In the crystal structure of
O,
O′-diethyl
N-(2,4,6-trimethylphenyl)thiophosphate, C
13H
22NO
2PS, two symmetrically independent thiophosphoramide molecules are linked through N—H
S and N—H
π hydrogen bonds to form a noncentrosymmetric dimer, with
Z′ = 2. The strengths of the hydrogen bonds were evaluated using density functional theory (DFT) at the M06-2X level within the 6-311++G(d,p) basis set, and by considering the quantum theory of atoms in molecules (QTAIM). It was found that the N—H
S hydrogen bond is slightly stronger than the N—H
π hydrogen bond. This is reflected in differences between the calculated N—H stretching frequencies of the isolated molecules and the frequencies of the same N—H units involved in the different hydrogen bonds of the hydrogen-bonded dimer. For these hydrogen bonds, the corresponding charge transfers,
i.e. lp (or π)→σ*, were studied, according to the second-order perturbation theory in natural bond orbital (NBO) methodology. Hirshfeld surface analysis was applied for a detailed investigation of all the contacts participating in the crystal packing.
Supporting information
CCDC reference: 1435273
Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OlexSys (Dolomanov et al., 2009).
O,
O'-Diethyl
N-(2,4,6-trimethylphenyl)thiophosphate
top
Crystal data top
C13H22NO2PS | Z = 2 |
Mr = 287.34 | F(000) = 308 |
Triclinic, P1 | Dx = 1.249 Mg m−3 |
a = 8.4954 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.6790 (3) Å | Cell parameters from 7603 reflections |
c = 10.7105 (4) Å | θ = 4.2–32.1° |
α = 100.366 (3)° | µ = 0.31 mm−1 |
β = 100.314 (3)° | T = 100 K |
γ = 90.093 (3)° | Bulk, light-yellow |
V = 763.79 (5) Å3 | 0.24 × 0.20 × 0.18 mm |
Data collection top
Agilent Xcalibur Sapphire3 Gemini diffractometer | 6232 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 6048 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 8.0151 pixels mm-1 | θmax = 26.4°, θmin = 3.4° |
ω scans | h = −10→10 |
Absorption correction: multi-scan CrysAlis PRO (Agilent, 2014) | k = −10→10 |
Tmin = 0.951, Tmax = 1 | l = −13→13 |
11026 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)] = 0.036 | w = 1/[σ2(Fo2) + (0.0551P)2 + 0.0309P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.089 | (Δ/σ)max < 0.001 |
S = 1.08 | Δρmax = 0.46 e Å−3 |
6232 reflections | Δρmin = −0.23 e Å−3 |
343 parameters | Absolute structure: Flack x determined using 2825 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
4 restraints | Absolute structure parameter: −0.01 (3) |
