Molecular salts, often observed as cocrystals, play an important role in the fields of pharmaceutics and materials science, where salt formation is used to tune the properties of active pharmaceutical ingredients (APIs) and improve the stability of solid-state materials. Salt formation via a proton-transfer reaction typically alters hydrogen-bonding motifs and influences supramolecular assembly patterns. We report here the molecular salts formed by the pyridyl bis-urea macrocycle 3,5,13,15,21,22-hexaazatricyclo[15.3.1.17,11]docosa-1(21),7(22),8,10,17,19-hexaene-4,14-dione, (1), and naphthalene-1,5-disulfonic acid (H2NDS) as two salt cocrystal solvates, namely 4,14-dioxo-3,5,13,15,21,22-hexaazatricyclo[15.3.1.17,11]docosa-1(21),7(22),8,10,17,19-hexaene-21,22-diium naphthalene-1,5-disulfonate dimethyl sulfoxide disolvate, C16H20N6O22+·C10H6O6S22−·2C2H6OS, (2), and the corresponding monosolvate, C16H20N6O22+·C10H6O6S22−·C2H6OS, (3). This follows the ΔpKa rule such that there is a proton transfer from H2NDS to (1), forming the reported molecular salts through hydrogen bonding. Prior to salt formation, (1) is relatively planar and assembles into columnar structures. The salt cocrystal solvates were obtained upon slow cooling of dimethyl sulfoxide–acetonitrile solutions of the molecular components from two temperatures (363 and 393 K). The proton transfer to (1) significantly alters the conformation of the macrocycle, changing the formerly planar macrocycle into a step-shaped conformation with trans–cis urea groups in (2) or into a bowl-shape conformation with trans–trans urea groups in (3).
Supporting information
CCDC references: 1590049; 1590048
Data collection: APEX2 (Bruker, 2014) for js16; APEX2 (Bruker, 2016) for pbu_ndsa. Cell refinement: SAINT (Bruker, 2013) for js16; SAINT (Bruker, 2015) for pbu_ndsa. Data reduction: SAINT (Bruker, 2013) for js16; SAINT (Bruker, 2015) for pbu_ndsa. For both structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
4,14-Dioxo-3,5,13,15,21,22-hexaazatricyclo[15.3.1.1
7,11]docosa-1(21),7(22),8,10,17,19-hexaene-21,22-diium naphthalene-1,5-disulfonate dimethyl sulfoxide
disolvate (js16)
top
Crystal data top
C16H20N6O22+·C10H6O6S22−·2C2H6OS | Z = 1 |
Mr = 770.90 | F(000) = 404 |
Triclinic, P1 | Dx = 1.552 Mg m−3 |
a = 8.5763 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.7305 (5) Å | Cell parameters from 9898 reflections |
c = 11.4194 (5) Å | θ = 2.3–30.1° |
α = 111.379 (1)° | µ = 0.36 mm−1 |
β = 108.656 (2)° | T = 100 K |
γ = 93.040 (2)° | Prism, colourless |
V = 825.08 (7) Å3 | 0.24 × 0.08 × 0.01 mm |
Data collection top
Bruker D8 Quest diffractometer | 4807 independent reflections |
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs | 4044 reflections with I > 2σ(I) |
Mirror optics monochromator | Rint = 0.027 |
Detector resolution: 10.4 pixels mm-1 | θmax = 30.1°, θmin = 2.3° |
ω and φ scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | k = −13→13 |
Tmin = 0.474, Tmax = 0.493 | l = −16→16 |
24789 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0424P)2 + 0.5072P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
4807 reflections | Δρmax = 0.61 e Å−3 |
240 parameters | Δρmin = −0.41 e Å−3 |
0 restraints | |
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. |
Refinement. X-ray intensity data from a colorless triclinic prism were collected at 100 (2) K
using a Bruker D8 QUEST diffractometer equipped with a PHOTON 100 CMOS area
detector and an Incoatec microfocus source. The raw area detector data frames
were reduced and corrected for absorption effects using the SAINT+ and
SADABS programs. Final unit-cell parameters were determined by
least-squares refinement of 9898 reflections taken from the data set. The
structure was solved by direct methods with SHELXT. Subsequent
difference Fourier calculations and full-matrix least-squares refinement
against F2 were performed with SHELXL2014 using OLEX2. The compound
crystallizes in the triclinic system. The space group P-1 (No. 2) was
confirmed by structure solution. The asymmetric unit consists of half of one
C16H20N6O22+ cationic cycle, half of one naphthalene-1,5- disulfonate
(C10H6O6S22-) anion and one DMSO molecule. The cycle and
naphthalene-1,5-disulfonate species are located on crystallographic inversion
centers. All non-hydrogen atoms were refined with anisotropic displacement
parameters. Hydrogen atoms bonded to carbon were located in Fourier difference
maps before being placed in geometrically idealized positions included as
riding atoms with d(C—H) = 0.95 A and Uiso(H) = 1.2Ueq(C) for
aromatic hydrogen atoms, d(C—H) = 0.99 A and Uiso(H) = 1.2Ueq(C)
for methylene hydrogen atoms and d(C—H) = 0.98 A and Uiso(H) =
1.5Ueq(C) for methyl H atoms. The methyl H atoms were allowed to rotate as a
rigid group to the orientation of maximum observed electron density. Hydrogen
atoms bonded to nitrogen were located in difference maps and refined freely.
