Crystal structures of 4-{(E)-3-[(imino-λ5-aza­nyl­idene)amino]­prop-1-en­yl}-N,N-di­methyl­imidazole-1-sulfonamide and 2-[(imino-λ5-aza­nyl­idene)amino]-4-{(E)-3-[(imino-λ5-aza­nyl­idene)amino]­prop-1-en­yl}-N,N-di­methyl­imidazole-1-sulfonamide

Cruz, L.M.; Moore, R.Y.; Gutierrez, M.T.; Herath, A.K.; Lovely, C.J.; Yousufuddin, M.

doi:10.1107/S205698901900519X

research communications

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ISSN: 2056-9890

Volume 75| Part 5| May 2019| Pages 695-699

https://doi.org/10.1107/S205698901900519X

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Crystal structures of 4-{(E)-3-[(imino-λ⁵-azanylidene)amino]prop-1-enyl}-N,N-dimethylimidazole-1-sulfonamide and 2-[(imino-λ⁵-azanylidene)amino]-4-{(E)-3-[(imino-λ⁵-azanylidene)amino]prop-1-enyl}-N,N-dimethylimidazole-1-sulfonamide

Lorenzo M. Cruz,^a Raakiyah Y. Moore,^a Marcela Torres Gutierrez,^a Apsara K. Herath,^b Carl J. Lovely ^b and Muhammed Yousufuddin ^a ^*

^aLife and Health Sciences Department, University of North Texas at Dallas, 7400 University Hills Blvd, Dallas, TX 75241, USA, and ^bDepartment of Chemistry and Biochemistry, University of Texas at Arlington, 700 Planetarium Pl., Arlington, TX 76019, USA
^*Correspondence e-mail: myousuf@untdallas.edu

Edited by M. Zeller, Purdue University, USA (Received 5 March 2019; accepted 15 April 2019; online 25 April 2019)

The structures of two azide containing imidazole derivatives are reported. Allylic azides are fairly reactive making them attractive starting compounds to convert into amides. The first, C₈H₁₂N₆O₂S, contains one azide group with an N_α—N_β distance of 1.229 (2) Å and an N_β—N_γ distance of 1.128 (2) Å. The second, C₈H₁₁N₉O₂S, contains two azide groups with an average N_α—N_β distance of 1.249 (2) Å and an average N_β—N_γ distance of 1.132 (2) Å. Each compound contains a bulky protecting group (dimethylaminosulfonyl) which can be easily removed under mildly acidic conditions.

Keywords: crystal structure; imidazole; nagelamide; azide; amide.

CCDC references: 1910313; 1910312

1. Chemical context

The efficient synthesis of nagelamide alkaloids (a subfamily of oroidin natural products derived from marine sponges) has garnered interest (Du et al., 2006 ; Das et al., 2016 ) since first reported (Endo et al., 2004 ). Allylic azides (Carlson & Topczewski, 2019 ) are fairly reactive making them attractive starting compounds to convert into amides. Our group has successfully synthesized a number of azide-containing imidazole derivatives and determined their structures. Many of our strategies have led to the successful synthesis of several nagelamide derivatives (Bhandari et al., 2009 ; Mukherjee et al., 2010 ). However, the application of our approaches to several other nagelamide congeners were unsuccessful, leading us to rethink our tactics. Recently, we reported the efficient synthesis of amide compounds from allylic azide-containing imidazoles (Herath et al., 2017 ). In that report we were also able to show that although the imidazoles contained dimethylaminosulfonyl (DMAS) protecting groups, efficient conversion to amides was still possible. In addition, the free imidazole (lacking the protecting group but still containing azide) underwent selective and rapid conversion to amide without the undesired hydrosulfenylation we observed with protected imidazoles. Here we present the crystal structures of two azide-containing imidazoles, 4-{(E)-3-[(imino-λ⁵-azanylidene)amino]prop-1-enyl}-N,N-dimethylimidazole-1-sulfonamide (1) and 2-[(imino-λ⁵-azanylidene)amino]-4-{(E)-3-[(imino-λ⁵-azanylidene)amino]prop-1-enyl}-N,N-dimethylimidazole-1-sulfonamide (2). These compounds were synthesized in the previous study but the structures were not reported. Figs. 1 and 2 show displacement ellipsoid plots of 1 and 2, respectively.