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 | Uiso*/Ueq | |
P1 | 0.14947 (9) | 0.99042 (9) | 0.62404 (7) | 0.01530 (18) | |
N1 | 0.1966 (3) | 0.8614 (3) | 0.5069 (3) | 0.0167 (6) | |
H1 | 0.164 (5) | 0.868 (5) | 0.431 (4) | 0.018 (10)* | |
C13 | 0.4854 (4) | 1.2492 (5) | 0.8604 (4) | 0.0288 (8) | |
H13A | 0.4981 | 1.3116 | 0.9477 | 0.043* | |
H13B | 0.4936 | 1.3183 | 0.7987 | 0.043* | |
H13C | 0.5696 | 1.1722 | 0.8573 | 0.043* | |
C22 | 0.6994 (4) | 0.5844 (4) | 0.2253 (3) | 0.0191 (7) | |
H22A | 0.6396 | 0.6607 | 0.2757 | 0.029* | |
H22B | 0.6911 | 0.6077 | 0.1382 | 0.029* | |
H22C | 0.8121 | 0.5903 | 0.2674 | 0.029* | |
O22 | 0.3949 (3) | 0.6375 (3) | 0.0305 (2) | 0.0197 (5) | |
C20 | 0.2344 (4) | 0.2108 (4) | 0.2171 (4) | 0.0238 (7) | |
H20A | 0.2279 | 0.1264 | 0.2657 | 0.036* | |
H20B | 0.1717 | 0.1800 | 0.1298 | 0.036* | |
H20C | 0.1915 | 0.3062 | 0.2608 | 0.036* | |
C18 | 0.7295 (4) | 0.2944 (4) | 0.2108 (3) | 0.0182 (7) | |
H18 | 0.8403 | 0.3122 | 0.2125 | 0.022* | |
C4 | 0.5190 (4) | 0.4918 (4) | 0.5428 (3) | 0.0175 (7) | |
C21 | 0.7858 (5) | 0.0071 (4) | 0.1993 (4) | 0.0252 (7) | |
H21A | 0.7251 | −0.0915 | 0.1615 | 0.038* | |
H21B | 0.8396 | 0.0024 | 0.2874 | 0.038* | |
H21C | 0.8659 | 0.0231 | 0.1470 | 0.038* | |
O21 | 0.1648 (3) | 0.4639 (3) | 0.0032 (2) | 0.0190 (5) | |
C17 | 0.6729 (4) | 0.1415 (4) | 0.2025 (3) | 0.0192 (7) | |
C16 | 0.5109 (4) | 0.1184 (4) | 0.2009 (3) | 0.0190 (7) | |
H16 | 0.4697 | 0.0147 | 0.1939 | 0.023* | |
C7 | 0.5290 (4) | 0.9175 (4) | 0.4958 (4) | 0.0245 (7) | |
H7A | 0.4549 | 0.9526 | 0.4261 | 0.037* | |
H7B | 0.6350 | 0.9049 | 0.4720 | 0.037* | |
H7C | 0.5367 | 0.9956 | 0.5753 | 0.037* | |
C15 | 0.4067 (4) | 0.2416 (4) | 0.2091 (3) | 0.0171 (6) | |
C14 | 0.4670 (4) | 0.3938 (3) | 0.2143 (3) | 0.0130 (6) | |
C1 | 0.3059 (4) | 0.7368 (4) | 0.5213 (3) | 0.0143 (6) | |
C19 | 0.6307 (4) | 0.4218 (4) | 0.2168 (3) | 0.0155 (6) | |
C12 | 0.3254 (5) | 1.1660 (5) | 0.8262 (4) | 0.0293 (8) | |
H12A | 0.3109 | 1.1056 | 0.8937 | 0.035* | |
H12B | 0.2396 | 1.2427 | 0.8198 | 0.035* | |
O12 | 0.0974 (3) | 0.8995 (3) | 0.7271 (2) | 0.0198 (5) | |
C24 | 0.4938 (4) | 0.7597 (5) | −0.1237 (4) | 0.0289 (8) | |
H24A | 0.4663 | 0.7936 | −0.2071 | 0.043* | |
H24B | 0.5761 | 0.6809 | −0.1281 | 0.043* | |
H24C | 0.5347 | 0.8501 | −0.0565 | 0.043* | |
C11 | −0.1083 (6) | 0.9680 (6) | 0.8518 (5) | 0.0474 (12) | |
H11A | −0.2174 | 0.9406 | 0.8600 | 0.071* | |
H11B | −0.1012 | 1.0789 | 0.8454 | 0.071* | |
H11C | −0.0329 | 0.9491 | 0.9277 | 0.071* | |
