 151.1, 149.0, 130.6, 126.9, 118.8, 118.3, 114.4, 35.7. UV/Vis (0.1 µM, CH₂Cl₂): λ (ε) = 455 nm. HRMS (ESI, N₂): m/z calculated for C₁₁H₁₃N₆O₂ [M + H]⁺ 261.1095, found 261.1094.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. The C-bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.95 and 0.98 Å for CH and CH₃ H atoms, respectively, with U_iso(H) = 1.5U_eq(C) for methyl H atoms and = 1.2U_eq(C) for other H atoms.

Related literature top

For related literature, see: Giraldi et al. (1990); Griess & Liebigs (1862); Jishkariani et al. (2013); Khramov & Bielawski (2005); Nicolaou et al. (1999); Oertel et al. (2011); Patil et al. (2014); Siddiki et al. (2013); Winberg & Coffman (1965).

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. A view of the molecular structure of the two independent molecules (A and B) of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view along the c axis of the crystal packing of title compound, with hydrogen bonds shown as dashed lines (see Table 2 for details).
	Fig. 3. A view along the a axis of the crystal packing of the title compound, with hydrogen bonds shown as dashed lines (see Table 2 for details; H atoms not involved in hydrogen bonds have been omitted for clarity).

(E)-1,3-Dimethyl-2-[3-(3-nitrophenyl)triaz-2-en-2-ylidene]-2,3-dihydro-1H-imidazole top

Crystal data top

C₁₁H₁₂N₆O₂	F(000) = 1088
M_r = 260.27	D_x = 1.456 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.0377 (5) Å	Cell parameters from 9007 reflections
b = 12.9071 (5) Å	θ = 3.1–40.1°
c = 14.2995 (5) Å	µ = 0.11 mm⁻¹
β = 113.6050 (8)°	T = 103 K
V = 2374.08 (15) Å³	Prism, orange
Z = 8	0.43 × 0.33 × 0.25 mm

Data collection top

Bruker SMART APEXII diffractometer	10565 reflections with I > 2σ(I)
ϕ and ω scans	R_int = 0.040
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 40.7°, θ_min = 2.9°
T_min = 0.952, T_max = 1.000	h = −25→25
60704 measured reflections	k = −23→23
14895 independent reflections	l = −26→26

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.060P)² + 0.4222P] where P = (F_o² + 2F_c²)/3
14895 reflections	(Δ/σ)_max = 0.001
347 parameters	Δρ_max = 0.69 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₁H₁₂N₆O₂	V = 2374.08 (15) Å³
M_r = 260.27	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.0377 (5) Å	µ = 0.11 mm⁻¹
b = 12.9071 (5) Å	T = 103 K
c = 14.2995 (5) Å	0.43 × 0.33 × 0.25 mm
β = 113.6050 (8)°

Data collection top

Bruker SMART APEXII diffractometer	14895 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2014)	10565 reflections with I > 2σ(I)
T_min = 0.952, T_max = 1.000	R_int = 0.040
60704 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.03	Δρ_max = 0.69 e Å⁻³
14895 reflections	Δρ_min = −0.30 e Å⁻³
347 parameters

