research communications
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
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
The structures of two azide containing imidazole derivatives are reported. Allylic 8H12N6O2S, contains one azide group with an Nα—Nβ distance of 1.229 (2) Å and an Nβ—Nγ distance of 1.128 (2) Å. The second, C8H11N9O2S, contains two azide groups with an average Nα—Nβ distance of 1.249 (2) Å and an average Nβ—Nγ distance of 1.132 (2) Å. Each compound contains a bulky protecting group (dimethylaminosulfonyl) which can be easily removed under mildly acidic conditions.
are fairly reactive making them attractive starting compounds to convert into The first, CKeywords: crystal structure; imidazole; nagelamide; azide; amide.
1. Chemical context
The efficient synthesis of nagelamide et al., 2006; Das et al., 2016) since first reported (Endo et al., 2004). Allylic (Carlson & Topczewski, 2019) are fairly reactive making them attractive starting compounds to convert into 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 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.
(a subfamily of oroidin natural products derived from marine sponges) has garnered interest (Du2. 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 Nα—Nβ distance and shorter Nβ—Nγ distance with a quasilinear geometry. This is typical for covalent with terminal Nβ—Nγ demonstrating more triple-bond character. A previously reported covalent azide occurring in the compound ethyl-2-[(azidocarbonyl)amino]benzoate demonstrated bond lengths Nα—Nβ of 1.264 (2) Å and Nβ—Nγ of 1.131 (2) Å and an Nα—Nβ—Nα angle of 174.7 (2)° (Yassine et al., 2016).
The torsion angles for the 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 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.
and dihedral angles between the and imidazole rings for both compounds have been measured. The allylic azide torsion angles betweenBoth 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.
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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 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 et al., 2017). This particular compound is a dimerized molecule with two allylic azides.
of a related allylic azide has been reported from our previous study (Herath5. 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.
6. Refinement
Crystal data, data collection and structure 1 and 2 are summarized in Table 3. 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 Uiso(H) = 1.5Ueq(C) for methyl H and 1.2Ueq(C) for other H atoms.
details for
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Supporting information
https://doi.org/10.1107/S205698901900519X/zl2753sup1.cif
contains datablocks compound_1, compound_2. DOI: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
For both structures, data collection: APEX3 (Bruker, 2016); cell
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).C8H12N6O2S | Z = 2 |
Mr = 256.30 | F(000) = 268 |
Triclinic, P1 | Dx = 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 |
Bruker D8 Quest diffractometer | 3477 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.033 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 33.4°, θmin = 3.2° |
Tmin = 0.616, Tmax = 0.746 | h = −8→8 |
9314 measured reflections | k = −15→15 |
4292 independent reflections | l = −17→17 |
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(Fo2) + (0.0486P)2 + 0.2224P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.104 | (Δ/σ)max = 0.001 |
S = 1.01 | Δρmax = 0.42 e Å−3 |
4292 reflections | Δρmin = −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 |
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 | ||
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* |
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) |
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 |
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. |
C8H11N9O2S | Z = 2 |
Mr = 297.32 | F(000) = 308 |
Triclinic, P1 | Dx = 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 |
Bruker D8 Quest diffractometer | 4051 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.030 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 33.7°, θmin = 3.2° |
Tmin = 0.634, Tmax = 0.747 | h = −10→10 |
11030 measured reflections | k = −14→14 |
5171 independent reflections | l = −17→18 |
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(Fo2) + (0.0401P)2 + 0.3565P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.109 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.46 e Å−3 |
5171 reflections | Δρmin = −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 |
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 | ||
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* |
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) |
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 |
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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