O11 | 0.3174 (3) | 1.0607 (3) | 0.7029 (2) | 0.0207 (5) | |
C23 | 0.3481 (4) | 0.6905 (5) | −0.0921 (4) | 0.0289 (8) | |
H23A | 0.2652 | 0.7699 | −0.0851 | 0.035* | |
H23B | 0.3037 | 0.6011 | −0.1608 | 0.035* | |
C10 | −0.0677 (4) | 0.8696 (5) | 0.7332 (4) | 0.0285 (8) | |
H10A | −0.0853 | 0.7573 | 0.7351 | 0.034* | |
H10B | −0.1378 | 0.8946 | 0.6557 | 0.034* | |
C26 | −0.1018 (5) | 0.4715 (6) | −0.1138 (5) | 0.0456 (12) | |
H26A | −0.2135 | 0.4384 | −0.1192 | 0.068* | |
H26B | −0.0638 | 0.4212 | −0.1918 | 0.068* | |
H26C | −0.0942 | 0.5856 | −0.1061 | 0.068* | |
C9 | 0.0744 (4) | 0.5551 (4) | 0.5284 (4) | 0.0262 (8) | |
H9A | 0.0100 | 0.6313 | 0.4863 | 0.039* | |
H9B | 0.0545 | 0.5624 | 0.6166 | 0.039* | |
H9C | 0.0449 | 0.4491 | 0.4797 | 0.039* | |
C25 | −0.0015 (4) | 0.4248 (4) | 0.0014 (4) | 0.0250 (8) | |
H25A | −0.0347 | 0.4806 | 0.0811 | 0.030* | |
H25B | −0.0155 | 0.3107 | −0.0022 | 0.030* | |
C8 | 0.6333 (4) | 0.3602 (4) | 0.5484 (3) | 0.0223 (7) | |
H8A | 0.6016 | 0.2908 | 0.6031 | 0.033* | |
H8B | 0.7419 | 0.4034 | 0.5848 | 0.033* | |
H8C | 0.6309 | 0.3006 | 0.4612 | 0.033* | |
C6 | 0.2492 (4) | 0.5895 (4) | 0.5325 (3) | 0.0178 (6) | |
C5 | 0.3580 (4) | 0.4701 (4) | 0.5444 (3) | 0.0180 (6) | |
H5 | 0.3201 | 0.3706 | 0.5540 | 0.022* | |
N2 | 0.3620 (3) | 0.5236 (3) | 0.2257 (2) | 0.0146 (5) | |
H2 | 0.357 (5) | 0.568 (5) | 0.301 (3) | 0.026 (11)* | |
P2 | 0.26274 (9) | 0.59936 (8) | 0.10798 (7) | 0.01365 (17) | |
C2 | 0.4682 (4) | 0.7628 (4) | 0.5174 (3) | 0.0158 (6) | |
S2 | 0.13503 (10) | 0.77150 (9) | 0.16919 (8) | 0.0229 (2) | |
S1 | −0.00294 (11) | 1.13550 (10) | 0.56163 (9) | 0.0270 (2) | |
C3 | 0.5712 (4) | 0.6398 (4) | 0.5288 (3) | 0.0165 (6) | |
H3 | 0.6812 | 0.6568 | 0.5272 | 0.020* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0175 (4) | 0.0103 (4) | 0.0176 (4) | 0.0042 (3) | 0.0032 (3) | 0.0012 (3) |
N1 | 0.0212 (14) | 0.0131 (13) | 0.0142 (14) | 0.0058 (11) | 0.0000 (11) | 0.0014 (10) |
C13 | 0.0266 (19) | 0.031 (2) | 0.0234 (18) | −0.0025 (15) | 0.0029 (14) | −0.0079 (15) |
C22 | 0.0158 (15) | 0.0174 (16) | 0.0246 (17) | 0.0001 (12) | 0.0042 (13) | 0.0050 (13) |
O22 | 0.0185 (11) | 0.0249 (12) | 0.0174 (11) | 0.0025 (9) | 0.0022 (9) | 0.0097 (9) |
C20 | 0.0196 (17) | 0.0187 (17) | 0.036 (2) | 0.0006 (13) | 0.0067 (14) | 0.0102 (15) |
C18 | 0.0171 (16) | 0.0222 (17) | 0.0164 (16) | 0.0028 (13) | 0.0058 (12) | 0.0036 (13) |
C4 | 0.0224 (17) | 0.0184 (16) | 0.0098 (14) | 0.0068 (13) | 0.0010 (12) | −0.0005 (12) |
