research papers
The structure of N,N′,N′′-tribenzylphosphorothioic triamide, C21H24N3PS, (I), and analysis of the bond-angle sums at the N atoms for this compound, and for 74 structures with a P(S)[N]3 skeleton and the N atom in a three-coordinate geometry found in the Cambridge Structural Database [CSD; Groom & Allen (2014). Angew. Chem. Int. Ed. 53, 662–671], are reported. For (I), the bond-angle sum at one of the N atoms [359 (1)°] shows a nearly planar configuration, while the other two show a nonplanar geometry with bond-angle sums of 342 (1) and 347 (1)°. The location of the atoms attached to the nonplanar N atoms suggests an anti orientation of the corresponding lone electron pairs (LEPs) on these N atoms with respect to the P=S group. For 74 structures with a P(S)[N]3 skeleton and with the N atom in a three-coordinate geometry, the bond-angle sums at the N atoms were found to be in the range 293–360°. Among 307 such three-coordinate N atoms, 39% (120 N atoms) have bond-angle sums in the range 359–360°, in accordance with sp2 hybridization, and 45% (138 N atoms) have bond-angle sums in the range 352–359°, with hybridization close to sp2. For the orientation of the LEP with respect to the P=S group, the anti orientation was found to be a general rule for N atoms, with the corresponding bond-angle sums deviating by more than 8° from the planar value of 360°. In the title structure, the S atom takes part in intermolecular (N—H)(N—H)S hydrogen bonds, connecting the molecules into extended chains parallel to the b axis. The co-operation of one N atom in an N—HS hydrogen bond as an H-atom donor, and in an N—HN hydrogen bond as an acceptor, is a novel feature of the crystal structure.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615004453/fn3190sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615004453/fn3190Isup2.hkl |
CCDC reference: 1052022
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: SUPERFLIP (Palatinus & Chapuis 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2014); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: enCIFer (Allen et al., 2004.
N,N',N''-Tribenzylphosphorothioic triamide top
Crystal data top
C21H24N3PS | F(000) = 808 |
Mr = 381.5 | Dx = 1.273 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: -P 2ybc | Cell parameters from 4793 reflections |
a = 19.1669 (10) Å | θ = 4.2–66.9° |
b = 4.9965 (2) Å | µ = 2.26 mm−1 |
c = 21.2416 (11) Å | T = 120 K |
β = 101.946 (4)° | Prism, colourless |
V = 1990.20 (17) Å3 | 0.42 × 0.27 × 0.22 mm |
Z = 4 |
Data collection top
Oxford Xcalibur Gemini ultra diffractometer with Atlas detector [OK?] | 3443 independent reflections |
Radiation source: X-ray tube | 2891 reflections with I > 3σ(I) |
Mirror monochromator | Rint = 0.049 |
Detector resolution: 5.1892 pixels mm-1 | θmax = 67.0°, θmin = 4.3° |
ω scans | h = −22→22 |
Absorption correction: analytical (CrysAlis PRO; Agilent, 2014) | k = −5→4 |
Tmin = 0.536, Tmax = 0.682 | l = −24→17 |
6594 measured reflections |
Refinement top
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
R[F > 3σ(F)] = 0.055 | Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0016I2] |
wR(F) = 0.138 | (Δ/σ)max = 0.012 |
S = 1.85 | Δρmax = 0.46 e Å−3 |
3443 reflections | Δρmin = −0.40 e Å−3 |
245 parameters | Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974a,b) |
3 restraints | Extinction coefficient: 1400 (300) |
87 constraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
S1 | 0.19132 (3) | 0.37255 (12) | 0.07551 (3) | 0.0232 (2) | |
P1 | 0.22306 (3) | 0.61578 (12) | 0.01467 (3) | 0.0188 (2) | |