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	1.41154 (5)	0.17070 (6)	0.07592 (6)	0.02761 (14)
O2	1.35616 (5)	0.32803 (5)	0.07112 (6)	0.02894 (15)
N1	0.69882 (5)	0.35407 (5)	0.09704 (5)	0.01430 (10)
N2	0.74421 (5)	0.19273 (5)	0.09668 (5)	0.01287 (10)
N3	0.86553 (5)	0.33461 (5)	0.09907 (5)	0.01281 (10)
N4	0.93463 (4)	0.26313 (5)	0.10078 (4)	0.01161 (9)
N5	1.01715 (5)	0.30405 (5)	0.09846 (5)	0.01286 (10)
N6	1.34736 (5)	0.23387 (6)	0.07898 (5)	0.01852 (12)
C1	0.64415 (5)	0.19428 (6)	0.09429 (6)	0.01542 (12)
H1	0.6029	0.1354	0.0927	0.019*
C2	0.61618 (5)	0.29407 (6)	0.09470 (6)	0.01605 (12)
H2	0.5519	0.3186	0.0936	0.019*
C3	0.77707 (5)	0.29211 (5)	0.09821 (5)	0.01153 (10)
C4	0.79822 (6)	0.09749 (6)	0.09254 (6)	0.01641 (12)
H4A	0.8149	0.0987	0.0322	0.025*
H4B	0.7535	0.0379	0.0884	0.025*
H4C	0.8626	0.0918	0.1542	0.025*
C5	0.70332 (7)	0.46623 (6)	0.09997 (8)	0.02396 (16)
H5A	0.7448	0.4892	0.1699	0.036*
H5B	0.6328	0.4943	0.0774	0.036*
H5C	0.7354	0.4910	0.0546	0.036*
C6	1.09080 (5)	0.22826 (5)	0.10102 (5)	0.01144 (10)
C7	1.08081 (6)	0.12097 (5)	0.11242 (6)	0.01449 (11)
H7	1.0200	0.0949	0.1180	0.017*
C8	1.15869 (6)	0.05259 (6)	0.11562 (6)	0.01589 (12)
H8	1.1512	−0.0194	0.1249	0.019*
C9	1.24754 (6)	0.08873 (6)	0.10535 (6)	0.01545 (12)
H9	1.3009	0.0426	0.1071	0.019*
C10	1.25535 (5)	0.19462 (6)	0.09241 (5)	0.01371 (11)
C11	1.18020 (5)	0.26503 (5)	0.09144 (5)	0.01285 (11)
H11	1.1893	0.3371	0.0844	0.015*
O3	0.37570 (6)	0.04437 (6)	0.82832 (7)	0.03536 (18)
O4	0.28471 (5)	0.17434 (6)	0.84106 (6)	0.02731 (14)
N7	1.02372 (4)	0.23808 (5)	0.84318 (5)	0.01204 (10)
N8	0.94498 (5)	0.37758 (5)	0.86112 (5)	0.01262 (10)
N9	0.86200 (5)	0.20437 (5)	0.84779 (5)	0.01280 (10)
N10	0.77639 (4)	0.25054 (5)	0.84548 (5)	0.01187 (9)
N11	0.70763 (5)	0.18431 (5)	0.84484 (5)	0.01359 (10)
N12	0.36319 (5)	0.13767 (6)	0.83579 (6)	0.01928 (12)
C12	1.08846 (5)	0.32082 (6)	0.84914 (6)	0.01436 (11)
H12	1.1547	0.3174	0.8459	0.017*
C13	1.03999 (6)	0.40748 (6)	0.86051 (6)	0.01455 (12)
H13	1.0660	0.4762	0.8669	0.017*
C14	0.93575 (5)	0.27292 (5)	0.85061 (5)	0.01114 (10)
C15	1.04585 (5)	0.12916 (6)	0.83482 (6)	0.01494 (12)
H15A	1.0610	0.0946	0.9003	0.022*
H15B	1.1061	0.1231	0.8169	0.022*
H15C	0.9854	0.0964	0.7817	0.022*
C16	0.87328 (6)	0.45063 (6)	0.87669 (7)	0.01784 (13)
H00A	0.8088	0.4537	0.8149	0.027*
H00B	0.9052	0.5195	0.8912	0.027*
H00C	0.8576	0.4277	0.9343	0.027*
C17	0.61624 (5)	0.23313 (5)	0.84061 (5)	0.01230 (11)
C18	0.59905 (6)	0.34078 (6)	0.83778 (6)	0.01640 (12)
H18	0.6516	0.3870	0.8374	0.020*
C19	0.50599 (6)	0.37999 (6)	0.83552 (7)	0.01905 (14)
H19	0.4958	0.4528	0.8338	0.023*
C20	0.42745 (6)	0.31436 (6)	0.83575 (6)	0.01717 (13)
H20	0.3641	0.3410	0.8352	0.021*
C21	0.44519 (5)	0.20858 (6)	0.83684 (6)	0.01418 (11)
C22	0.53703 (5)	0.16660 (6)	0.83938 (6)	0.01394 (11)