C21 | 0.0298 (19) | 0.0203 (17) | 0.0255 (18) | 0.0119 (15) | 0.0049 (15) | 0.0042 (14) |
O21 | 0.0180 (11) | 0.0177 (12) | 0.0195 (12) | 0.0020 (9) | 0.0028 (9) | −0.0012 (9) |
C17 | 0.0261 (18) | 0.0189 (16) | 0.0131 (15) | 0.0092 (14) | 0.0038 (13) | 0.0044 (12) |
C16 | 0.0269 (17) | 0.0110 (15) | 0.0198 (16) | 0.0024 (13) | 0.0044 (13) | 0.0044 (12) |
C7 | 0.0270 (18) | 0.0189 (17) | 0.0294 (18) | 0.0020 (14) | 0.0100 (15) | 0.0045 (14) |
C15 | 0.0194 (16) | 0.0155 (15) | 0.0171 (15) | 0.0025 (12) | 0.0028 (12) | 0.0049 (12) |
C14 | 0.0167 (15) | 0.0108 (14) | 0.0116 (14) | 0.0035 (12) | 0.0024 (12) | 0.0024 (11) |
C1 | 0.0184 (15) | 0.0109 (14) | 0.0118 (14) | 0.0040 (12) | 0.0012 (11) | −0.0010 (11) |
C19 | 0.0210 (16) | 0.0152 (15) | 0.0112 (14) | 0.0037 (13) | 0.0038 (12) | 0.0038 (12) |
C12 | 0.031 (2) | 0.030 (2) | 0.0224 (18) | −0.0033 (16) | 0.0099 (15) | −0.0116 (15) |
O12 | 0.0185 (12) | 0.0199 (12) | 0.0221 (12) | 0.0031 (9) | 0.0052 (9) | 0.0053 (9) |
C24 | 0.0271 (19) | 0.038 (2) | 0.0246 (18) | 0.0034 (16) | 0.0039 (15) | 0.0134 (16) |
C11 | 0.042 (3) | 0.042 (3) | 0.063 (3) | −0.002 (2) | 0.034 (2) | −0.005 (2) |
O11 | 0.0216 (12) | 0.0185 (12) | 0.0192 (12) | 0.0016 (10) | 0.0053 (9) | −0.0055 (9) |
C23 | 0.0255 (19) | 0.043 (2) | 0.0219 (17) | 0.0013 (17) | −0.0002 (14) | 0.0198 (16) |
C10 | 0.0240 (18) | 0.0266 (19) | 0.037 (2) | −0.0069 (15) | 0.0091 (16) | 0.0068 (16) |
C26 | 0.022 (2) | 0.060 (3) | 0.053 (3) | −0.003 (2) | −0.0078 (19) | 0.020 (2) |
C9 | 0.0210 (17) | 0.0157 (17) | 0.041 (2) | 0.0000 (14) | 0.0066 (15) | 0.0022 (15) |
C25 | 0.0205 (17) | 0.0213 (17) | 0.0304 (19) | −0.0093 (14) | 0.0019 (14) | 0.0001 (14) |
C8 | 0.0272 (18) | 0.0196 (17) | 0.0200 (16) | 0.0081 (14) | 0.0019 (14) | 0.0056 (13) |
C6 | 0.0201 (16) | 0.0161 (16) | 0.0155 (15) | 0.0023 (12) | 0.0020 (12) | −0.0004 (12) |
C5 | 0.0239 (17) | 0.0113 (15) | 0.0182 (15) | 0.0008 (12) | 0.0030 (12) | 0.0023 (12) |
N2 | 0.0190 (13) | 0.0122 (13) | 0.0129 (13) | 0.0051 (11) | 0.0050 (10) | 0.0012 (10) |
P2 | 0.0148 (4) | 0.0113 (4) | 0.0144 (4) | 0.0035 (3) | 0.0019 (3) | 0.0021 (3) |
C2 | 0.0207 (16) | 0.0136 (15) | 0.0115 (14) | 0.0010 (12) | 0.0024 (12) | −0.0012 (11) |
S2 | 0.0288 (4) | 0.0162 (4) | 0.0216 (4) | 0.0122 (3) | 0.0024 (3) | 0.0004 (3) |
S1 | 0.0314 (5) | 0.0189 (4) | 0.0313 (5) | 0.0139 (4) | 0.0038 (4) | 0.0083 (4) |
C3 | 0.0154 (15) | 0.0191 (16) | 0.0147 (15) | 0.0011 (12) | 0.0036 (12) | 0.0012 (12) |
Geometric parameters (Å, º) top
P1—O11 | 1.581 (2) | C14—C19 | 1.406 (4) |
