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In the crystal structure of O,O′-diethyl N-(2,4,6-tri­methyl­phen­yl)thio­phosphate, C13H22NO2PS, 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618007933/ky3141sup1.cif
Contains datablocks global, I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229618007933/ky3141sup2.cml
Supplementary material

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229618007933/ky3141sup3.pdf
Spectra

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229618007933/ky3141Isup4.hkl
Contains datablock I

CCDC reference: 1435273

Computing details top

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
C13H22NO2PSZ = 2
Mr = 287.34F(000) = 308
Triclinic, P1Dx = 1.249 Mg m3
a = 8.4954 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.6790 (3) ÅCell parameters from 7603 reflections
c = 10.7105 (4) Åθ = 4.2–32.1°
α = 100.366 (3)°µ = 0.31 mm1
β = 100.314 (3)°T = 100 K
γ = 90.093 (3)°Bulk, light-yellow
V = 763.79 (5) Å30.24 × 0.20 × 0.18 mm
Data collection top
Agilent Xcalibur Sapphire3 Gemini
diffractometer
6232 independent reflections
Radiation source: Enhance (Mo) X-ray Source6048 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
Detector resolution: 8.0151 pixels mm-1θmax = 26.4°, θmin = 3.4°
ω scansh = 1010
Absorption correction: multi-scan
CrysAlis PRO (Agilent, 2014)
k = 1010
Tmin = 0.951, Tmax = 1l = 1313
11026 measured reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH 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 = 1.08Δρmax = 0.46 e Å3
6232 reflectionsΔρmin = 0.23 e Å3
343 parametersAbsolute structure: Flack x determined using 2825 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
4 restraintsAbsolute 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
xyzUiso*/Ueq
P10.14947 (9)0.99042 (9)0.62404 (7)0.01530 (18)
N10.1966 (3)0.8614 (3)0.5069 (3)0.0167 (6)
H10.164 (5)0.868 (5)0.431 (4)0.018 (10)*
C130.4854 (4)1.2492 (5)0.8604 (4)0.0288 (8)
H13A0.49811.31160.94770.043*
H13B0.49361.31830.79870.043*
H13C0.56961.17220.85730.043*
C220.6994 (4)0.5844 (4)0.2253 (3)0.0191 (7)
H22A0.63960.66070.27570.029*
H22B0.69110.60770.13820.029*
H22C0.81210.59030.26740.029*
O220.3949 (3)0.6375 (3)0.0305 (2)0.0197 (5)
C200.2344 (4)0.2108 (4)0.2171 (4)0.0238 (7)
H20A0.22790.12640.26570.036*
H20B0.17170.18000.12980.036*
H20C0.19150.30620.26080.036*
C180.7295 (4)0.2944 (4)0.2108 (3)0.0182 (7)
H180.84030.31220.21250.022*