H22	0.5461	0.0936	0.8403	0.017*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0170 (3)	0.0305 (3)	0.0415 (4)	0.0060 (2)	0.0181 (3)	0.0032 (3)
O2	0.0208 (3)	0.0227 (3)	0.0491 (4)	−0.0023 (2)	0.0200 (3)	0.0063 (3)
N1	0.0111 (2)	0.0138 (2)	0.0193 (3)	0.00077 (18)	0.0074 (2)	−0.0021 (2)
N2	0.0114 (2)	0.0121 (2)	0.0160 (2)	−0.00117 (18)	0.00653 (19)	−0.00044 (19)
N3	0.0110 (2)	0.0111 (2)	0.0178 (3)	0.00034 (17)	0.00737 (19)	−0.00037 (19)
N4	0.0106 (2)	0.0111 (2)	0.0141 (2)	0.00008 (17)	0.00600 (18)	−0.00066 (18)
N5	0.0115 (2)	0.0108 (2)	0.0184 (3)	0.00012 (17)	0.0082 (2)	0.00033 (19)
N6	0.0117 (2)	0.0232 (3)	0.0219 (3)	0.0010 (2)	0.0081 (2)	0.0025 (2)
C1	0.0117 (3)	0.0181 (3)	0.0177 (3)	−0.0026 (2)	0.0071 (2)	−0.0003 (2)
C2	0.0112 (3)	0.0201 (3)	0.0183 (3)	−0.0011 (2)	0.0074 (2)	−0.0017 (2)
C3	0.0104 (2)	0.0118 (2)	0.0129 (3)	−0.00022 (19)	0.0053 (2)	−0.0012 (2)
C4	0.0168 (3)	0.0109 (3)	0.0226 (3)	−0.0004 (2)	0.0091 (3)	−0.0003 (2)
C5	0.0183 (3)	0.0141 (3)	0.0405 (5)	0.0018 (2)	0.0129 (3)	−0.0054 (3)
C6	0.0114 (2)	0.0105 (2)	0.0133 (3)	0.00012 (19)	0.0059 (2)	−0.0003 (2)
C7	0.0151 (3)	0.0110 (2)	0.0198 (3)	−0.0003 (2)	0.0096 (2)	−0.0001 (2)
C8	0.0169 (3)	0.0111 (3)	0.0206 (3)	0.0013 (2)	0.0085 (2)	−0.0004 (2)
C9	0.0134 (3)	0.0147 (3)	0.0181 (3)	0.0027 (2)	0.0062 (2)	−0.0014 (2)
C10	0.0104 (2)	0.0160 (3)	0.0156 (3)	0.0001 (2)	0.0061 (2)	−0.0002 (2)
C11	0.0114 (2)	0.0127 (3)	0.0154 (3)	−0.0003 (2)	0.0063 (2)	0.0004 (2)
O3	0.0258 (3)	0.0183 (3)	0.0696 (6)	−0.0036 (2)	0.0271 (4)	0.0009 (3)
O4	0.0134 (2)	0.0315 (3)	0.0412 (4)	0.0020 (2)	0.0153 (3)	0.0029 (3)
N7	0.0102 (2)	0.0114 (2)	0.0153 (2)	−0.00043 (17)	0.00589 (18)	−0.00002 (18)
N8	0.0132 (2)	0.0096 (2)	0.0164 (2)	−0.00070 (18)	0.00730 (19)	0.00062 (18)
N9	0.0106 (2)	0.0106 (2)	0.0190 (3)	−0.00018 (17)	0.00774 (19)	0.00041 (19)
N10	0.0105 (2)	0.0119 (2)	0.0140 (2)	0.00009 (17)	0.00575 (18)	0.00015 (18)
N11	0.0114 (2)	0.0120 (2)	0.0194 (3)	0.00001 (18)	0.0083 (2)	0.00108 (19)
N12	0.0125 (2)	0.0210 (3)	0.0260 (3)	−0.0008 (2)	0.0093 (2)	0.0023 (2)
C12	0.0117 (3)	0.0150 (3)	0.0172 (3)	−0.0023 (2)	0.0067 (2)	0.0013 (2)
C13	0.0139 (3)	0.0131 (3)	0.0172 (3)	−0.0029 (2)	0.0068 (2)	0.0010 (2)
C14	0.0105 (2)	0.0104 (2)	0.0130 (3)	−0.00021 (19)	0.0052 (2)	0.00045 (19)
C15	0.0134 (3)	0.0124 (3)	0.0200 (3)	0.0021 (2)	0.0077 (2)	0.0006 (2)
C16	0.0198 (3)	0.0102 (3)	0.0278 (4)	0.0011 (2)	0.0140 (3)	−0.0004 (2)
C17	0.0108 (2)	0.0124 (3)	0.0145 (3)	0.00085 (19)	0.0058 (2)	0.0005 (2)
C18	0.0150 (3)	0.0124 (3)	0.0237 (3)	0.0004 (2)	0.0098 (3)	0.0003 (2)
C19	0.0167 (3)	0.0134 (3)	0.0289 (4)	0.0030 (2)	0.0111 (3)	0.0004 (3)
C20	0.0131 (3)	0.0173 (3)	0.0222 (3)	0.0029 (2)	0.0082 (2)	0.0001 (2)
C21	0.0105 (2)	0.0157 (3)	0.0172 (3)	−0.0002 (2)	0.0064 (2)	0.0004 (2)
C22	0.0115 (2)	0.0131 (3)	0.0184 (3)	0.0006 (2)	0.0071 (2)	0.0010 (2)