The largest residual electron density peak in the final difference map is 0.61
e-/A3, located 0.71 A from S1. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.81427 (12) | 0.36129 (11) | 0.38362 (10) | 0.01500 (19) | |
N1 | 0.87827 (14) | 0.49577 (13) | 0.60781 (11) | 0.0133 (2) | |
H1 | 0.965 (2) | 0.541 (2) | 0.6072 (18) | 0.020 (4)* | |
N2 | 0.65295 (14) | 0.29424 (13) | 0.48400 (12) | 0.0142 (2) | |
H2 | 0.631 (3) | 0.310 (2) | 0.555 (2) | 0.029 (5)* | |
N3 | 0.33561 (14) | 0.32659 (12) | 0.29475 (12) | 0.0118 (2) | |
H3 | 0.331 (3) | 0.343 (2) | 0.373 (2) | 0.035 (6)* | |
C1 | 0.78352 (16) | 0.38224 (14) | 0.48736 (13) | 0.0126 (2) | |
C2 | 0.54392 (16) | 0.17607 (15) | 0.35676 (13) | 0.0141 (2) | |
H2A | 0.4676 | 0.1133 | 0.3748 | 0.017* | |
H2B | 0.6133 | 0.1109 | 0.3154 | 0.017* | |
C3 | 0.44048 (16) | 0.23444 (14) | 0.25748 (13) | 0.0122 (2) | |
C4 | 0.44811 (17) | 0.19913 (15) | 0.13154 (14) | 0.0149 (3) | |
H4 | 0.5195 | 0.1339 | 0.1030 | 0.018* | |
C5 | 0.35117 (17) | 0.25905 (15) | 0.04628 (14) | 0.0164 (3) | |
H5 | 0.3561 | 0.2347 | −0.0408 | 0.020* | |
C6 | 0.24735 (17) | 0.35428 (15) | 0.08812 (14) | 0.0155 (3) | |
H6 | 0.1815 | 0.3965 | 0.0306 | 0.019* | |
C7 | 0.24068 (16) | 0.38719 (14) | 0.21494 (13) | 0.0125 (2) | |
C8 | 0.12751 (17) | 0.48889 (15) | 0.26287 (13) | 0.0144 (2) | |
H8A | 0.1651 | 0.5899 | 0.2687 | 0.017* | |
H8B | 0.0124 | 0.4498 | 0.1944 | 0.017* | |
S1 | 0.26651 (4) | 0.79161 (4) | 0.12772 (3) | 0.01500 (8) | |
O2 | 0.17885 (14) | 0.64608 (12) | 0.02100 (11) | 0.0253 (2) | |
O3 | 0.30892 (14) | 0.79425 (12) | 0.26315 (11) | 0.0223 (2) | |
O4 | 0.40943 (13) | 0.85619 (12) | 0.10967 (11) | 0.0199 (2) | |
C9 | 0.12016 (16) | 0.91552 (15) | 0.11696 (14) | 0.0142 (2) | |
C10 | 0.06926 (18) | 0.97755 (16) | 0.22374 (14) | 0.0172 (3) | |
H10 | 0.1103 | 0.9526 | 0.2997 | 0.021* | |
C11 | −0.04363 (18) | 1.07833 (16) | 0.22237 (14) | 0.0174 (3) | |
H11 | −0.0765 | 1.1215 | 0.2978 | 0.021* | |
C12 | −0.10551 (17) | 1.11383 (15) | 0.11345 (14) | 0.0155 (3) | |
H12 | −0.1813 | 1.1816 | 0.1137 | 0.019* | |
C13 | 0.05774 (16) | 0.94970 (14) | 0.00090 (13) | 0.0130 (2) | |
S2 | 0.23117 (4) | 0.30337 (4) | 0.59884 (4) | 0.01831 (9) | |
O5 | 0.36314 (14) | 0.33789 (13) | 0.54692 (11) | 0.0224 (2) | |
C14 | 0.2593 (2) | 0.12976 (18) | 0.61615 (18) | 0.0294 (4) | |
H14A | 0.2327 | 0.0488 | 0.5268 | 0.044* | |
H14B | 0.1847 | 0.1067 | 0.6587 | 0.044* | |
H14C | 0.3760 | 0.1388 | 0.6725 | 0.044* | |
C15 | 0.3084 (2) | 0.42181 (18) | 0.77460 (15) | 0.0249 (3) | |
H15A | 0.4208 | 0.4065 | 0.8179 | 0.037* | |
H15B | 0.2331 | 0.3969 | 0.8160 | 0.037* | |
H15C | 0.3136 | 0.5272 | 0.7866 | 0.037* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0130 (5) | 0.0175 (5) | 0.0149 (4) | 0.0026 (4) | 0.0074 (4) | 0.0051 (4) |
N1 | 0.0114 (5) | 0.0149 (5) | 0.0143 (5) | 0.0022 (4) | 0.0066 (4) | 0.0050 (4) |
N2 | 0.0133 (5) | 0.0167 (5) | 0.0129 (5) | 0.0018 (4) | 0.0060 (4) | 0.0053 (4) |
N3 | 0.0122 (5) | 0.0119 (5) | 0.0136 (5) | 0.0026 (4) | 0.0072 (4) | 0.0054 (4) |
C1 | 0.0105 (6) | 0.0131 (6) | 0.0161 (6) | 0.0057 (4) | 0.0063 (5) | 0.0061 (5) |
C2 | 0.0134 (6) | 0.0127 (6) | 0.0166 (6) | 0.0032 (5) | 0.0056 (5) | 0.0060 (5) |
C3 | 0.0103 (6) | 0.0097 (5) | 0.0164 (6) | 0.0008 (4) | 0.0055 (5) | 0.0045 (5) |
C4 | 0.0138 (6) | 0.0134 (6) | 0.0173 (6) | 0.0025 (5) | 0.0080 (5) | 0.0039 (5) |
C5 | 0.0171 (6) | 0.0184 (6) | 0.0155 (6) | 0.0023 (5) | 0.0094 (5) | 0.0061 (5) |
C6 | 0.0151 (6) | 0.0177 (6) | 0.0167 (6) | 0.0039 (5) | 0.0069 (5) | 0.0090 (5) |
C7 | 0.0109 (6) | 0.0120 (6) | 0.0154 (6) | 0.0016 (4) | 0.0059 (5) | 0.0056 (5) |
C8 | 0.0144 (6) | 0.0164 (6) | 0.0148 (6) | 0.0057 (5) | 0.0072 (5) | 0.0070 (5) |
S1 | 0.01379 (16) | 0.01361 (15) | 0.01839 (17) | 0.00426 (11) | 0.00511 (12) | 0.00773 (13) |
O2 | 0.0254 (6) | 0.0132 (5) | 0.0276 (6) | 0.0039 (4) | 0.0005 (5) | 0.0054 (4) |
O3 | 0.0213 (5) | 0.0270 (6) | 0.0227 (5) | 0.0066 (4) | 0.0067 (4) | 0.0155 (5) |