Figure 1
The molecular structure of compound 1, with atom labels and 50% probability displacement ellipsoids for non-H atoms.

Figure 2
The molecular structure of compound 2, with atom labels and 50% probability displacement ellipsoids for non-H atoms.

2. Structural commentary

Compound 1 contains one allylic azide while compound 2 contains two azide groups, an allylic azide and one azide bound directly to the imidazole ring at C2. The azide group in 1 shows an N3—N4 distance of 1.229 (2) Å and an N4—N5 distance of 1.128 (2) Å. The N3—N4—N5 angle is 172.32 (13)°. The azide groups in 2 show an N3—N4 distance of 1.253 (2) Å, N4—N5 distance of 1.129 (2) Å, N6—N7 distance of 1.239 (2) Å, and N7—N8 distance of 1.134 (2) Å. The N3—N4—N5 angle is 171.58 (15)° and the N6—N7—N8 angle is 173.95 (15)°. All three azide moieties in both compounds show the same general trend of a longer N_α—N_β distance and shorter N_β—N_γ distance with a quasilinear geometry. This is typical for covalent azides with terminal N_β—N_γ demonstrating more triple-bond character. A previously reported covalent azide occurring in the compound ethyl-2-[(azidocarbonyl)amino]benzoate demonstrated bond lengths N_α—N_β of 1.264 (2) Å and N_β—N_γ of 1.131 (2) Å and an N_α—N_β—N_α angle of 174.7 (2)° (Yassine et al., 2016 ).

The torsion angles for the azides and dihedral angles between the azides and imidazole rings for both compounds have been measured. The allylic azide torsion angles between 1 and 2 are quite different. The measured torsion angle for the allylic azide (C5—C6—N3—N4) in 1 was −115.21 (13)° while the related torsion angle (C5—C6—N6—N7) in 2 was 50.25 (18)°. 2 contains one azide group bound to the imidazole at C2 and shows a torsion angle N1—C2—N3—N4 of −174.82 (11)°. The allylic azides in both compounds exhibit a similar dihedral angle between the azide and the imidazole ring, 70.3 (11)° for 1 and 77.3 (17)° for 2. While the imidazole-bound azide in 2 shows a dihedral angle of 5.0 (10)°. Indeed, the torsion angle and dihedral angle for this particular azide demonstrate the near planarity between the imidazole and its covalently bound azide. Figs. 3 and 4 show the dihedral planes for 1 and 2, respectively.

Figure 3
Dihedral planes between imidazole and allylic azide for compound 1

Figure 4
Dihedral planes between imidazole and allylic azide for compound 2

Both title compounds contain a DMAS protecting group. The amine component of this protecting group is sp³-hybridized, as validated by the C—N—C bond angles C6—N6—C8 = 113.86 (10)° for 1 and C7—N9—C8 = 113.93 (12)° for 2. Both compounds also contain a double bond between C4 and C5. The measured bond distance is 1.333 (2) Å for 1 and 1.340 (2) Å for 2.

The imidazole ring in 1 is substituted at the N1 and C3 position with no substitution at C2. The N1—C2 distance is 1.378 (2) Å while the N2—C2 distance is 1.301 (2) Å. However, in 2, the imidazole ring is substituted with an azide group at C2 but this seemingly has no effect on the ring bond distances. The measured bond distances for N1—C2 and N2—C2 in 2 are 1.385 (2) and 1.310 (2) Å, respectively.

There is, however, a significant difference in the measured N1—S1 distance for the two compounds. The imidazole ring is substituted at the N1 position for both compounds with DMAS. The N1—S1 distance for 1 is 1.686 (1) Å and 1.718 (1) Å for 2. The disparity may be attributed to the presence of azide, which is substituted at the C2 position for 2.