P1—O12 | 1.588 (2) | C14—N2 | 1.440 (4) |
P1—N1 | 1.632 (3) | C1—C6 | 1.398 (4) |
P1—S1 | 1.9254 (11) | C1—C2 | 1.406 (4) |
N1—C1 | 1.438 (4) | C12—O11 | 1.455 (4) |
N1—H1 | 0.83 (4) | C12—H12A | 0.9900 |
C13—C12 | 1.492 (5) | C12—H12B | 0.9900 |
C13—H13A | 0.9800 | O12—C10 | 1.441 (4) |
C13—H13B | 0.9800 | C24—C23 | 1.493 (5) |
C13—H13C | 0.9800 | C24—H24A | 0.9800 |
C22—C19 | 1.507 (4) | C24—H24B | 0.9800 |
C22—H22A | 0.9800 | C24—H24C | 0.9800 |
C22—H22B | 0.9800 | C11—C10 | 1.493 (6) |
C22—H22C | 0.9800 | C11—H11A | 0.9800 |
O22—C23 | 1.458 (4) | C11—H11B | 0.9800 |
O22—P2 | 1.578 (2) | C11—H11C | 0.9800 |
C20—C15 | 1.508 (4) | C23—H23A | 0.9900 |
C20—H20A | 0.9800 | C23—H23B | 0.9900 |
C20—H20B | 0.9800 | C10—H10A | 0.9900 |
C20—H20C | 0.9800 | C10—H10B | 0.9900 |
C18—C19 | 1.389 (5) | C26—C25 | 1.489 (6) |
C18—C17 | 1.393 (5) | C26—H26A | 0.9800 |
C18—H18 | 0.9500 | C26—H26B | 0.9800 |
C4—C5 | 1.384 (5) | C26—H26C | 0.9800 |
C4—C3 | 1.400 (5) | C9—C6 | 1.505 (5) |
C4—C8 | 1.502 (5) | C9—H9A | 0.9800 |
C21—C17 | 1.511 (5) | C9—H9B | 0.9800 |
C21—H21A | 0.9800 | C9—H9C | 0.9800 |
C21—H21B | 0.9800 | C25—H25A | 0.9900 |
C21—H21C | 0.9800 | C25—H25B | 0.9900 |
O21—C25 | 1.448 (4) | C8—H8A | 0.9800 |
O21—P2 | 1.588 (2) | C8—H8B | 0.9800 |
C17—C16 | 1.388 (5) | C8—H8C | 0.9800 |
C16—C15 | 1.390 (5) | C6—C5 | 1.398 (5) |
C16—H16 | 0.9500 | C5—H5 | 0.9500 |
C7—C2 | 1.509 (5) | N2—P2 | 1.629 (3) |
C7—H7A | 0.9800 | N2—H2 | 0.83 (3) |
C7—H7B | 0.9800 | P2—S2 | 1.9355 (11) |
C7—H7C | 0.9800 | C2—C3 | 1.390 (5) |
C15—C14 | 1.404 (4) | C3—H3 | 0.9500 |
| | | |
O11—P1—O12 | 99.04 (13) | C10—O12—P1 | 122.8 (2) |
O11—P1—N1 | 103.50 (13) | C23—C24—H24A | 109.5 |
O12—P1—N1 | 108.27 (14) | C23—C24—H24B | 109.5 |
O11—P1—S1 | 117.29 (10) | H24A—C24—H24B | 109.5 |
O12—P1—S1 | 115.18 (10) | C23—C24—H24C | 109.5 |
N1—P1—S1 | 112.17 (11) | H24A—C24—H24C | 109.5 |
C1—N1—P1 | 125.9 (2) | H24B—C24—H24C | 109.5 |
C1—N1—H1 | 113 (3) | C10—C11—H11A | 109.5 |
P1—N1—H1 | 121 (3) | C10—C11—H11B | 109.5 |
C12—C13—H13A | 109.5 | H11A—C11—H11B | 109.5 |
C12—C13—H13B | 109.5 | C10—C11—H11C | 109.5 |
H13A—C13—H13B | 109.5 | H11A—C11—H11C | 109.5 |
C12—C13—H13C | 109.5 | H11B—C11—H11C | 109.5 |
H13A—C13—H13C | 109.5 | C12—O11—P1 | 119.6 (2) |
H13B—C13—H13C | 109.5 | O22—C23—C24 | 107.8 (3) |
C19—C22—H22A | 109.5 | O22—C23—H23A | 110.1 |
C19—C22—H22B | 109.5 | C24—C23—H23A | 110.1 |
H22A—C22—H22B | 109.5 | O22—C23—H23B | 110.1 |
C19—C22—H22C | 109.5 | C24—C23—H23B | 110.1 |