O4 | 0.0160 (5) | 0.0232 (5) | 0.0233 (5) | 0.0066 (4) | 0.0096 (4) | 0.0099 (4) |
C9 | 0.0123 (6) | 0.0129 (6) | 0.0179 (6) | 0.0017 (5) | 0.0061 (5) | 0.0064 (5) |
C10 | 0.0184 (7) | 0.0180 (6) | 0.0165 (6) | 0.0026 (5) | 0.0080 (5) | 0.0073 (5) |
C11 | 0.0197 (7) | 0.0176 (6) | 0.0162 (6) | 0.0028 (5) | 0.0110 (5) | 0.0046 (5) |
C12 | 0.0152 (6) | 0.0137 (6) | 0.0185 (6) | 0.0025 (5) | 0.0092 (5) | 0.0049 (5) |
C13 | 0.0114 (6) | 0.0108 (5) | 0.0162 (6) | 0.0003 (4) | 0.0053 (5) | 0.0050 (5) |
S2 | 0.01513 (17) | 0.02561 (18) | 0.01969 (17) | 0.00682 (13) | 0.00699 (13) | 0.01418 (14) |
O5 | 0.0223 (5) | 0.0352 (6) | 0.0233 (5) | 0.0148 (5) | 0.0155 (4) | 0.0191 (5) |
C14 | 0.0322 (9) | 0.0221 (7) | 0.0281 (8) | 0.0005 (6) | 0.0007 (7) | 0.0131 (7) |
C15 | 0.0345 (9) | 0.0268 (8) | 0.0210 (7) | 0.0112 (6) | 0.0155 (7) | 0.0127 (6) |
Geometric parameters (Å, º) top
O1—C1 | 1.2426 (16) | S1—O2 | 1.4486 (11) |
N1—H1 | 0.845 (19) | S1—O3 | 1.4611 (11) |
N1—C1 | 1.3618 (17) | S1—O4 | 1.4540 (11) |
N1—C8i | 1.4465 (17) | S1—C9 | 1.7928 (14) |
N2—H2 | 0.85 (2) | C9—C10 | 1.3688 (19) |
N2—C1 | 1.3548 (17) | C9—C13 | 1.4282 (19) |
N2—C2 | 1.4514 (17) | C10—H10 | 0.9500 |
N3—H3 | 0.86 (2) | C10—C11 | 1.415 (2) |
N3—C3 | 1.3587 (16) | C11—H11 | 0.9500 |
N3—C7 | 1.3451 (17) | C11—C12 | 1.363 (2) |
C2—H2A | 0.9900 | C12—H12 | 0.9500 |
C2—H2B | 0.9900 | C12—C13ii | 1.4269 (18) |
C2—C3 | 1.5081 (18) | C13—C12ii | 1.4268 (18) |
C3—C4 | 1.3759 (18) | C13—C13ii | 1.430 (3) |
C4—H4 | 0.9500 | S2—O5 | 1.5098 (11) |
C4—C5 | 1.388 (2) | S2—C14 | 1.7909 (17) |
C5—H5 | 0.9500 | S2—C15 | 1.7825 (16) |
C5—C6 | 1.3844 (19) | C14—H14A | 0.9800 |
C6—H6 | 0.9500 | C14—H14B | 0.9800 |
C6—C7 | 1.3857 (18) | C14—H14C | 0.9800 |
C7—C8 | 1.5059 (18) | C15—H15A | 0.9800 |
C8—N1i | 1.4465 (17) | C15—H15B | 0.9800 |
C8—H8A | 0.9900 | C15—H15C | 0.9800 |
C8—H8B | 0.9900 | | |
| | | |
C1—N1—H1 | 114.3 (12) | H8A—C8—H8B | 107.5 |
C1—N1—C8i | 124.68 (11) | O2—S1—O3 | 113.47 (7) |
C8i—N1—H1 | 117.9 (12) | O2—S1—O4 | 113.56 (7) |
C1—N2—H2 | 120.7 (14) | O2—S1—C9 | 105.79 (6) |
C1—N2—C2 | 119.73 (11) | O3—S1—C9 | 105.06 (6) |
C2—N2—H2 | 119.5 (14) | O4—S1—O3 | 112.28 (6) |
C3—N3—H3 | 116.2 (14) | O4—S1—C9 | 105.75 (6) |
C7—N3—H3 | 120.8 (14) | C10—C9—S1 | 118.14 (11) |
C7—N3—C3 | 122.99 (12) | C10—C9—C13 | 120.40 (13) |
O1—C1—N1 | 121.17 (12) | C13—C9—S1 | 121.46 (10) |
O1—C1—N2 | 121.08 (12) | C9—C10—H10 | 119.6 |
N2—C1—N1 | 117.74 (12) | C9—C10—C11 | 120.82 (13) |
N2—C2—H2A | 108.9 | C11—C10—H10 | 119.6 |
N2—C2—H2B | 108.9 | C10—C11—H11 | 119.8 |
N2—C2—C3 | 113.47 (11) | C12—C11—C10 | 120.40 (13) |
H2A—C2—H2B | 107.7 | C12—C11—H11 | 119.8 |
C3—C2—H2A | 108.9 | C11—C12—H12 | 119.6 |
C3—C2—H2B | 108.9 | C11—C12—C13ii | 120.72 (13) |
N3—C3—C2 | 118.29 (11) | C13ii—C12—H12 | 119.6 |
N3—C3—C4 | 118.70 (12) | C9—C13—C13ii | 118.69 (15) |
C4—C3—C2 | 123.01 (12) | C12ii—C13—C9 | 122.36 (12) |
C3—C4—H4 | 120.1 | C12ii—C13—C13ii | 118.95 (15) |
C3—C4—C5 | 119.83 (12) | O5—S2—C14 | 105.65 (8) |
C5—C4—H4 | 120.1 | O5—S2—C15 | 105.79 (7) |
C4—C5—H5 | 120.0 | C15—S2—C14 | 97.01 (8) |
C6—C5—C4 | 120.00 (13) | S2—C14—H14A | 109.5 |
C6—C5—H5 | 120.0 | S2—C14—H14B | 109.5 |
C5—C6—H6 | 120.4 | S2—C14—H14C | 109.5 |
C5—C6—C7 | 119.13 (13) | H14A—C14—H14B | 109.5 |
C7—C6—H6 | 120.4 | H14A—C14—H14C | 109.5 |
N3—C7—C6 | 119.34 (12) | H14B—C14—H14C | 109.5 |
N3—C7—C8 | 120.20 (12) | S2—C15—H15A | 109.5 |
C6—C7—C8 | 120.46 (12) | S2—C15—H15B | 109.5 |
N1i—C8—C7 | 114.95 (11) | S2—C15—H15C | 109.5 |
N1i—C8—H8A | 108.5 | H15A—C15—H15B | 109.5 |
N1i—C8—H8B | 108.5 | H15A—C15—H15C | 109.5 |
C7—C8—H8A | 108.5 | H15B—C15—H15C | 109.5 |
C7—C8—H8B | 108.5 | | |
| | | |
N2—C2—C3—N3 | −58.65 (15) | C8i—N1—C1—O1 | −167.63 (12) |
N2—C2—C3—C4 | 121.07 (13) | C8i—N1—C1—N2 | 13.35 (19) |
N3—C3—C4—C5 | 0.78 (19) | S1—C9—C10—C11 | 178.84 (11) |
N3—C7—C8—N1i | −4.48 (18) | S1—C9—C13—C12ii | 0.98 (18) |
C1—N2—C2—C3 | −67.51 (15) | S1—C9—C13—C13ii | −179.52 (12) |