3. Supramolecular features

The title compounds each contain bulky DMAS protecting groups and hydrogen bond distances that influence the molecule packing. Compound 1 shows C1—H1⋯O1ⁱ and C2—H2⋯O2ⁱⁱ interactions of 2.53 and 2.39 Å, respectively. There is also a C4—H4⋯N5ⁱⁱⁱ interaction of 2.70 Å (symmetry codes as in Table 1). Compound 2 demonstrates a C7—H7B⋯O1ⁱ interaction of 2.51 Å. There are also C6—H6A⋯N8ⁱⁱ and C7—H7C⋯N6ⁱⁱⁱ interactions of 2.70 and 2.62 Å, respectively (symmetry codes as in Table 2). Figs. 5 and 6 show the close contacts for 1 and 2, respectively.

Table 1
Hydrogen-bond geometry (Å, °) for 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.95	2.53	3.4487 (18)	164
C2—H2⋯O2ⁱⁱ	0.95	2.39	3.2861 (18)	157
C4—H4⋯N5ⁱⁱⁱ	0.95	2.70	3.1920 (17)	113
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+2, -y+1, -z+2; (iii) x+1, y, z.

Table 2
Hydrogen-bond geometry (Å, °) for 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O1ⁱ	0.98	2.51	3.444 (2)	160
C6—H6A⋯N8ⁱⁱ	0.99	2.70	3.337 (2)	123
C7—H7C⋯N6ⁱⁱⁱ	0.98	2.62	3.357 (2)	132
Symmetry codes: (i) -x+1, -y, -z; (ii) x+1, y, z; (iii) x-1, y, z-1.

Figure 5
Close contacts for compound 1.

Figure 6
Close contacts for compound 2.

Although both compounds contain aromatic rings, there appears to be no π-stacking present in the crystals of either compound. The stacking appears more staggered, most likely due to the presence of bulky DMAS groups on both compounds. However, the staggering in 1 appears more pronounced than in 2. In other words, the molecules are further apart in 1. This is most likely due to the larger torsion angle for the azide in 1 than in 2.

4. Database survey

A search of related compounds was conducted in the Cambridge Structural Database (Version 5.38; Groom et al., 2016 ). One very closely related compound, methyl 3-(1-(dimethylsulfamoyl)-1H-imidazol-5-yl)acrylate, was reported (Lovely et al., 2010 ). This particular compound contains an imidazole with a DMAS protecting group and an allylic ester moiety. The DMAS amine has a C—N—C angle of 114.33 (14)°, showing the same amine hybridization exhibited in 1 and 2. The C4=C5 double bond distance is measured to be 1.330 (2) Å which is similar to the bond distances in 1 and 2 [1.333 (2) and 1.340 (2) Å respectively].

The crystal structure of a related allylic azide has been reported from our previous study (Herath et al., 2017). This particular compound is a dimerized molecule with two allylic azides.

5. Synthesis and crystallization

The syntheses of the title compounds were previously reported by our group (Lovely et al., 2017). As shown in Fig. 7, the parent allylic azide 1 was prepared from the known alcohol starting compound (He et al., 2003 ) by treatment with diphenylphosphorylazide (DPPA) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) according to the procedure described previously (Thompson et al., 1993 ). Crystals were acquired by dissolving title compounds in ethanol with heating and slowly cooling in a freezer. Crystals appeared after about 1 week.

Figure 7
Synthetic scheme for both compounds. The title compounds are highlighted in red.

6. Refinement

Crystal data, data collection and structure refinement details for 1 and 2 are summarized in Table 3. Refinement for both compounds were routine. H atoms were positioned geometrically (C—H = 0.95–0.98 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.5U_eq(C) for methyl H and 1.2U_eq(C) for other H atoms.

Table 3
Experimental details

	1	2
Crystal data
Chemical formula	C₈H₁₂N₆O₂S	C₈H₁₁N₉O₂S
M_r	256.30	297.32
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	100	100
a, b, c (Å)	5.4252 (15), 9.830 (3), 11.137 (3)	6.6151 (18), 9.563 (3), 11.634 (3)
α, β, γ (°)	74.636 (5), 83.418 (5), 80.255 (5)	108.645 (4), 105.994 (4), 93.828 (4)
V (Å³)	563.0 (3)	660.6 (3)
Z	2	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.29	0.26
Crystal size (mm)	0.25 × 0.20 × 0.05	0.80 × 0.28 × 0.08