Geometric parameters (Å, º) top

O1—N6	1.2288 (9)	O3—N12	1.2278 (10)
O2—N6	1.2313 (10)	O4—N12	1.2287 (9)
N1—C3	1.3534 (9)	N7—C14	1.3578 (9)
N1—C2	1.3841 (9)	N7—C12	1.3827 (9)
N1—C5	1.4489 (10)	N7—C15	1.4549 (9)
N2—C3	1.3603 (9)	N8—C14	1.3597 (9)
N2—C1	1.3914 (9)	N8—C13	1.3918 (9)
N2—C4	1.4578 (9)	N8—C16	1.4598 (9)
N3—C3	1.3532 (9)	N9—C14	1.3501 (9)
N3—N4	1.3318 (8)	N9—N10	1.3299 (8)
N4—N5	1.2856 (8)	N10—N11	1.2866 (8)
N5—C6	1.4132 (9)	N11—C17	1.4087 (9)
N6—C10	1.4699 (9)	N12—C21	1.4659 (10)
C1—C2	1.3473 (11)	C12—C13	1.3525 (10)
C1—H1	0.9500	C12—H12	0.9500
C2—H2	0.9500	C13—H13	0.9500
C4—H4A	0.9800	C15—H15A	0.9800
C4—H4B	0.9800	C15—H15B	0.9800
C4—H4C	0.9800	C15—H15C	0.9800
C5—H5A	0.9800	C16—H00A	0.9800
C5—H5B	0.9800	C16—H00B	0.9800
C5—H5C	0.9800	C16—H00C	0.9800
C6—C11	1.3987 (9)	C17—C22	1.3994 (10)
C6—C7	1.4078 (10)	C17—C18	1.4081 (10)
C7—C8	1.3916 (10)	C18—C19	1.3893 (10)
C7—H7	0.9500	C18—H18	0.9500
C8—C9	1.3934 (10)	C19—C20	1.3913 (11)
C8—H8	0.9500	C19—H19	0.9500
C9—C10	1.3893 (10)	C20—C21	1.3868 (11)
C9—H9	0.9500	C20—H20	0.9500
C10—C11	1.3884 (10)	C21—C22	1.3855 (10)
C11—H11	0.9500	C22—H22	0.9500