C2—N2—C1—O1 | −1.74 (19) | O2—S1—C9—C10 | 116.33 (12) |
C2—N2—C1—N1 | 177.28 (11) | O2—S1—C9—C13 | −63.79 (12) |
C2—C3—C4—C5 | −178.94 (12) | O3—S1—C9—C10 | −3.98 (13) |
C3—N3—C7—C6 | 0.62 (19) | O3—S1—C9—C13 | 175.90 (11) |
C3—N3—C7—C8 | −179.80 (12) | O4—S1—C9—C10 | −122.92 (11) |
C3—C4—C5—C6 | 0.1 (2) | O4—S1—C9—C13 | 56.96 (12) |
C4—C5—C6—C7 | −0.7 (2) | C9—C10—C11—C12 | 0.9 (2) |
C5—C6—C7—N3 | 0.31 (19) | C10—C9—C13—C12ii | −179.15 (12) |
C5—C6—C7—C8 | −179.27 (12) | C10—C9—C13—C13ii | 0.4 (2) |
C6—C7—C8—N1i | 175.10 (12) | C10—C11—C12—C13ii | 0.0 (2) |
C7—N3—C3—C2 | 178.57 (11) | C13—C9—C10—C11 | −1.0 (2) |
C7—N3—C3—C4 | −1.16 (19) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1iii | 0.845 (19) | 2.029 (19) | 2.8712 (15) | 174.4 (18) |
N2—H2···O3i | 0.85 (2) | 2.55 (2) | 3.2286 (16) | 136.9 (17) |
N2—H2···O5 | 0.85 (2) | 2.30 (2) | 2.8118 (15) | 118.4 (16) |
N3—H3···O5 | 0.86 (2) | 1.94 (2) | 2.7733 (15) | 163 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (iii) −x+2, −y+1, −z+1. |
4,14-Dioxo-3,5,13,15,21,22-hexaazatricyclo[15.3.1.1
7,11]docosa-1(21),7(22),8,10,17,19-hexaene-21,22-diium naphthalene-1,5-disulfonate dimethyl sulfoxide
monosolvate (pbu_ndsa)
top
Crystal data top
C16H20N6O22+·C10H6O6S22−·C2H6OS | F(000) = 1448 |
Mr = 692.77 | Dx = 1.537 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9076 (4) Å | Cell parameters from 9930 reflections |
b = 25.5878 (11) Å | θ = 2.6–27.1° |
c = 13.6411 (6) Å | µ = 0.31 mm−1 |
β = 105.644 (2)° | T = 200 K |
V = 2994.0 (2) Å3 | Wedge, colourless |
Z = 4 | 0.22 × 0.18 × 0.14 mm |
Data collection top
Bruker D8 Quest diffractometer | 6634 independent reflections |
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs | 5142 reflections with I > 2σ(I) |
Mirror optics monochromator | Rint = 0.065 |
Detector resolution: 10.4 pixels mm-1 | θmax = 27.2°, θmin = 2.2° |
ω and φ scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −32→32 |
Tmin = 0.773, Tmax = 0.862 | l = −17→17 |
52398 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.031P)2 + 2.4238P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.091 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.48 e Å−3 |
6634 reflections | Δρmin = −0.38 e Å−3 |
442 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00059 (16) |
Primary atom site location: dual | |
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. |
Refinement. Crystals formed as clusters of colorless wedge-shaped crystals from which
individual single crystals were cleaved apart. The crystals visibly fractured
when placed in to the diffractometer cold stream at 100 K. Crystal integrity
was maintained upon flash-cooling the crystals to 200 K, at which temperature
data were collected. The temperature at which the material undergoes the
crystallinity-destroying transition is not known. X-ray intensities were
measured using a Bruker D8 QUEST diffractometer equipped with a PHOTON-100
CMOS area detector and an Incoatec microfocus source. The raw area detector
data frames were reduced and corrected for absorption effects using the Bruker
APEX3, SAINT+ and SADABS programs. Final unit-cell
parameters were determined by least-squares refinement of 9930 reflections
taken from the data set. The structure was solved with SHELXT.
Subsequent difference Fourier calculations and full-matrix least-squares
refinement against F2 were performed with SHELXL2017 using OLEX2. The
compound crystallizes in the monoclinic system. The pattern of systematic
absences in the intensity data was consistent with the space group P21/n,
which was confirmed by structure solution. The asymmetric unit consists of one
complete C16H20N6O22+ cation, half each of two C10H6O6S22- anions and one
C2H6SO molecule. Both C10H6O6S2- anions are located on crystallographic
inversion centers. All non-hydrogen atoms were refined with anisotropic
displacement parameters. Hydrogen atoms bonded to carbon were located in