Data collection
Diffractometer	Bruker D8 Quest	Bruker D8 Quest
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )	Multi-scan (SADABS; Bruker, 2016)
T_min, T_max	0.616, 0.746	0.634, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	9314, 4292, 3477	11030, 5171, 4051
R_int	0.033	0.030
(sin θ/λ)_max (Å⁻¹)	0.774	0.780

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.104, 1.01	0.043, 0.109, 1.07
No. of reflections	4292	5171
No. of parameters	157	184
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.48	0.46, −0.60
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT2014 (Sheldrick, 2015a ), SHELXL2017 (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC references: 1910313; 1910312

Crystal structure: contains datablocks compound_1, compound_2. DOI: https://doi.org/10.1107/S205698901900519X/zl2753sup1.cif

Structure factors: contains datablock compound_1. DOI: https://doi.org/10.1107/S205698901900519X/zl2753compound_1sup2.hkl

Structure factors: contains datablock compound_2. DOI: https://doi.org/10.1107/S205698901900519X/zl2753compound_2sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901900519X/zl2753compound_1sup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S205698901900519X/zl2753compound_2sup5.cml

checkCIF report

Computing details top

For both structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

4-{(E)-3-[(Imino-λ⁵-azanylidene)amino]prop-1-enyl}-N,N-dimethylimidazole-1-sulfonamide (compound_1) top

Crystal data top

C₈H₁₂N₆O₂S	Z = 2
M_r = 256.30	F(000) = 268
Triclinic, P1	D_x = 1.512 Mg m⁻³
a = 5.4252 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.830 (3) Å	Cell parameters from 4940 reflections
c = 11.137 (3) Å	θ = 3.2–33.3°
α = 74.636 (5)°	µ = 0.29 mm⁻¹
β = 83.418 (5)°	T = 100 K
γ = 80.255 (5)°	Prism, colourless
V = 563.0 (3) Å³	0.25 × 0.20 × 0.05 mm

Data collection top

Bruker D8 Quest diffractometer	3477 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.033
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 33.4°, θ_min = 3.2°
T_min = 0.616, T_max = 0.746	h = −8→8
9314 measured reflections	k = −15→15
4292 independent reflections	l = −17→17

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.039	w = 1/[σ²(F_o²) + (0.0486P)² + 0.2224P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.104	(Δ/σ)_max = 0.001
S = 1.01	Δρ_max = 0.42 e Å⁻³
4292 reflections	Δρ_min = −0.48 e Å⁻³
157 parameters	Extinction correction: SHELXL2017 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.035 (6)
Primary atom site location: structure-invariant direct methods