C40.5190 (4)0.4918 (4)0.5428 (3)0.0175 (7)
C210.7858 (5)0.0071 (4)0.1993 (4)0.0252 (7)
H21A0.72510.09150.16150.038*
H21B0.83960.00240.28740.038*
H21C0.86590.02310.14700.038*
O210.1648 (3)0.4639 (3)0.0032 (2)0.0190 (5)
C170.6729 (4)0.1415 (4)0.2025 (3)0.0192 (7)
C160.5109 (4)0.1184 (4)0.2009 (3)0.0190 (7)
H160.46970.01470.19390.023*
C70.5290 (4)0.9175 (4)0.4958 (4)0.0245 (7)
H7A0.45490.95260.42610.037*
H7B0.63500.90490.47200.037*
H7C0.53670.99560.57530.037*
C150.4067 (4)0.2416 (4)0.2091 (3)0.0171 (6)
C140.4670 (4)0.3938 (3)0.2143 (3)0.0130 (6)
C10.3059 (4)0.7368 (4)0.5213 (3)0.0143 (6)
C190.6307 (4)0.4218 (4)0.2168 (3)0.0155 (6)
C120.3254 (5)1.1660 (5)0.8262 (4)0.0293 (8)
H12A0.31091.10560.89370.035*
H12B0.23961.24270.81980.035*
O120.0974 (3)0.8995 (3)0.7271 (2)0.0198 (5)
C240.4938 (4)0.7597 (5)0.1237 (4)0.0289 (8)
H24A0.46630.79360.20710.043*
H24B0.57610.68090.12810.043*
H24C0.53470.85010.05650.043*
C110.1083 (6)0.9680 (6)0.8518 (5)0.0474 (12)
H11A0.21740.94060.86000.071*
H11B0.10121.07890.84540.071*
H11C0.03290.94910.92770.071*
O110.3174 (3)1.0607 (3)0.7029 (2)0.0207 (5)
C230.3481 (4)0.6905 (5)0.0921 (4)0.0289 (8)
H23A0.26520.76990.08510.035*
H23B0.30370.60110.16080.035*
C100.0677 (4)0.8696 (5)0.7332 (4)0.0285 (8)
H10A0.08530.75730.73510.034*
H10B0.13780.89460.65570.034*
C260.1018 (5)0.4715 (6)0.1138 (5)0.0456 (12)
H26A0.21350.43840.11920.068*
H26B0.06380.42120.19180.068*
H26C0.09420.58560.10610.068*
C90.0744 (4)0.5551 (4)0.5284 (4)0.0262 (8)
H9A0.01000.63130.48630.039*
H9B0.05450.56240.61660.039*
H9C0.04490.44910.47970.039*
C250.0015 (4)0.4248 (4)0.0014 (4)0.0250 (8)
H25A0.03470.48060.08110.030*
H25B0.01550.31070.00220.030*
C80.6333 (4)0.3602 (4)0.5484 (3)0.0223 (7)
H8A0.60160.29080.60310.033*
H8B0.74190.40340.58480.033*
H8C0.63090.30060.46120.033*
C60.2492 (4)0.5895 (4)0.5325 (3)0.0178 (6)
C50.3580 (4)0.4701 (4)0.5444 (3)0.0180 (6)
H50.32010.37060.55400.022*
N20.3620 (3)0.5236 (3)0.2257 (2)0.0146 (5)
H20.357 (5)0.568 (5)0.301 (3)0.026 (11)*
P20.26274 (9)0.59936 (8)0.10798 (7)0.01365 (17)
C20.4682 (4)0.7628 (4)0.5174 (3)0.0158 (6)
S20.13503 (10)0.77150 (9)0.16919 (8)0.0229 (2)
S10.00294 (11)1.13550 (10)0.56163 (9)0.0270 (2)
C30.5712 (4)0.6398 (4)0.5288 (3)0.0165 (6)
H30.68120.65680.52720.020*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0175 (4)0.0103 (4)0.0176 (4)0.0042 (3)0.0032 (3)0.0012 (3)
N10.0212 (14)0.0131 (13)0.0142 (14)0.0058 (11)0.0000 (11)0.0014 (10)