Fourier difference maps before being placed in geometrically idealized
positions and included as riding atoms with d(C—H) = 0.95 A and
Uiso(H) = 1.2Ueq(C) for aromatic hydrogen atoms, d(C—H) = 0.99 A
and Uiso(H) = 1.2Ueq(C) for methylene hydrogen atoms, and d(C—H) =
0.98 A and Uiso(H) = 1.5Ueq(C) for methyl H atoms. The methyl H atoms
were allowed to rotate as a rigid group to the orientation of maximum observed
electron density. The six unique hydrogen atoms bonded to nitrogen were
located in difference maps and refined freely. The largest residual electron
density peak in the final difference map is 0.48 e-/A3, located 1.01 A from
C31. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 1.14704 (16) | 0.25475 (5) | 0.70006 (10) | 0.0273 (3) | |
O2 | 0.82446 (15) | 0.26036 (5) | 0.45086 (10) | 0.0256 (3) | |
N1 | 1.21232 (19) | 0.30250 (6) | 0.57785 (13) | 0.0212 (3) | |
H1 | 1.238 (3) | 0.3032 (8) | 0.5243 (17) | 0.028 (6)* | |
N2 | 1.19305 (19) | 0.21318 (6) | 0.56434 (13) | 0.0226 (4) | |
H2 | 1.221 (2) | 0.2161 (8) | 0.5102 (17) | 0.025 (6)* | |
N3 | 0.91563 (19) | 0.16183 (7) | 0.54030 (13) | 0.0237 (4) | |
H3 | 0.933 (3) | 0.1873 (10) | 0.504 (2) | 0.049 (8)* | |
N4 | 0.5996 (2) | 0.22025 (7) | 0.45905 (14) | 0.0286 (4) | |
H4 | 0.503 (3) | 0.2252 (9) | 0.4459 (17) | 0.029 (6)* | |
N5 | 0.6093 (2) | 0.30934 (7) | 0.44549 (14) | 0.0282 (4) | |
H5 | 0.514 (3) | 0.3082 (9) | 0.4360 (17) | 0.034 (7)* | |
N6 | 0.94343 (19) | 0.35932 (6) | 0.54606 (12) | 0.0211 (3) | |
H6 | 0.964 (3) | 0.3389 (10) | 0.5023 (19) | 0.044 (7)* | |
C1 | 1.1812 (2) | 0.25681 (7) | 0.61904 (14) | 0.0195 (4) | |
C2 | 1.1972 (2) | 0.16280 (8) | 0.61198 (17) | 0.0281 (5) | |
H2A | 1.259225 | 0.165529 | 0.683883 | 0.034* | |
H2B | 1.250608 | 0.137706 | 0.577551 | 0.034* | |
C3 | 1.0381 (2) | 0.14171 (7) | 0.60884 (15) | 0.0235 (4) | |
C4 | 1.0135 (3) | 0.10070 (8) | 0.66869 (16) | 0.0290 (5) | |
H4A | 1.098668 | 0.085426 | 0.717742 | 0.035* | |
C5 | 0.8647 (3) | 0.08225 (8) | 0.65656 (17) | 0.0337 (5) | |
H5A | 0.846330 | 0.054757 | 0.698707 | 0.040* | |
C6 | 0.7413 (3) | 0.10366 (8) | 0.58300 (18) | 0.0329 (5) | |
H6A | 0.638657 | 0.090607 | 0.574075 | 0.040* | |
C7 | 0.7680 (2) | 0.14402 (8) | 0.52272 (16) | 0.0251 (4) | |
C8 | 0.6491 (2) | 0.16846 (8) | 0.43619 (17) | 0.0310 (5) | |
H8A | 0.692762 | 0.171052 | 0.376875 | 0.037* | |
H8B | 0.556644 | 0.145360 | 0.416819 | 0.037* | |
C9 | 0.6855 (2) | 0.26322 (8) | 0.44995 (14) | 0.0231 (4) | |
C10 | 0.6830 (2) | 0.35805 (8) | 0.43099 (15) | 0.0271 (4) | |
H10A | 0.601659 | 0.384945 | 0.406448 | 0.032* | |
H10B | 0.738882 | 0.353188 | 0.377984 | 0.032* | |
C11 | 0.7959 (2) | 0.37701 (7) | 0.52699 (14) | 0.0208 (4) | |
C12 | 0.7602 (2) | 0.41029 (7) | 0.59634 (16) | 0.0255 (4) | |
H12 | 0.656879 | 0.422994 | 0.585732 | 0.031* | |
C13 | 0.8754 (2) | 0.42522 (8) | 0.68170 (16) | 0.0274 (5) | |
H13 | 0.851748 | 0.448637 | 0.729485 | 0.033* | |
C14 | 1.0251 (2) | 0.40604 (7) | 0.69742 (15) | 0.0240 (4) | |
H14 | 1.104408 | 0.416125 | 0.756181 | 0.029* | |
C15 | 1.0592 (2) | 0.37229 (7) | 0.62777 (14) | 0.0196 (4) | |
C16 | 1.2181 (2) | 0.35027 (7) | 0.63490 (15) | 0.0242 (4) | |
H16A | 1.279837 | 0.376516 | 0.609174 | 0.029* | |
H16B | 1.272132 | 0.343475 | 0.707272 | 0.029* | |
S2 | 1.15740 (6) | 0.41264 (2) | 0.36116 (4) | 0.02325 (12) | |
O21 | 1.05263 (18) | 0.37030 (5) | 0.37035 (11) | 0.0328 (4) | |
O22 | 1.31909 (18) | 0.39627 (6) | 0.38710 (12) | 0.0382 (4) | |
O23 | 1.10614 (18) | 0.44032 (6) | 0.26547 (11) | 0.0336 (4) | |
C22 | 1.1460 (2) | 0.45892 (7) | 0.45807 (14) | 0.0194 (4) | |
C23 | 1.2790 (2) | 0.47002 (7) | 0.53217 (15) | 0.0237 (4) | |
H23 | 1.374949 | 0.454786 | 0.529151 | 0.028* | |
C24 | 1.2759 (2) | 0.50382 (7) | 0.61314 (15) | 0.0237 (4) | |
H24 | 1.369049 | 0.510569 | 0.664993 | 0.028* | |
C25 | 1.1399 (2) | 0.52691 (7) | 0.61752 (14) | 0.0206 (4) | |
H25 | 1.139256 | 0.549598 | 0.672537 | 0.025* | |