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	1.02066 (5)	0.56887 (3)	0.72049 (3)	0.01267 (8)
O1	1.14077 (17)	0.54225 (11)	0.60703 (8)	0.01878 (19)
O2	1.15939 (17)	0.56915 (10)	0.82106 (8)	0.01797 (18)
N1	0.84664 (19)	0.43637 (11)	0.77979 (9)	0.01388 (19)
N2	0.6248 (2)	0.28893 (12)	0.91880 (10)	0.0177 (2)
N3	0.1658 (2)	−0.00361 (13)	0.71066 (11)	0.0199 (2)
N4	−0.0161 (2)	0.04337 (11)	0.64781 (10)	0.0164 (2)
N5	−0.1668 (2)	0.08138 (15)	0.57975 (11)	0.0256 (3)
N6	0.82889 (19)	0.71510 (11)	0.68919 (10)	0.01508 (19)
C1	0.7216 (2)	0.37309 (13)	0.71178 (11)	0.0140 (2)
H1	0.728564	0.389191	0.623584	0.017*
C2	0.7775 (3)	0.38185 (14)	0.90406 (11)	0.0176 (2)
H2	0.834333	0.408815	0.970797	0.021*
C3	0.5864 (2)	0.28275 (13)	0.79888 (11)	0.0139 (2)
C4	0.4234 (2)	0.19129 (12)	0.77555 (11)	0.0144 (2)
H4	0.407866	0.192306	0.691209	0.017*
C5	0.2939 (2)	0.10591 (13)	0.86438 (11)	0.0160 (2)
H5	0.306699	0.106802	0.948514	0.019*
C6	0.1298 (2)	0.00877 (14)	0.84143 (12)	0.0174 (2)
H6A	0.168435	−0.086933	0.898507	0.021*
H6B	−0.047919	0.045775	0.860031	0.021*
C7	0.6774 (3)	0.73822 (15)	0.58222 (13)	0.0211 (3)
H7A	0.536984	0.683286	0.607359	0.032*
H7B	0.781837	0.706956	0.513923	0.032*
H7C	0.612380	0.839831	0.554136	0.032*
C8	0.6881 (3)	0.75732 (15)	0.79801 (13)	0.0211 (3)
H8A	0.611434	0.857329	0.772839	0.032*
H8B	0.802632	0.745666	0.863140	0.032*
H8C	0.556684	0.697062	0.830419	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01100 (13)	0.01655 (14)	0.01073 (13)	−0.00187 (9)	−0.00111 (9)	−0.00383 (10)
O1	0.0157 (4)	0.0266 (5)	0.0153 (4)	−0.0035 (3)	0.0026 (3)	−0.0087 (4)
O2	0.0151 (4)	0.0247 (5)	0.0155 (4)	−0.0014 (3)	−0.0055 (3)	−0.0066 (3)
N1	0.0176 (5)	0.0138 (4)	0.0102 (4)	−0.0028 (4)	−0.0014 (3)	−0.0025 (3)
N2	0.0248 (5)	0.0166 (5)	0.0110 (4)	−0.0035 (4)	−0.0011 (4)	−0.0023 (4)
N3	0.0150 (5)	0.0256 (6)	0.0204 (5)	−0.0007 (4)	−0.0020 (4)	−0.0091 (4)
N4	0.0163 (5)	0.0170 (5)	0.0164 (5)	−0.0033 (4)	0.0022 (4)	−0.0057 (4)
N5	0.0231 (6)	0.0337 (7)	0.0202 (5)	0.0032 (5)	−0.0023 (4)	−0.0113 (5)
N6	0.0145 (4)	0.0154 (5)	0.0145 (4)	−0.0021 (4)	−0.0026 (4)	−0.0017 (4)
C1	0.0164 (5)	0.0154 (5)	0.0107 (5)	−0.0019 (4)	−0.0014 (4)	−0.0040 (4)
C2	0.0251 (6)	0.0176 (5)	0.0104 (5)	−0.0040 (5)	−0.0021 (4)	−0.0028 (4)
C3	0.0165 (5)	0.0133 (5)	0.0112 (5)	−0.0003 (4)	−0.0009 (4)	−0.0029 (4)
C4	0.0151 (5)	0.0145 (5)	0.0127 (5)	−0.0005 (4)	−0.0012 (4)	−0.0027 (4)
C5	0.0171 (5)	0.0174 (5)	0.0129 (5)	−0.0014 (4)	−0.0012 (4)	−0.0032 (4)
C6	0.0166 (5)	0.0190 (5)	0.0154 (5)	−0.0035 (4)	−0.0003 (4)	−0.0020 (4)
C7	0.0201 (6)	0.0213 (6)	0.0200 (6)	−0.0045 (5)	−0.0075 (5)	0.0014 (5)
C8	0.0207 (6)	0.0191 (6)	0.0231 (6)	0.0008 (5)	0.0013 (5)	−0.0079 (5)

Geometric parameters (Å, º) top

S1—O2	1.4200 (9)	C2—H2	0.9500
S1—O1	1.4209 (10)	C3—C4	1.4505 (17)
S1—N6	1.6067 (11)	C4—C5	1.3332 (17)
S1—N1	1.6858 (11)	C4—H4	0.9500
N1—C2	1.3783 (15)	C5—C6	1.4963 (18)
N1—C1	1.3896 (15)	C5—H5	0.9500
N2—C2	1.3012 (17)	C6—H6A	0.9900
N2—C3	1.3934 (15)	C6—H6B	0.9900
N3—N4	1.2288 (15)	C7—H7A	0.9800
N3—C6	1.4814 (17)	C7—H7B	0.9800
N4—N5	1.1277 (16)	C7—H7C	0.9800
N6—C7	1.4711 (16)	C8—H8A	0.9800
N6—C8	1.4736 (17)	C8—H8B	0.9800
C1—C3	1.3668 (16)	C8—H8C	0.9800
C1—H1	0.9500