C130.0266 (19)0.031 (2)0.0234 (18)0.0025 (15)0.0029 (14)0.0079 (15)
C220.0158 (15)0.0174 (16)0.0246 (17)0.0001 (12)0.0042 (13)0.0050 (13)
O220.0185 (11)0.0249 (12)0.0174 (11)0.0025 (9)0.0022 (9)0.0097 (9)
C200.0196 (17)0.0187 (17)0.036 (2)0.0006 (13)0.0067 (14)0.0102 (15)
C180.0171 (16)0.0222 (17)0.0164 (16)0.0028 (13)0.0058 (12)0.0036 (13)
C40.0224 (17)0.0184 (16)0.0098 (14)0.0068 (13)0.0010 (12)0.0005 (12)
C210.0298 (19)0.0203 (17)0.0255 (18)0.0119 (15)0.0049 (15)0.0042 (14)
O210.0180 (11)0.0177 (12)0.0195 (12)0.0020 (9)0.0028 (9)0.0012 (9)
C170.0261 (18)0.0189 (16)0.0131 (15)0.0092 (14)0.0038 (13)0.0044 (12)
C160.0269 (17)0.0110 (15)0.0198 (16)0.0024 (13)0.0044 (13)0.0044 (12)
C70.0270 (18)0.0189 (17)0.0294 (18)0.0020 (14)0.0100 (15)0.0045 (14)
C150.0194 (16)0.0155 (15)0.0171 (15)0.0025 (12)0.0028 (12)0.0049 (12)
C140.0167 (15)0.0108 (14)0.0116 (14)0.0035 (12)0.0024 (12)0.0024 (11)
C10.0184 (15)0.0109 (14)0.0118 (14)0.0040 (12)0.0012 (11)0.0010 (11)
C190.0210 (16)0.0152 (15)0.0112 (14)0.0037 (13)0.0038 (12)0.0038 (12)
C120.031 (2)0.030 (2)0.0224 (18)0.0033 (16)0.0099 (15)0.0116 (15)
O120.0185 (12)0.0199 (12)0.0221 (12)0.0031 (9)0.0052 (9)0.0053 (9)
C240.0271 (19)0.038 (2)0.0246 (18)0.0034 (16)0.0039 (15)0.0134 (16)
C110.042 (3)0.042 (3)0.063 (3)0.002 (2)0.034 (2)0.005 (2)
O110.0216 (12)0.0185 (12)0.0192 (12)0.0016 (10)0.0053 (9)0.0055 (9)
C230.0255 (19)0.043 (2)0.0219 (17)0.0013 (17)0.0002 (14)0.0198 (16)
C100.0240 (18)0.0266 (19)0.037 (2)0.0069 (15)0.0091 (16)0.0068 (16)
C260.022 (2)0.060 (3)0.053 (3)0.003 (2)0.0078 (19)0.020 (2)
C90.0210 (17)0.0157 (17)0.041 (2)0.0000 (14)0.0066 (15)0.0022 (15)
C250.0205 (17)0.0213 (17)0.0304 (19)0.0093 (14)0.0019 (14)0.0001 (14)
C80.0272 (18)0.0196 (17)0.0200 (16)0.0081 (14)0.0019 (14)0.0056 (13)
C60.0201 (16)0.0161 (16)0.0155 (15)0.0023 (12)0.0020 (12)0.0004 (12)
C50.0239 (17)0.0113 (15)0.0182 (15)0.0008 (12)0.0030 (12)0.0023 (12)
N20.0190 (13)0.0122 (13)0.0129 (13)0.0051 (11)0.0050 (10)0.0012 (10)
P20.0148 (4)0.0113 (4)0.0144 (4)0.0035 (3)0.0019 (3)0.0021 (3)
C20.0207 (16)0.0136 (15)0.0115 (14)0.0010 (12)0.0024 (12)0.0012 (11)
S20.0288 (4)0.0162 (4)0.0216 (4)0.0122 (3)0.0024 (3)0.0004 (3)
S10.0314 (5)0.0189 (4)0.0313 (5)0.0139 (4)0.0038 (4)0.0083 (4)
C30.0154 (15)0.0191 (16)0.0147 (15)0.0011 (12)0.0036 (12)0.0012 (12)
Geometric parameters (Å, º) top
P1—O111.581 (2)C14—C191.406 (4)
P1—O121.588 (2)C14—N21.440 (4)
P1—N11.632 (3)C1—C61.398 (4)
P1—S11.9254 (11)C1—C21.406 (4)