C26 | 1.0011 (2) | 0.48255 (7) | 0.45930 (14) | 0.0175 (4) | |
S1 | 1.12368 (6) | 0.09233 (2) | 0.35432 (4) | 0.02462 (12) | |
O11 | 1.00857 (19) | 0.13071 (6) | 0.36473 (12) | 0.0376 (4) | |
O12 | 1.27974 (18) | 0.11384 (6) | 0.37669 (12) | 0.0389 (4) | |
O13 | 1.07702 (18) | 0.06376 (6) | 0.25914 (11) | 0.0340 (4) | |
C17 | 1.1310 (2) | 0.04509 (7) | 0.45248 (14) | 0.0201 (4) | |
C18 | 1.2702 (2) | 0.03665 (7) | 0.52257 (15) | 0.0249 (4) | |
H18 | 1.360905 | 0.054272 | 0.516046 | 0.030* | |
C19 | 1.2810 (2) | 0.00201 (8) | 0.60465 (16) | 0.0266 (4) | |
H19 | 1.378235 | −0.002963 | 0.653788 | 0.032* | |
C20 | 1.1522 (2) | −0.02439 (7) | 0.61374 (15) | 0.0230 (4) | |
H20 | 1.160684 | −0.047438 | 0.669570 | 0.028* | |
C21 | 0.9939 (2) | 0.01790 (7) | 0.45889 (13) | 0.0181 (4) | |
S3 | 0.22270 (6) | 0.27338 (2) | 0.28689 (4) | 0.02191 (12) | |
O31 | 0.29552 (15) | 0.26400 (5) | 0.40013 (10) | 0.0222 (3) | |
C31 | 0.2914 (3) | 0.22068 (9) | 0.22520 (16) | 0.0334 (5) | |
H31A | 0.401887 | 0.226088 | 0.229323 | 0.050* | |
H31B | 0.231253 | 0.219256 | 0.153597 | 0.050* | |
H31C | 0.278957 | 0.187732 | 0.258780 | 0.050* | |
C32 | 0.0268 (2) | 0.25268 (9) | 0.26502 (17) | 0.0325 (5) | |
H32A | 0.024549 | 0.216790 | 0.289677 | 0.049* | |
H32B | −0.024938 | 0.253971 | 0.191908 | 0.049* | |
H32C | −0.027564 | 0.275804 | 0.301371 | 0.049* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0262 (8) | 0.0349 (8) | 0.0232 (7) | 0.0004 (6) | 0.0105 (6) | 0.0017 (6) |
O2 | 0.0157 (7) | 0.0343 (8) | 0.0264 (7) | −0.0012 (6) | 0.0047 (6) | −0.0016 (6) |
N1 | 0.0225 (9) | 0.0208 (8) | 0.0217 (9) | 0.0030 (6) | 0.0081 (7) | 0.0010 (7) |
N2 | 0.0236 (9) | 0.0218 (8) | 0.0229 (9) | −0.0023 (7) | 0.0071 (7) | −0.0014 (7) |
N3 | 0.0241 (9) | 0.0248 (9) | 0.0224 (9) | −0.0058 (7) | 0.0067 (7) | −0.0009 (7) |
N4 | 0.0145 (9) | 0.0362 (10) | 0.0338 (10) | −0.0034 (7) | 0.0042 (8) | −0.0010 (8) |
N5 | 0.0129 (9) | 0.0369 (10) | 0.0332 (10) | −0.0004 (7) | 0.0035 (7) | −0.0024 (8) |
N6 | 0.0208 (8) | 0.0229 (8) | 0.0195 (9) | 0.0036 (7) | 0.0053 (7) | 0.0001 (7) |
C1 | 0.0118 (9) | 0.0254 (10) | 0.0199 (10) | 0.0004 (7) | 0.0019 (7) | 0.0005 (7) |
C2 | 0.0244 (11) | 0.0219 (10) | 0.0349 (12) | −0.0021 (8) | 0.0024 (9) | 0.0010 (8) |
C3 | 0.0267 (11) | 0.0209 (9) | 0.0223 (10) | −0.0013 (8) | 0.0054 (8) | −0.0046 (8) |
C4 | 0.0390 (13) | 0.0239 (10) | 0.0264 (11) | 0.0022 (9) | 0.0130 (9) | −0.0011 (8) |
C5 | 0.0447 (14) | 0.0254 (11) | 0.0397 (13) | −0.0003 (10) | 0.0266 (11) | 0.0016 (9) |
C6 | 0.0329 (12) | 0.0292 (11) | 0.0443 (13) | −0.0084 (9) | 0.0236 (11) | −0.0075 (10) |
C7 | 0.0227 (10) | 0.0260 (10) | 0.0290 (11) | −0.0063 (8) | 0.0112 (8) | −0.0095 (8) |
C8 | 0.0222 (11) | 0.0361 (12) | 0.0325 (12) | −0.0091 (9) | 0.0035 (9) | −0.0073 (9) |
C9 | 0.0171 (10) | 0.0363 (11) | 0.0142 (9) | −0.0011 (8) | 0.0012 (7) | −0.0025 (8) |
C10 | 0.0198 (10) | 0.0350 (11) | 0.0245 (11) | 0.0049 (8) | 0.0029 (8) | 0.0050 (8) |
C11 | 0.0174 (9) | 0.0216 (9) | 0.0244 (10) | 0.0024 (7) | 0.0073 (8) | 0.0066 (8) |
C12 | 0.0225 (10) | 0.0225 (10) | 0.0356 (12) | 0.0026 (8) | 0.0149 (9) | 0.0051 (8) |
C13 | 0.0351 (12) | 0.0205 (10) | 0.0323 (12) | −0.0021 (8) | 0.0189 (10) | −0.0038 (8) |
C14 | 0.0285 (11) | 0.0203 (9) | 0.0231 (10) | −0.0042 (8) | 0.0064 (8) | −0.0015 (8) |
C15 | 0.0202 (10) | 0.0171 (9) | 0.0207 (10) | −0.0013 (7) | 0.0042 (8) | 0.0025 (7) |
C16 | 0.0194 (10) | 0.0215 (10) | 0.0283 (11) | 0.0013 (8) | 0.0007 (8) | −0.0014 (8) |
S2 | 0.0278 (3) | 0.0196 (2) | 0.0266 (3) | 0.00356 (19) | 0.0147 (2) | −0.00263 (19) |
O21 | 0.0459 (9) | 0.0216 (7) | 0.0386 (9) | −0.0057 (7) | 0.0245 (7) | −0.0083 (6) |
O22 | 0.0314 (9) | 0.0393 (9) | 0.0464 (10) | 0.0119 (7) | 0.0148 (7) | −0.0107 (7) |
O23 | 0.0452 (9) | 0.0344 (8) | 0.0270 (8) | 0.0073 (7) | 0.0196 (7) | 0.0032 (6) |
C22 | 0.0231 (10) | 0.0141 (8) | 0.0228 (10) | 0.0014 (7) | 0.0090 (8) | 0.0011 (7) |
C23 | 0.0212 (10) | 0.0189 (9) | 0.0318 (11) | 0.0047 (8) | 0.0089 (9) | 0.0022 (8) |