O2—S1—O1	121.78 (6)	C5—C4—C3	124.48 (11)
O2—S1—N6	108.51 (6)	C5—C4—H4	117.8
O1—S1—N6	108.95 (6)	C3—C4—H4	117.8
O2—S1—N1	104.30 (6)	C4—C5—C6	124.87 (11)
O1—S1—N1	105.35 (5)	C4—C5—H5	117.6
N6—S1—N1	106.96 (6)	C6—C5—H5	117.6
C2—N1—C1	106.84 (10)	N3—C6—C5	111.73 (10)
C2—N1—S1	126.59 (9)	N3—C6—H6A	109.3
C1—N1—S1	126.18 (8)	C5—C6—H6A	109.3
C2—N2—C3	105.77 (10)	N3—C6—H6B	109.3
N4—N3—C6	116.05 (11)	C5—C6—H6B	109.3
N5—N4—N3	172.32 (13)	H6A—C6—H6B	107.9
C7—N6—C8	113.86 (10)	N6—C7—H7A	109.5
C7—N6—S1	116.58 (9)	N6—C7—H7B	109.5
C8—N6—S1	115.49 (9)	H7A—C7—H7B	109.5
C3—C1—N1	105.29 (10)	N6—C7—H7C	109.5
C3—C1—H1	127.4	H7A—C7—H7C	109.5
N1—C1—H1	127.4	H7B—C7—H7C	109.5
N2—C2—N1	111.73 (11)	N6—C8—H8A	109.5
N2—C2—H2	124.1	N6—C8—H8B	109.5
N1—C2—H2	124.1	H8A—C8—H8B	109.5
C1—C3—N2	110.36 (11)	N6—C8—H8C	109.5
C1—C3—C4	127.00 (11)	H8A—C8—H8C	109.5
N2—C3—C4	122.65 (11)	H8B—C8—H8C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.95	2.53	3.4487 (18)	164
C2—H2···O2ⁱⁱ	0.95	2.39	3.2861 (18)	157
C4—H4···N5ⁱⁱⁱ	0.95	2.70	3.1920 (17)	113

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

2-[(Imino-λ⁵-azanylidene)amino]-4-{(E)-3-[(imino-λ⁵-azanylidene)amino]prop-1-enyl}-N,N-dimethylimidazole-1-sulfonamide (compound_2) top

Crystal data top

C₈H₁₁N₉O₂S	Z = 2
M_r = 297.32	F(000) = 308
Triclinic, P1	D_x = 1.495 Mg m⁻³
a = 6.6151 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.563 (3) Å	Cell parameters from 5257 reflections
c = 11.634 (3) Å	θ = 3.2–33.6°
α = 108.645 (4)°	µ = 0.26 mm⁻¹
β = 105.994 (4)°	T = 100 K
γ = 93.828 (4)°	Needle, colourless
V = 660.6 (3) Å³	0.80 × 0.28 × 0.08 mm

Data collection top

Bruker D8 Quest diffractometer	4051 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.030
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 33.7°, θ_min = 3.2°
T_min = 0.634, T_max = 0.747	h = −10→10
11030 measured reflections	k = −14→14
5171 independent reflections	l = −17→18

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0401P)² + 0.3565P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.109	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.46 e Å⁻³
5171 reflections	Δρ_min = −0.60 e Å⁻³
184 parameters	Extinction correction: SHELXL2017 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.022 (3)
Primary atom site location: structure-invariant direct methods