C3—N1—C2	109.75 (6)	C14—N7—C12	109.60 (6)
C3—N1—C5	124.35 (6)	C14—N7—C15	123.86 (6)
C2—N1—C5	125.89 (6)	C12—N7—C15	126.49 (6)
C3—N2—C1	108.62 (6)	C14—N8—C13	108.90 (6)
C3—N2—C4	128.12 (6)	C14—N8—C16	128.14 (6)
C1—N2—C4	123.19 (6)	C13—N8—C16	122.88 (6)
N4—N3—C3	112.23 (6)	N10—N9—C14	112.44 (6)
N5—N4—N3	111.84 (6)	N11—N10—N9	111.74 (6)
N4—N5—C6	111.86 (6)	N10—N11—C17	111.77 (6)
O1—N6—O2	123.36 (7)	O3—N12—O4	123.10 (7)
O1—N6—C10	118.10 (7)	O3—N12—C21	118.31 (6)
O2—N6—C10	118.54 (7)	O4—N12—C21	118.59 (7)
C2—C1—N2	107.86 (6)	C13—C12—N7	107.23 (6)
C2—C1—H1	126.1	C13—C12—H12	126.4
N2—C1—H1	126.1	N7—C12—H12	126.4
C1—C2—N1	106.98 (6)	C12—C13—N8	107.52 (6)
C1—C2—H2	126.5	C12—C13—H13	126.2
N1—C2—H2	126.5	N8—C13—H13	126.2
N1—C3—N3	119.86 (6)	N9—C14—N7	119.42 (6)
N1—C3—N2	106.78 (6)	N9—C14—N8	133.82 (6)
N3—C3—N2	133.35 (6)	N7—C14—N8	106.75 (6)
N2—C4—H4A	109.5	N7—C15—H15A	109.5
N2—C4—H4B	109.5	N7—C15—H15B	109.5
H4A—C4—H4B	109.5	H15A—C15—H15B	109.5
N2—C4—H4C	109.5	N7—C15—H15C	109.5
H4A—C4—H4C	109.5	H15A—C15—H15C	109.5
H4B—C4—H4C	109.5	H15B—C15—H15C	109.5
N1—C5—H5A	109.5	N8—C16—H00A	109.5
N1—C5—H5B	109.5	N8—C16—H00B	109.5
H5A—C5—H5B	109.5	H00A—C16—H00B	109.5
N1—C5—H5C	109.5	N8—C16—H00C	109.5
H5A—C5—H5C	109.5	H00A—C16—H00C	109.5
H5B—C5—H5C	109.5	H00B—C16—H00C	109.5
C11—C6—C7	118.69 (6)	C22—C17—C18	118.63 (6)
C11—C6—N5	115.99 (6)	C22—C17—N11	115.56 (6)
C7—C6—N5	125.31 (6)	C18—C17—N11	125.81 (6)
C8—C7—C6	120.95 (6)	C19—C18—C17	120.58 (7)
C8—C7—H7	119.5	C19—C18—H18	119.7
C6—C7—H7	119.5	C17—C18—H18	119.7
C7—C8—C9	120.58 (7)	C18—C19—C20	121.12 (7)
C7—C8—H8	119.7	C18—C19—H19	119.4
C9—C8—H8	119.7	C20—C19—H19	119.4
C10—C9—C8	117.72 (6)	C21—C20—C19	117.42 (7)
C10—C9—H9	121.1	C21—C20—H20	121.3
C8—C9—H9	121.1	C19—C20—H20	121.3
C11—C10—C9	123.03 (6)	C22—C21—C20	123.12 (7)
C11—C10—N6	118.49 (6)	C22—C21—N12	118.34 (6)
C9—C10—N6	118.48 (6)	C20—C21—N12	118.55 (6)
C10—C11—C6	119.00 (6)	C21—C22—C17	119.12 (6)
C10—C11—H11	120.5	C21—C22—H22	120.4
C6—C11—H11	120.5	C17—C22—H22	120.4