C24 | 0.0208 (10) | 0.0205 (9) | 0.0270 (11) | −0.0007 (8) | 0.0016 (8) | 0.0004 (8) |
C25 | 0.0241 (10) | 0.0165 (9) | 0.0215 (10) | 0.0002 (7) | 0.0068 (8) | −0.0001 (7) |
C26 | 0.0210 (10) | 0.0127 (8) | 0.0201 (10) | 0.0002 (7) | 0.0079 (8) | 0.0029 (7) |
S1 | 0.0303 (3) | 0.0232 (2) | 0.0222 (3) | −0.0048 (2) | 0.0103 (2) | 0.00447 (19) |
O11 | 0.0530 (10) | 0.0253 (8) | 0.0387 (9) | 0.0093 (7) | 0.0196 (8) | 0.0107 (7) |
O12 | 0.0385 (9) | 0.0396 (9) | 0.0382 (9) | −0.0182 (7) | 0.0097 (7) | 0.0092 (7) |
O13 | 0.0386 (9) | 0.0431 (9) | 0.0238 (8) | −0.0107 (7) | 0.0144 (7) | −0.0022 (6) |
C17 | 0.0243 (10) | 0.0162 (9) | 0.0214 (10) | −0.0011 (7) | 0.0086 (8) | 0.0006 (7) |
C18 | 0.0223 (10) | 0.0218 (10) | 0.0311 (11) | −0.0054 (8) | 0.0082 (9) | 0.0006 (8) |
C19 | 0.0203 (10) | 0.0273 (10) | 0.0285 (11) | 0.0006 (8) | 0.0000 (8) | 0.0035 (8) |
C20 | 0.0256 (11) | 0.0208 (9) | 0.0212 (10) | 0.0020 (8) | 0.0041 (8) | 0.0057 (7) |
C21 | 0.0227 (10) | 0.0145 (8) | 0.0180 (9) | 0.0002 (7) | 0.0071 (8) | −0.0008 (7) |
S3 | 0.0214 (2) | 0.0215 (2) | 0.0217 (2) | −0.00154 (19) | 0.00384 (19) | 0.00153 (18) |
O31 | 0.0168 (7) | 0.0297 (7) | 0.0193 (7) | 0.0008 (5) | 0.0032 (5) | −0.0016 (5) |
C31 | 0.0376 (13) | 0.0402 (13) | 0.0249 (11) | 0.0056 (10) | 0.0128 (10) | −0.0030 (9) |
C32 | 0.0192 (11) | 0.0386 (12) | 0.0351 (12) | 0.0003 (9) | −0.0008 (9) | −0.0035 (10) |
Geometric parameters (Å, º) top
O1—C1 | 1.224 (2) | C14—H14 | 0.9500 |
O2—C9 | 1.236 (2) | C14—C15 | 1.377 (3) |
N1—H1 | 0.82 (2) | C15—C16 | 1.503 (3) |
N1—C1 | 1.358 (2) | C16—H16A | 0.9900 |
N1—C16 | 1.442 (2) | C16—H16B | 0.9900 |
N2—H2 | 0.84 (2) | S2—O21 | 1.4573 (15) |
N2—C1 | 1.363 (2) | S2—O22 | 1.4492 (15) |
N2—C2 | 1.440 (2) | S2—O23 | 1.4467 (15) |
N3—H3 | 0.86 (3) | S2—C22 | 1.7979 (19) |
N3—C3 | 1.334 (3) | C22—C23 | 1.364 (3) |
N3—C7 | 1.350 (2) | C22—C26 | 1.429 (3) |
N4—H4 | 0.84 (2) | C23—H23 | 0.9500 |
N4—C8 | 1.457 (3) | C23—C24 | 1.409 (3) |
N4—C9 | 1.364 (3) | C24—H24 | 0.9500 |
N5—H5 | 0.83 (2) | C24—C25 | 1.363 (3) |
N5—C9 | 1.354 (3) | C25—H25 | 0.9500 |
N5—C10 | 1.447 (3) | C25—C26i | 1.423 (3) |
N6—H6 | 0.85 (3) | C26—C26i | 1.429 (4) |
N6—C11 | 1.347 (2) | S1—O11 | 1.4540 (16) |
N6—C15 | 1.340 (2) | S1—O12 | 1.4490 (15) |
C2—H2A | 0.9900 | S1—O13 | 1.4500 (15) |
C2—H2B | 0.9900 | S1—C17 | 1.7920 (19) |
C2—C3 | 1.506 (3) | C17—C18 | 1.364 (3) |
C3—C4 | 1.383 (3) | C17—C21 | 1.429 (3) |
C4—H4A | 0.9500 | C18—H18 | 0.9500 |
C4—C5 | 1.375 (3) | C18—C19 | 1.411 (3) |
C5—H5A | 0.9500 | C19—H19 | 0.9500 |
C5—C6 | 1.386 (3) | C19—C20 | 1.365 (3) |
C6—H6A | 0.9500 | C20—H20 | 0.9500 |
C6—C7 | 1.380 (3) | C20—C21ii | 1.417 (3) |
C7—C8 | 1.494 (3) | C21—C21ii | 1.429 (3) |
C8—H8A | 0.9900 | S3—O31 | 1.5245 (14) |
C8—H8B | 0.9900 | S3—C31 | 1.783 (2) |
C10—H10A | 0.9900 | S3—C32 | 1.770 (2) |
C10—H10B | 0.9900 | C31—H31A | 0.9800 |
C10—C11 | 1.500 (3) | C31—H31B | 0.9800 |
C11—C12 | 1.372 (3) | C31—H31C | 0.9800 |
C12—H12 | 0.9500 | C32—H32A | 0.9800 |
C12—C13 | 1.382 (3) | C32—H32B | 0.9800 |
C13—H13 | 0.9500 | C32—H32C | 0.9800 |
C13—C14 | 1.383 (3) | | |
| | | |
C1—N1—H1 | 121.5 (16) | C15—C14—H14 | 120.1 |
C1—N1—C16 | 119.22 (17) | N6—C15—C14 | 117.78 (18) |
C16—N1—H1 | 118.9 (16) | N6—C15—C16 | 117.47 (16) |
C1—N2—H2 | 119.4 (15) | C14—C15—C16 | 124.72 (17) |
C1—N2—C2 | 118.86 (17) | N1—C16—C15 | 112.74 (16) |
C2—N2—H2 | 119.8 (15) | N1—C16—H16A | 109.0 |
C3—N3—H3 | 117.0 (18) | N1—C16—H16B | 109.0 |
C3—N3—C7 | 124.55 (18) | C15—C16—H16A | 109.0 |
C7—N3—H3 | 118.4 (18) | C15—C16—H16B | 109.0 |
C8—N4—H4 | 116.2 (15) | H16A—C16—H16B | 107.8 |
C9—N4—H4 | 115.4 (16) | O21—S2—C22 | 105.18 (8) |
C9—N4—C8 | 120.26 (17) | O22—S2—O21 | 112.42 (9) |
C9—N5—H5 | 117.4 (17) | O22—S2—C22 | 105.10 (9) |
C9—N5—C10 | 121.09 (17) | O23—S2—O21 | 112.83 (10) |
C10—N5—H5 | 119.6 (17) | O23—S2—O22 | 114.39 (9) |
C11—N6—H6 | 117.2 (17) | O23—S2—C22 | 105.92 (8) |