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.58817 (5)	0.32361 (4)	0.11881 (3)	0.01478 (8)
O1	0.65163 (17)	0.18829 (12)	0.05384 (10)	0.0219 (2)
O2	0.66446 (17)	0.46415 (12)	0.11471 (10)	0.0215 (2)
N1	0.68124 (18)	0.33810 (13)	0.27604 (10)	0.0146 (2)
N2	0.75962 (17)	0.42326 (13)	0.48977 (10)	0.0144 (2)
N3	0.64496 (19)	0.59233 (13)	0.37520 (11)	0.0174 (2)
N4	0.67946 (18)	0.69635 (13)	0.48007 (11)	0.0164 (2)
N5	0.7040 (2)	0.80092 (15)	0.56596 (13)	0.0242 (3)
N6	0.8624 (2)	0.18310 (17)	0.83285 (12)	0.0237 (3)
N7	0.66897 (19)	0.15149 (14)	0.77329 (12)	0.0193 (2)
N8	0.4889 (2)	0.12679 (17)	0.72893 (15)	0.0287 (3)
N9	0.33102 (18)	0.29742 (13)	0.07962 (11)	0.0156 (2)
C1	0.7358 (2)	0.21797 (15)	0.31603 (13)	0.0156 (2)
H1	0.738643	0.119381	0.263572	0.019*
C2	0.69706 (19)	0.45659 (15)	0.38610 (12)	0.0139 (2)
C3	0.78417 (19)	0.27227 (15)	0.44638 (12)	0.0144 (2)
C4	0.8525 (2)	0.19077 (15)	0.53300 (12)	0.0156 (2)
H4	0.836577	0.084831	0.497346	0.019*
C5	0.9364 (2)	0.25679 (16)	0.66005 (13)	0.0159 (2)
H5	0.954749	0.362879	0.695491	0.019*
C6	1.0028 (2)	0.17314 (17)	0.74931 (13)	0.0181 (3)
H6A	1.152396	0.214636	0.803867	0.022*
H6B	0.996255	0.066642	0.699097	0.022*
C7	0.2306 (2)	0.15853 (17)	0.08670 (15)	0.0221 (3)
H7A	0.250179	0.171110	0.176261	0.033*
H7B	0.297367	0.074636	0.048982	0.033*
H7C	0.077775	0.137969	0.039540	0.033*
C8	0.2288 (2)	0.42873 (17)	0.12339 (15)	0.0221 (3)
H8A	0.079649	0.408488	0.069371	0.033*
H8B	0.304630	0.516510	0.117531	0.033*
H8C	0.234224	0.448176	0.212252	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01499 (14)	0.01799 (16)	0.01287 (14)	0.00388 (11)	0.00554 (11)	0.00623 (11)
O1	0.0251 (5)	0.0260 (5)	0.0168 (5)	0.0108 (4)	0.0107 (4)	0.0057 (4)
O2	0.0222 (5)	0.0242 (5)	0.0211 (5)	−0.0001 (4)	0.0076 (4)	0.0122 (4)
N1	0.0157 (5)	0.0157 (5)	0.0123 (4)	0.0037 (4)	0.0040 (4)	0.0049 (4)
N2	0.0120 (4)	0.0159 (5)	0.0151 (5)	0.0010 (4)	0.0043 (4)	0.0055 (4)
N3	0.0198 (5)	0.0148 (5)	0.0169 (5)	0.0027 (4)	0.0053 (4)	0.0052 (4)
N4	0.0130 (5)	0.0164 (5)	0.0206 (5)	0.0021 (4)	0.0064 (4)	0.0066 (4)
N5	0.0221 (6)	0.0208 (6)	0.0261 (6)	0.0026 (5)	0.0090 (5)	0.0025 (5)
N6	0.0176 (5)	0.0379 (7)	0.0179 (5)	0.0039 (5)	0.0057 (4)	0.0129 (5)
N7	0.0188 (5)	0.0212 (6)	0.0225 (6)	0.0048 (4)	0.0100 (4)	0.0105 (5)
N8	0.0185 (6)	0.0307 (7)	0.0381 (8)	0.0026 (5)	0.0097 (5)	0.0134 (6)
N9	0.0139 (5)	0.0152 (5)	0.0169 (5)	0.0026 (4)	0.0030 (4)	0.0060 (4)
C1	0.0154 (5)	0.0160 (6)	0.0160 (5)	0.0034 (4)	0.0047 (4)	0.0063 (5)
C2	0.0106 (5)	0.0148 (5)	0.0159 (5)	0.0004 (4)	0.0044 (4)	0.0051 (4)
C3	0.0107 (5)	0.0169 (6)	0.0156 (5)	0.0015 (4)	0.0037 (4)	0.0063 (5)
C4	0.0131 (5)	0.0178 (6)	0.0168 (6)	0.0032 (4)	0.0044 (4)	0.0076 (5)
C5	0.0132 (5)	0.0193 (6)	0.0167 (6)	0.0031 (4)	0.0053 (4)	0.0078 (5)
C6	0.0141 (5)	0.0254 (7)	0.0167 (6)	0.0050 (5)	0.0051 (4)	0.0093 (5)
C7	0.0192 (6)	0.0195 (7)	0.0245 (7)	−0.0017 (5)	0.0028 (5)	0.0080 (5)
C8	0.0180 (6)	0.0203 (7)	0.0251 (7)	0.0074 (5)	0.0042 (5)	0.0057 (5)