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg3 are the centroids of the benzene ring (C6–C11) of molecule A and the imidazole ring (N7/N8/C12–C14) ring of molecule B, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3ⁱ	0.95	2.55	3.3223 (11)	139
C16—H00B···N5ⁱⁱ	0.98	2.50	3.4757 (11)	172
C16—H00C···N3ⁱⁱⁱ	0.98	2.61	3.5557 (11)	163
C8—H8···N9^iv	0.95	2.44	3.3882 (10)	178
C13—H13···N3ⁱⁱ	0.95	2.60	3.5441 (10)	174
C15—H15B···O4^v	0.98	2.48	3.3692 (11)	151
C4—H4C···Cg3^vi	0.98	2.96	3.8391 (9)	150
C15—H15A···Cg2ⁱⁱⁱ	0.98	2.80	3.5398 (9)	132

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

Selected geometric parameters (Å, º) top

N3—C3	1.3532 (9)	N9—C14	1.3501 (9)
N3—N4	1.3318 (8)	N9—N10	1.3299 (8)
N4—N5	1.2856 (8)	N10—N11	1.2866 (8)

N4—N3—C3	112.23 (6)	N10—N9—C14	112.44 (6)
N5—N4—N3	111.84 (6)	N11—N10—N9	111.74 (6)
N4—N5—C6	111.86 (6)	N10—N11—C17	111.77 (6)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₆O₂
M_r	260.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	103
a, b, c (Å)	14.0377 (5), 12.9071 (5), 14.2995 (5)
β (°)	113.6050 (8)
V (Å³)	2374.08 (15)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.43 × 0.33 × 0.25

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2014)
T_min, T_max	0.952, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	60704, 14895, 10565
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.916

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.128, 1.03
No. of reflections	14895
No. of parameters	347
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.30

Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick 2008), Mercury (Macrae et al., 2008), SHELXL2013 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg3 are the centroids of the benzene ring (C6–C11) of molecule A and the imidazole ring (N7/N8/C12–C14) ring of molecule B, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3ⁱ	0.95	2.55	3.3223 (11)	139
C16—H00B···N5ⁱⁱ	0.98	2.50	3.4757 (11)	172
C16—H00C···N3ⁱⁱⁱ	0.98	2.61	3.5557 (11)	163
C8—H8···N9^iv	0.95	2.44	3.3882 (10)	178
C13—H13···N3ⁱⁱ	0.95	2.60	3.5441 (10)	174
C15—H15B···O4^v	0.98	2.48	3.3692 (11)	151
C4—H4C···Cg3^vi	0.98	2.96	3.8391 (9)	150
C15—H15A···Cg2ⁱⁱⁱ	0.98	2.80	3.5398 (9)	132

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

Acknowledgements

We thank the University of Texas at Arlington for financial support. We are grateful to Dr Muhammed Yousufuddin, Shimadzu Center, for the X-ray data collection, and to the NSF for grants (CHE-0234811 and CHE-0840509) for additional instrumentation.

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of (E)-1,3-di­methyl-2-[3-(3-nitro­phen­yl)triaz-2-en-1-yl­­idene]-2,3-di­hydro-1H-imidazole

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of (E)-1,3-dimethyl-2-[3-(3-nitrophenyl)triaz-2-en-1-ylidene]-2,3-dihydro-1H-imidazole

3. Supramolecular features