C15—N6—H6 | 118.1 (17) | C23—C22—S2 | 118.15 (14) |
C15—N6—C11 | 124.68 (17) | C23—C22—C26 | 120.66 (17) |
O1—C1—N1 | 122.61 (18) | C26—C22—S2 | 121.18 (14) |
O1—C1—N2 | 122.27 (18) | C22—C23—H23 | 119.6 |
N1—C1—N2 | 115.11 (17) | C22—C23—C24 | 120.76 (18) |
N2—C2—H2A | 108.9 | C24—C23—H23 | 119.6 |
N2—C2—H2B | 108.9 | C23—C24—H24 | 119.8 |
N2—C2—C3 | 113.50 (17) | C25—C24—C23 | 120.41 (18) |
H2A—C2—H2B | 107.7 | C25—C24—H24 | 119.8 |
C3—C2—H2A | 108.9 | C24—C25—H25 | 119.6 |
C3—C2—H2B | 108.9 | C24—C25—C26i | 120.82 (17) |
N3—C3—C2 | 117.84 (17) | C26i—C25—H25 | 119.6 |
N3—C3—C4 | 118.49 (19) | C22—C26—C26i | 118.4 (2) |
C4—C3—C2 | 123.55 (19) | C25i—C26—C22 | 122.67 (16) |
C3—C4—H4A | 120.3 | C25i—C26—C26i | 118.9 (2) |
C5—C4—C3 | 119.4 (2) | O11—S1—C17 | 105.48 (9) |
C5—C4—H4A | 120.3 | O12—S1—O11 | 112.62 (10) |
C4—C5—H5A | 119.9 | O12—S1—O13 | 114.03 (9) |
C4—C5—C6 | 120.1 (2) | O12—S1—C17 | 105.04 (9) |
C6—C5—H5A | 119.9 | O13—S1—O11 | 112.87 (10) |
C5—C6—H6A | 120.1 | O13—S1—C17 | 105.83 (9) |
C7—C6—C5 | 119.8 (2) | C18—C17—S1 | 118.25 (14) |
C7—C6—H6A | 120.1 | C18—C17—C21 | 120.73 (17) |
N3—C7—C6 | 117.6 (2) | C21—C17—S1 | 121.00 (14) |
N3—C7—C8 | 116.61 (18) | C17—C18—H18 | 119.7 |
C6—C7—C8 | 125.76 (19) | C17—C18—C19 | 120.68 (18) |
N4—C8—C7 | 113.76 (17) | C19—C18—H18 | 119.7 |
N4—C8—H8A | 108.8 | C18—C19—H19 | 119.9 |
N4—C8—H8B | 108.8 | C20—C19—C18 | 120.25 (18) |
C7—C8—H8A | 108.8 | C20—C19—H19 | 119.9 |
C7—C8—H8B | 108.8 | C19—C20—H20 | 119.5 |
H8A—C8—H8B | 107.7 | C19—C20—C21ii | 120.94 (18) |
O2—C9—N4 | 122.41 (19) | C21ii—C20—H20 | 119.5 |
O2—C9—N5 | 122.69 (19) | C17—C21—C21ii | 118.3 (2) |
N5—C9—N4 | 114.80 (18) | C20ii—C21—C17 | 122.63 (17) |
N5—C10—H10A | 109.1 | C20ii—C21—C21ii | 119.0 (2) |
N5—C10—H10B | 109.1 | O31—S3—C31 | 104.63 (9) |
N5—C10—C11 | 112.41 (16) | O31—S3—C32 | 104.74 (9) |
H10A—C10—H10B | 107.9 | C32—S3—C31 | 98.19 (11) |
C11—C10—H10A | 109.1 | S3—C31—H31A | 109.5 |
C11—C10—H10B | 109.1 | S3—C31—H31B | 109.5 |
N6—C11—C10 | 116.68 (17) | S3—C31—H31C | 109.5 |
N6—C11—C12 | 118.07 (18) | H31A—C31—H31B | 109.5 |
C12—C11—C10 | 125.25 (18) | H31A—C31—H31C | 109.5 |
C11—C12—H12 | 120.2 | H31B—C31—H31C | 109.5 |
C11—C12—C13 | 119.68 (18) | S3—C32—H32A | 109.5 |
C13—C12—H12 | 120.2 | S3—C32—H32B | 109.5 |
C12—C13—H13 | 120.1 | S3—C32—H32C | 109.5 |
C12—C13—C14 | 119.89 (18) | H32A—C32—H32B | 109.5 |
C14—C13—H13 | 120.1 | H32A—C32—H32C | 109.5 |
C13—C14—H14 | 120.1 | H32B—C32—H32C | 109.5 |
C15—C14—C13 | 119.89 (19) | | |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O31iii | 0.82 (2) | 2.15 (2) | 2.892 (2) | 151 (2) |
N2—H2···O31iii | 0.84 (2) | 2.18 (2) | 2.940 (2) | 151 (2) |
N3—H3···O2 | 0.86 (3) | 2.14 (3) | 2.823 (2) | 136 (2) |
N3—H3···O11 | 0.86 (3) | 2.62 (3) | 2.851 (2) | 96.8 (19) |
N4—H4···O31 | 0.84 (2) | 2.04 (2) | 2.839 (2) | 158 (2) |
N5—H5···O31 | 0.83 (2) | 2.19 (2) | 2.934 (2) | 150 (2) |
N6—H6···O2 | 0.85 (3) | 2.37 (3) | 2.912 (2) | 122 (2) |
N6—H6···O21 | 0.85 (3) | 2.30 (3) | 2.833 (2) | 121 (2) |
Symmetry code: (iii) x+1, y, z. |
Geometrical data for hydrogen bonding in DMSO-solvated salts (2) and
(3) topMolecular salt | D—H···A | D—H | H···A | D···A | D—H···A |
(2) | N1—H1···O1i | 0.845 (19) | 2.029 (19) | 2.8712 (15) | 174.4 (18) |
| N2—H2···O3ii | 0.85 (2) | 2.55 (2) | 3.2286 (16) | 136.9 (17) |
| N3—H3···O5 | 0.86 (2) | 1.94 (2) | 2.7733 (15) | 163.0 (2) |
(3) | N1—H1···O31iii | 0.82 (2) | 2.15 (2) | 2.892 (2) | 151.0 (2) |
| N2—H2···O31iii | 0.84 (2) | 2.18 (2) | 2.940 (2) | 151.0 (2) |
| N3—H3···O2 | 0.86 (3) | 2.14 (3) | 2.823 (2) | 136.0 (2) |
| N3—H3···O11 | 0.86 (3) | 2.62 (3) | 2.851 (2) | 96.8 (19) |
| N4—H4···O31 | 0.84 (2) | 2.04 (2) | 2.839 (2) | 158.0 (2) |
| N5—H5···O31 | 0.83 (2) | 2.19 (2) | 2.934 (2) | 150.0 (2) |
| N6—H6···O2 | 0.85 (3) | 2.37 (3) | 2.912 (2) | 122.0 (2) |
| N6—H6···O21 | 0.85 (3) | 2.30 (3) | 2.833 (2) | 121.0 (2) |
Symmetry codes: (i) -x+2, -y+1, -z+1;
(ii) -x+1, -y+1, -z+1;
(iii) x+1, y, z. |