N1—C11.438 (4)C12—O111.455 (4)
N1—H10.83 (4)C12—H12A0.9900
C13—C121.492 (5)C12—H12B0.9900
C13—H13A0.9800O12—C101.441 (4)
C13—H13B0.9800C24—C231.493 (5)
C13—H13C0.9800C24—H24A0.9800
C22—C191.507 (4)C24—H24B0.9800
C22—H22A0.9800C24—H24C0.9800
C22—H22B0.9800C11—C101.493 (6)
C22—H22C0.9800C11—H11A0.9800
O22—C231.458 (4)C11—H11B0.9800
O22—P21.578 (2)C11—H11C0.9800
C20—C151.508 (4)C23—H23A0.9900
C20—H20A0.9800C23—H23B0.9900
C20—H20B0.9800C10—H10A0.9900
C20—H20C0.9800C10—H10B0.9900
C18—C191.389 (5)C26—C251.489 (6)
C18—C171.393 (5)C26—H26A0.9800
C18—H180.9500C26—H26B0.9800
C4—C51.384 (5)C26—H26C0.9800
C4—C31.400 (5)C9—C61.505 (5)
C4—C81.502 (5)C9—H9A0.9800
C21—C171.511 (5)C9—H9B0.9800
C21—H21A0.9800C9—H9C0.9800
C21—H21B0.9800C25—H25A0.9900
C21—H21C0.9800C25—H25B0.9900
O21—C251.448 (4)C8—H8A0.9800
O21—P21.588 (2)C8—H8B0.9800
C17—C161.388 (5)C8—H8C0.9800
C16—C151.390 (5)C6—C51.398 (5)
C16—H160.9500C5—H50.9500
C7—C21.509 (5)N2—P21.629 (3)
C7—H7A0.9800N2—H20.83 (3)
C7—H7B0.9800P2—S21.9355 (11)
C7—H7C0.9800C2—C31.390 (5)
C15—C141.404 (4)C3—H30.9500
O11—P1—O1299.04 (13)C10—O12—P1122.8 (2)
O11—P1—N1103.50 (13)C23—C24—H24A109.5
O12—P1—N1108.27 (14)C23—C24—H24B109.5
O11—P1—S1117.29 (10)H24A—C24—H24B109.5
O12—P1—S1115.18 (10)C23—C24—H24C109.5
N1—P1—S1112.17 (11)H24A—C24—H24C109.5
C1—N1—P1125.9 (2)H24B—C24—H24C109.5
C1—N1—H1113 (3)C10—C11—H11A109.5
P1—N1—H1121 (3)C10—C11—H11B109.5
C12—C13—H13A109.5H11A—C11—H11B109.5
C12—C13—H13B109.5C10—C11—H11C109.5
H13A—C13—H13B109.5H11A—C11—H11C109.5
C12—C13—H13C109.5H11B—C11—H11C109.5
H13A—C13—H13C109.5C12—O11—P1119.6 (2)
H13B—C13—H13C109.5O22—C23—C24107.8 (3)
C19—C22—H22A109.5O22—C23—H23A110.1
C19—C22—H22B109.5C24—C23—H23A110.1
H22A—C22—H22B109.5O22—C23—H23B110.1
C19—C22—H22C109.5C24—C23—H23B110.1
H22A—C22—H22C109.5H23A—C23—H23B108.5
H22B—C22—H22C109.5O12—C10—C11109.5 (3)
C23—O22—P2119.9 (2)O12—C10—H10A109.8
C15—C20—H20A109.5C11—C10—H10A109.8
C15—C20—H20B109.5O12—C10—H10B109.8
H20A—C20—H20B109.5C11—C10—H10B109.8
C15—C20—H20C109.5H10A—C10—H10B108.2
H20A—C20—H20C109.5C25—C26—H26A109.5
H20B—C20—H20C109.5C25—C26—H26B109.5
C19—C18—C17122.7 (3)H26A—C26—H26B109.5
C19—C18—H18118.7C25—C26—H26C109.5
C17—C18—H18118.7H26A—C26—H26C109.5
C5—C4—C3117.5 (3)H26B—C26—H26C109.5
C5—C4—C8121.8 (3)C6—C9—H9A109.5
C3—C4—C8120.6 (3)C6—C9—H9B109.5
C17—C21—H21A109.5H9A—C9—H9B109.5
C17—C21—H21B109.5C6—C9—H9C109.5
H21A—C21—H21B109.5H9A—C9—H9C109.5
C17—C21—H21C109.5H9B—C9—H9C109.5