Geometric parameters (Å, º) top

S1—O2	1.4237 (11)	C1—C3	1.3707 (18)
S1—O1	1.4297 (11)	C1—H1	0.9500
S1—N9	1.6146 (12)	C3—C4	1.4579 (18)
S1—N1	1.7177 (12)	C4—C5	1.3402 (19)
N1—C2	1.3846 (17)	C4—H4	0.9500
N1—C1	1.4039 (17)	C5—C6	1.4961 (19)
N2—C2	1.3099 (17)	C5—H5	0.9500
N2—C3	1.4058 (18)	C6—H6A	0.9900
N3—N4	1.2531 (16)	C6—H6B	0.9900
N3—C2	1.4002 (18)	C7—H7A	0.9800
N4—N5	1.1291 (17)	C7—H7B	0.9800
N6—N7	1.2389 (17)	C7—H7C	0.9800
N6—C6	1.5053 (18)	C8—H8A	0.9800
N7—N8	1.1342 (18)	C8—H8B	0.9800
N9—C8	1.4792 (18)	C8—H8C	0.9800
N9—C7	1.4814 (19)

O2—S1—O1	121.70 (7)	N2—C3—C4	122.43 (12)
O2—S1—N9	109.81 (6)	C5—C4—C3	123.73 (13)
O1—S1—N9	108.59 (6)	C5—C4—H4	118.1
O2—S1—N1	106.16 (6)	C3—C4—H4	118.1
O1—S1—N1	102.88 (6)	C4—C5—C6	123.82 (13)
N9—S1—N1	106.52 (6)	C4—C5—H5	118.1
C2—N1—C1	105.71 (11)	C6—C5—H5	118.1
C2—N1—S1	129.94 (10)	C5—C6—N6	111.84 (11)
C1—N1—S1	124.00 (9)	C5—C6—H6A	109.2
C2—N2—C3	104.81 (11)	N6—C6—H6A	109.2
N4—N3—C2	114.19 (12)	C5—C6—H6B	109.2
N5—N4—N3	171.58 (15)	N6—C6—H6B	109.2
N7—N6—C6	113.91 (12)	H6A—C6—H6B	107.9
N8—N7—N6	173.95 (15)	N9—C7—H7A	109.5
C8—N9—C7	113.93 (12)	N9—C7—H7B	109.5
C8—N9—S1	117.77 (10)	H7A—C7—H7B	109.5
C7—N9—S1	115.55 (9)	N9—C7—H7C	109.5
C3—C1—N1	105.82 (11)	H7A—C7—H7C	109.5
C3—C1—H1	127.1	H7B—C7—H7C	109.5
N1—C1—H1	127.1	N9—C8—H8A	109.5
N2—C2—N1	113.05 (12)	N9—C8—H8B	109.5
N2—C2—N3	128.30 (12)	H8A—C8—H8B	109.5
N1—C2—N3	118.64 (11)	N9—C8—H8C	109.5
C1—C3—N2	110.59 (11)	H8A—C8—H8C	109.5
C1—C3—C4	126.98 (13)	H8B—C8—H8C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1ⁱ	0.98	2.51	3.444 (2)	160
C6—H6A···N8ⁱⁱ	0.99	2.70	3.337 (2)	123
C7—H7C···N6ⁱⁱⁱ	0.98	2.62	3.357 (2)	132

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

Acknowledgements

The authors thank the Center for Nanostructured Materials at the University of Texas at Arlington for the use of their diffractometer.

Funding information

Funding for this research was provided by: Robert Welch Foundation (grant No. Y-1362).

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