H22A—C22—H22C | 109.5 | H23A—C23—H23B | 108.5 |
H22B—C22—H22C | 109.5 | O12—C10—C11 | 109.5 (3) |
C23—O22—P2 | 119.9 (2) | O12—C10—H10A | 109.8 |
C15—C20—H20A | 109.5 | C11—C10—H10A | 109.8 |
C15—C20—H20B | 109.5 | O12—C10—H10B | 109.8 |
H20A—C20—H20B | 109.5 | C11—C10—H10B | 109.8 |
C15—C20—H20C | 109.5 | H10A—C10—H10B | 108.2 |
H20A—C20—H20C | 109.5 | C25—C26—H26A | 109.5 |
H20B—C20—H20C | 109.5 | C25—C26—H26B | 109.5 |
C19—C18—C17 | 122.7 (3) | H26A—C26—H26B | 109.5 |
C19—C18—H18 | 118.7 | C25—C26—H26C | 109.5 |
C17—C18—H18 | 118.7 | H26A—C26—H26C | 109.5 |
C5—C4—C3 | 117.5 (3) | H26B—C26—H26C | 109.5 |
C5—C4—C8 | 121.8 (3) | C6—C9—H9A | 109.5 |
C3—C4—C8 | 120.6 (3) | C6—C9—H9B | 109.5 |
C17—C21—H21A | 109.5 | H9A—C9—H9B | 109.5 |
C17—C21—H21B | 109.5 | C6—C9—H9C | 109.5 |
H21A—C21—H21B | 109.5 | H9A—C9—H9C | 109.5 |
C17—C21—H21C | 109.5 | H9B—C9—H9C | 109.5 |
H21A—C21—H21C | 109.5 | O21—C25—C26 | 109.0 (3) |
H21B—C21—H21C | 109.5 | O21—C25—H25A | 109.9 |
C25—O21—P2 | 122.4 (2) | C26—C25—H25A | 109.9 |
C16—C17—C18 | 117.6 (3) | O21—C25—H25B | 109.9 |
C16—C17—C21 | 121.6 (3) | C26—C25—H25B | 109.9 |
C18—C17—C21 | 120.8 (3) | H25A—C25—H25B | 108.3 |
C17—C16—C15 | 122.3 (3) | C4—C8—H8A | 109.5 |
C17—C16—H16 | 118.9 | C4—C8—H8B | 109.5 |
C15—C16—H16 | 118.9 | H8A—C8—H8B | 109.5 |
C2—C7—H7A | 109.5 | C4—C8—H8C | 109.5 |
C2—C7—H7B | 109.5 | H8A—C8—H8C | 109.5 |
H7A—C7—H7B | 109.5 | H8B—C8—H8C | 109.5 |
C2—C7—H7C | 109.5 | C5—C6—C1 | 118.7 (3) |
H7A—C7—H7C | 109.5 | C5—C6—C9 | 119.3 (3) |
H7B—C7—H7C | 109.5 | C1—C6—C9 | 121.9 (3) |
C16—C15—C14 | 118.6 (3) | C4—C5—C6 | 122.3 (3) |
C16—C15—C20 | 119.9 (3) | C4—C5—H5 | 118.9 |
C14—C15—C20 | 121.5 (3) | C6—C5—H5 | 118.9 |
C15—C14—C19 | 120.7 (3) | C14—N2—P2 | 126.6 (2) |
C15—C14—N2 | 119.5 (3) | C14—N2—H2 | 116 (3) |
C19—C14—N2 | 119.7 (3) | P2—N2—H2 | 117 (3) |
C6—C1—C2 | 120.7 (3) | O22—P2—O21 | 99.10 (12) |
C6—C1—N1 | 120.0 (3) | O22—P2—N2 | 103.90 (13) |
C2—C1—N1 | 119.2 (3) | O21—P2—N2 | 109.23 (13) |
C18—C19—C14 | 118.1 (3) | O22—P2—S2 | 116.85 (10) |
C18—C19—C22 | 120.1 (3) | O21—P2—S2 | 114.39 (9) |
C14—C19—C22 | 121.8 (3) | N2—P2—S2 | 112.17 (10) |
O11—C12—C13 | 108.2 (3) | C3—C2—C1 | 118.3 (3) |
O11—C12—H12A | 110.1 | C3—C2—C7 | 120.4 (3) |
C13—C12—H12A | 110.1 | C1—C2—C7 | 121.3 (3) |
O11—C12—H12B | 110.1 | C2—C3—C4 | 122.5 (3) |
C13—C12—H12B | 110.1 | C2—C3—H3 | 118.7 |
H12A—C12—H12B | 108.4 | C4—C3—H3 | 118.7 |
| | | |
O11—P1—N1—C1 | 53.1 (3) | P1—O12—C10—C11 | −109.6 (4) |
O12—P1—N1—C1 | −51.4 (3) | P2—O21—C25—C26 | 110.8 (3) |