H21A—C21—H21C109.5O21—C25—C26109.0 (3)
H21B—C21—H21C109.5O21—C25—H25A109.9
C25—O21—P2122.4 (2)C26—C25—H25A109.9
C16—C17—C18117.6 (3)O21—C25—H25B109.9
C16—C17—C21121.6 (3)C26—C25—H25B109.9
C18—C17—C21120.8 (3)H25A—C25—H25B108.3
C17—C16—C15122.3 (3)C4—C8—H8A109.5
C17—C16—H16118.9C4—C8—H8B109.5
C15—C16—H16118.9H8A—C8—H8B109.5
C2—C7—H7A109.5C4—C8—H8C109.5
C2—C7—H7B109.5H8A—C8—H8C109.5
H7A—C7—H7B109.5H8B—C8—H8C109.5
C2—C7—H7C109.5C5—C6—C1118.7 (3)
H7A—C7—H7C109.5C5—C6—C9119.3 (3)
H7B—C7—H7C109.5C1—C6—C9121.9 (3)
C16—C15—C14118.6 (3)C4—C5—C6122.3 (3)
C16—C15—C20119.9 (3)C4—C5—H5118.9
C14—C15—C20121.5 (3)C6—C5—H5118.9
C15—C14—C19120.7 (3)C14—N2—P2126.6 (2)
C15—C14—N2119.5 (3)C14—N2—H2116 (3)
C19—C14—N2119.7 (3)P2—N2—H2117 (3)
C6—C1—C2120.7 (3)O22—P2—O2199.10 (12)
C6—C1—N1120.0 (3)O22—P2—N2103.90 (13)
C2—C1—N1119.2 (3)O21—P2—N2109.23 (13)
C18—C19—C14118.1 (3)O22—P2—S2116.85 (10)
C18—C19—C22120.1 (3)O21—P2—S2114.39 (9)
C14—C19—C22121.8 (3)N2—P2—S2112.17 (10)
O11—C12—C13108.2 (3)C3—C2—C1118.3 (3)
O11—C12—H12A110.1C3—C2—C7120.4 (3)
C13—C12—H12A110.1C1—C2—C7121.3 (3)
O11—C12—H12B110.1C2—C3—C4122.5 (3)
C13—C12—H12B110.1C2—C3—H3118.7
H12A—C12—H12B108.4C4—C3—H3118.7
O11—P1—N1—C153.1 (3)P1—O12—C10—C11109.6 (4)
O12—P1—N1—C151.4 (3)P2—O21—C25—C26110.8 (3)
S1—P1—N1—C1179.5 (2)C2—C1—C6—C52.3 (5)
C19—C18—C17—C160.3 (5)N1—C1—C6—C5179.1 (3)
C19—C18—C17—C21178.6 (3)C2—C1—C6—C9176.0 (3)
C18—C17—C16—C151.0 (5)N1—C1—C6—C90.8 (5)
C21—C17—C16—C15177.3 (3)C3—C4—C5—C60.2 (5)
C17—C16—C15—C142.5 (5)C8—C4—C5—C6176.6 (3)
C17—C16—C15—C20175.4 (3)C1—C6—C5—C41.4 (5)
C16—C15—C14—C192.8 (4)C9—C6—C5—C4176.9 (3)
C20—C15—C14—C19175.1 (3)C15—C14—N2—P294.1 (3)
C16—C15—C14—N2178.6 (3)C19—C14—N2—P290.0 (3)
C20—C15—C14—N20.8 (5)C23—O22—P2—O2160.2 (3)
P1—N1—C1—C691.3 (3)C23—O22—P2—N2172.7 (3)
P1—N1—C1—C291.8 (3)C23—O22—P2—S263.2 (3)
C17—C18—C19—C140.0 (5)C25—O21—P2—O22156.3 (2)
C17—C18—C19—C22179.8 (3)C25—O21—P2—N295.5 (3)
C15—C14—C19—C181.5 (4)C25—O21—P2—S231.2 (3)
N2—C14—C19—C18177.4 (3)C14—N2—P2—O2253.4 (3)
C15—C14—C19—C22178.6 (3)C14—N2—P2—O2151.6 (3)
N2—C14—C19—C222.8 (5)C14—N2—P2—S2179.5 (2)
O11—P1—O12—C10152.6 (3)C6—C1—C2—C31.9 (5)
N1—P1—O12—C1099.8 (3)N1—C1—C2—C3178.7 (3)
S1—P1—O12—C1026.6 (3)C6—C1—C2—C7175.6 (3)
C13—C12—O11—P1164.0 (3)N1—C1—C2—C71.2 (5)
O12—P1—O11—C1260.3 (3)C1—C2—C3—C40.6 (5)
N1—P1—O11—C12171.6 (3)C7—C2—C3—C4176.9 (3)
S1—P1—O11—C1264.3 (3)C5—C4—C3—C20.2 (5)
P2—O22—C23—C24164.2 (3)C8—C4—C3—C2177.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S20.83 (4)2.74 (4)3.503 (3)154 (4)