S1—P1—N1—C1 | −179.5 (2) | C2—C1—C6—C5 | 2.3 (5) |
C19—C18—C17—C16 | −0.3 (5) | N1—C1—C6—C5 | 179.1 (3) |
C19—C18—C17—C21 | −178.6 (3) | C2—C1—C6—C9 | −176.0 (3) |
C18—C17—C16—C15 | −1.0 (5) | N1—C1—C6—C9 | 0.8 (5) |
C21—C17—C16—C15 | 177.3 (3) | C3—C4—C5—C6 | 0.2 (5) |
C17—C16—C15—C14 | 2.5 (5) | C8—C4—C5—C6 | −176.6 (3) |
C17—C16—C15—C20 | −175.4 (3) | C1—C6—C5—C4 | −1.4 (5) |
C16—C15—C14—C19 | −2.8 (4) | C9—C6—C5—C4 | 176.9 (3) |
C20—C15—C14—C19 | 175.1 (3) | C15—C14—N2—P2 | −94.1 (3) |
C16—C15—C14—N2 | −178.6 (3) | C19—C14—N2—P2 | 90.0 (3) |
C20—C15—C14—N2 | −0.8 (5) | C23—O22—P2—O21 | 60.2 (3) |
P1—N1—C1—C6 | 91.3 (3) | C23—O22—P2—N2 | 172.7 (3) |
P1—N1—C1—C2 | −91.8 (3) | C23—O22—P2—S2 | −63.2 (3) |
C17—C18—C19—C14 | 0.0 (5) | C25—O21—P2—O22 | −156.3 (2) |
C17—C18—C19—C22 | −179.8 (3) | C25—O21—P2—N2 | 95.5 (3) |
C15—C14—C19—C18 | 1.5 (4) | C25—O21—P2—S2 | −31.2 (3) |
N2—C14—C19—C18 | 177.4 (3) | C14—N2—P2—O22 | −53.4 (3) |
C15—C14—C19—C22 | −178.6 (3) | C14—N2—P2—O21 | 51.6 (3) |
N2—C14—C19—C22 | −2.8 (5) | C14—N2—P2—S2 | 179.5 (2) |
O11—P1—O12—C10 | 152.6 (3) | C6—C1—C2—C3 | −1.9 (5) |
N1—P1—O12—C10 | −99.8 (3) | N1—C1—C2—C3 | −178.7 (3) |
S1—P1—O12—C10 | 26.6 (3) | C6—C1—C2—C7 | 175.6 (3) |
C13—C12—O11—P1 | −164.0 (3) | N1—C1—C2—C7 | −1.2 (5) |
O12—P1—O11—C12 | −60.3 (3) | C1—C2—C3—C4 | 0.6 (5) |
N1—P1—O11—C12 | −171.6 (3) | C7—C2—C3—C4 | −176.9 (3) |
S1—P1—O11—C12 | 64.3 (3) | C5—C4—C3—C2 | 0.2 (5) |
P2—O22—C23—C24 | 164.2 (3) | C8—C4—C3—C2 | 177.1 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S2 | 0.83 (4) | 2.74 (4) | 3.503 (3) | 154 (4) |
N2—H2···CG1 | 0.83 (2) | 2.39 (3) | 3.175 (3) | 158 (4) |
The experimental and optimized selected bond lengths (Å) and bond angles (°) top | Experimental | Optimized | |
| | Individual molecule | Dimer |
Bond | | | |
P1—S1|P2—S2 | 1.9254 (11)|1.9354 (11) | 1.93 | 1.93|1.95 |
P1—N1|P2—N2 | 1.632 (3)|1.629 (3) | 1.66 | 1.66|1.66 |
P1—O11|P2—O22 | 1.581 (2)|1.578 (2) | 1.60 | 1.61|1.62 |
P1—O12|P2—O21 | 1.588 (2)|1.588 (2) | 1.60 | 1.62|1.59 |
N1—H1|N2—H2 | 0.83 (4)|0.83 (2) | 1.01 | 1.02|1.01 |
N1—C1|N2—C14 | 1.438 (4)|1.440 (4) | 1.44 | 1.43|1.43 |
C12—O11|C23—O22 | 1.456 (4)|1.458 (4) | 1.44 | 1.44|1.44 |
C10—O12|C25—O21 | 1.440 (4)|1.448 (4) | 1.44 | 1.44|1.44 |
| | | |
Angle | | | |
S1—P1—N1|S2—P2—N2 | 112.17 (11)|112.17 (10) | 112.8 | 113.2|112.4 |
S1—P1—O11|S2—P2—O22 | 117.29 (10)|116.85 (10) | 117.8 | 118.0|114.0 |
S1—P1—O12|S2—P2—O21 | 115.18 (10)|114.40 (9) | 115.6 | 115.3|117.6 |