N2—H2···CG10.83 (2)2.39 (3)3.175 (3)158 (4)
The experimental and optimized selected bond lengths (Å) and bond angles (°) top
ExperimentalOptimized
Individual moleculeDimer
Bond
P1—S1|P2—S21.9254 (11)|1.9354 (11)1.931.93|1.95
P1—N1|P2—N21.632 (3)|1.629 (3)1.661.66|1.66
P1—O11|P2—O221.581 (2)|1.578 (2)1.601.61|1.62
P1—O12|P2—O211.588 (2)|1.588 (2)1.601.62|1.59
N1—H1|N2—H20.83 (4)|0.83 (2)1.011.02|1.01
N1—C1|N2—C141.438 (4)|1.440 (4)1.441.43|1.43
C12—O11|C23—O221.456 (4)|1.458 (4)1.441.44|1.44
C10—O12|C25—O211.440 (4)|1.448 (4)1.441.44|1.44
Angle
S1—P1—N1|S2—P2—N2112.17 (11)|112.17 (10)112.8113.2|112.4
S1—P1—O11|S2—P2—O22117.29 (10)|116.85 (10)117.8118.0|114.0
S1—P1—O12|S2—P2—O21115.18 (10)|114.40 (9)115.6115.3|117.6
N1—P1—O11|N2—P2—O22103.50 (13)|103.89 (13)103.1103.1|108.3
N1—P1—O12|N2—P2—O21108.26 (14)|109.22 (13)106.8106.9|103.5
O11—P1—O12|O21—P2—O2299.04 (13)|99.10 (12)99.098.5|99.6
P1—N1—H1|P2—N2—H2121 (3)|117 (3)111.5113.7|112.3
P1—N1—C1|P2—N2—C14125.9 (2)|126.6 (2)123.1124.1|127.3
H1—N1—C1|H2—N2—C14113 (3)|116 (3)115.0114.2|114.0
C12—O11—P1|C23—O22—P2119.6 (2)|119.9 (2)120.1118.44|121.79
C10—O12—P1|C25—O21—P2122.8 (2)|122.4 (2)121.6120.23|119.91
Natural charge at the M06-2X/6-311++G(d,p) level and D3 correction top
Natural charge (<q)
Type of atomIndividual moleculeDimer
N—H···SPD3N—H···πD3
S-0.60-0.63-0.63
P2.012.052.05
N-1.02-1.09-1.09-1.10-1.10
H0.420.450.450.450.45
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···SP and N—H···π interactions at the M06-2X/6-311++G(d,p) level of theory and after D3 correction top
Type of interactionDonor orbitalAcceptor orbitalE(2) (kcal mol-1)E(2)-D3 (kcal mol-1)
N—H···SPLP (S)σ*(N—H)4.014.07
N—H···ππ(C—C)Phσ*(N—H)3.043.09
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)-D3Nabla2ρ(r)Nabla2ρ(r)-D3V(r)V(r)-D3G(r)G(r)-D3H(r)H(r)-D3
N—H···SP0.10110.10180.28920.2907-0.4805-0.48370.60180.60520.12130.1215
N—H···π0.13510.13610.45300.4494-0.7078-0.71720.91560.92490.20780.2077
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 top
Experimental (cm-1)Theoretical (cm-1)
Individual moleculeDimer
N—H···SPN—H···π
3350359835003558
Computed energies for the selected molecular orbitals of the individual molecule and dimer top
CompoundLUMO (+1)LUMOHOMO'HOMO(-1)'
Individual molecule-0.171-0.179-0.274-0.277
Dimer-0.005-0.106-0.275-0.284
 

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