N1—P1—O11|N2—P2—O22 | 103.50 (13)|103.89 (13) | 103.1 | 103.1|108.3 |
N1—P1—O12|N2—P2—O21 | 108.26 (14)|109.22 (13) | 106.8 | 106.9|103.5 |
O11—P1—O12|O21—P2—O22 | 99.04 (13)|99.10 (12) | 99.0 | 98.5|99.6 |
P1—N1—H1|P2—N2—H2 | 121 (3)|117 (3) | 111.5 | 113.7|112.3 |
P1—N1—C1|P2—N2—C14 | 125.9 (2)|126.6 (2) | 123.1 | 124.1|127.3 |
H1—N1—C1|H2—N2—C14 | 113 (3)|116 (3) | 115.0 | 114.2|114.0 |
C12—O11—P1|C23—O22—P2 | 119.6 (2)|119.9 (2) | 120.1 | 118.44|121.79 |
C10—O12—P1|C25—O21—P2 | 122.8 (2)|122.4 (2) | 121.6 | 120.23|119.91 |
Natural charge at the M06-2X/6-311++G(d,p) level and D3 correction top | | Natural charge (<q) | | | |
Type of atom | Individual molecule | Dimer | | | |
| | N—H···S═P | D3 | N—H···π | D3 |
S | -0.60 | -0.63 | -0.63 | – | – |
P | 2.01 | 2.05 | 2.05 | – | – |
N | -1.02 | -1.09 | -1.09 | -1.10 | -1.10 |
H | 0.42 | 0.45 | 0.45 | 0.45 | 0.45 |
Ca | -0.35 | – | – | -0.35 | -0.35 |
Note: (a) the natural charge given is the average value for aromatic
C atoms participating in N—H···π interactions. |
Results from the second-order perturbation theory analysis of the Fock matrix
within the NBO for the N—H···S═P and N—H···π interactions at
the M06-2X/6-311++G(d,p) level of theory and after D3 correction topType of interaction | Donor orbital | Acceptor orbital | E(2) (kcal mol-1) | E(2)-D3 (kcal mol-1) |
N—H···S═P | LP (S) | σ*(N—H) | 4.01 | 4.07 |
N—H···π | π(C—C)Ph | σ*(N—H) | 3.04 | 3.09 |
Topological properties: charge density, ρ(r), density
Laplacian, Nabla2ρ(r), potential energy density,
V(r), kinetic energy density, G(r), and electronic
energy density, H(r), along the atoms involved in the hydrogen
bond calculated at the M06-2X/6-311++G(d,p) level and after D3 correction top | ρ(r) | ρ(r)-D3 | Nabla2ρ(r) | Nabla2ρ(r)-D3 | V(r) | V(r)-D3 | G(r) | G(r)-D3 | H(r) | H(r)-D3 |
N—H···S═P | 0.1011 | 0.1018 | 0.2892 | 0.2907 | -0.4805 | -0.4837 | 0.6018 | 0.6052 | 0.1213 | 0.1215 |
N—H···π | 0.1351 | 0.1361 | 0.4530 | 0.4494 | -0.7078 | -0.7172 | 0.9156 | 0.9249 | 0.2078 | 0.2077 |
The experimental and computed vibrational frequency (cm-1) of the N—H bond
using the M06-2X/6-311++G(d,p) level of the theory topExperimental (cm-1) | Theoretical (cm-1) | | |
| Individual molecule | Dimer | |
| | N—H···S═P | N—H···π |
3350 | 3598 | 3500 | 3558 |
Computed energies for the selected molecular orbitals of the
individual molecule and dimer topCompound | LUMO (+1) | LUMO | HOMO'HOMO | (-1)' |
Individual molecule | -0.171 | -0.179 | -0.274 | -0.277 |
Dimer | -0.005 | -0.106 | -0.275 | -0.284 |