N1 | 0.28463 (11) | 0.8412 (4) | 0.04528 (10) | 0.0219 (6) | |
C1 | 0.34904 (14) | 0.7389 (5) | 0.08933 (13) | 0.0298 (8) | |
C2 | 0.40189 (13) | 0.9603 (5) | 0.11005 (12) | 0.0246 (8) | |
C3 | 0.44503 (15) | 1.0533 (6) | 0.06967 (15) | 0.0345 (9) | |
C4 | 0.49425 (15) | 1.2569 (6) | 0.08949 (17) | 0.0406 (10) | |
C5 | 0.50043 (15) | 1.3698 (5) | 0.14982 (16) | 0.0363 (9) | |
C6 | 0.45723 (16) | 1.2806 (6) | 0.18998 (14) | 0.0354 (9) | |
C7 | 0.40819 (15) | 1.0786 (5) | 0.16994 (13) | 0.0298 (8) | |
N2 | 0.25592 (12) | 0.4394 (4) | −0.03717 (10) | 0.0251 (7) | |
C8 | 0.29064 (17) | 0.5619 (6) | −0.08539 (14) | 0.0378 (10) | |
C9 | 0.28320 (15) | 0.3861 (5) | −0.14406 (13) | 0.0280 (9) | |
C10 | 0.22378 (16) | 0.4065 (6) | −0.19432 (14) | 0.0341 (9) | |
C11 | 0.21634 (16) | 0.2440 (6) | −0.24715 (14) | 0.0381 (10) | |
C12 | 0.26748 (18) | 0.0542 (6) | −0.25150 (13) | 0.0381 (10) | |
C13 | 0.32698 (17) | 0.0300 (6) | −0.20216 (14) | 0.0371 (10) | |
C14 | 0.33483 (15) | 0.1960 (6) | −0.14900 (13) | 0.0310 (9) | |
N3 | 0.16183 (11) | 0.8151 (4) | −0.02715 (10) | 0.0243 (7) | |
C15 | 0.09230 (14) | 0.6978 (5) | −0.05676 (13) | 0.0320 (9) | |
C16 | 0.04654 (14) | 0.8978 (5) | −0.09974 (12) | 0.0243 (8) | |
C17 | 0.07197 (14) | 1.0349 (5) | −0.14721 (13) | 0.0279 (8) | |
C18 | 0.02926 (15) | 1.2168 (6) | −0.18673 (13) | 0.0312 (9) | |
C19 | −0.03972 (15) | 1.2638 (6) | −0.17896 (13) | 0.0338 (9) | |
C20 | −0.06537 (16) | 1.1280 (6) | −0.13231 (14) | 0.0367 (10) | |
C21 | −0.02288 (15) | 0.9466 (6) | −0.09281 (13) | 0.0323 (9) | |
H1C1 | 0.370603 | 0.60186 | 0.068039 | 0.0357* | |
H2C1 | 0.335855 | 0.661116 | 0.126509 | 0.0357* | |
H1C3 | 0.440863 | 0.976289 | 0.02765 | 0.0414* | |
H1C4 | 0.523932 | 1.318974 | 0.061238 | 0.0487* | |
H1C5 | 0.534579 | 1.509347 | 0.163687 | 0.0435* | |
H1C6 | 0.461173 | 1.35875 | 0.231862 | 0.0425* | |
H1C7 | 0.378008 | 1.019516 | 0.198053 | 0.0357* | |
H1C8 | 0.340274 | 0.589464 | −0.067162 | 0.0454* | |
H2C8 | 0.269422 | 0.733188 | −0.097633 | 0.0454* | |
H1C10 | 0.187545 | 0.536349 | −0.191824 | 0.041* | |
H1C11 | 0.175257 | 0.262172 | −0.281454 | 0.0457* | |
H1C12 | 0.261829 | −0.060389 | −0.288496 | 0.0457* | |
H1C13 | 0.362716 | −0.101717 | −0.204831 | 0.0446* | |
H1C14 | 0.376405 | 0.179835 | −0.115136 | 0.0372* | |
H1C15 | 0.068297 | 0.640922 | −0.023634 | 0.0384* | |
H2C15 | 0.09954 | 0.543337 | −0.08152 | 0.0384* | |
H1C17 | 0.119755 | 1.003223 | −0.152701 | 0.0335* | |
H1C18 | 0.047383 | 1.310142 | −0.219454 | 0.0374* | |
H1C19 | −0.069419 | 1.39067 | −0.206058 | 0.0406* | |
H1C20 | −0.113258 | 1.159547 | −0.127111 | 0.044* | |
H1C21 | −0.041423 | 0.853396 | −0.060298 | 0.0388* | |
H1N1 | 0.2686 (15) | 0.984 (3) | 0.0619 (12) | 0.0263* | |
H1N2 | 0.2607 (16) | 0.2649 (9) | −0.0327 (14) | 0.0301* | |
H1N3 | 0.1599 (16) | 0.974 (3) | −0.0096 (13) | 0.0292* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0278 (3) | 0.0191 (4) | 0.0243 (3) | 0.0017 (2) | 0.0091 (2) | 0.0015 (2) |
P1 | 0.0205 (3) | 0.0153 (4) | 0.0206 (3) | −0.0006 (2) | 0.0040 (2) | −0.0009 (2) |
N1 | 0.0231 (11) | 0.0143 (10) | 0.0267 (10) | 0.0010 (8) | 0.0012 (9) | −0.0016 (8) |
C1 | 0.0255 (13) | 0.0222 (14) | 0.0374 (14) | 0.0007 (11) | −0.0034 (11) | 0.0004 (11) |
C2 | 0.0185 (12) | 0.0184 (13) | 0.0339 (13) | 0.0036 (10) | −0.0013 (10) | 0.0003 (11) |
C3 | 0.0309 (14) | 0.0331 (15) | 0.0415 (16) | −0.0013 (12) | 0.0123 (12) | −0.0082 (13) |
C4 | 0.0272 (14) | 0.0351 (17) | 0.063 (2) | −0.0024 (12) | 0.0185 (14) | −0.0014 (15) |
C5 | 0.0225 (13) | 0.0246 (15) | 0.0555 (18) | −0.0004 (11) | −0.0060 (13) | −0.0022 (13) |
C6 | 0.0404 (16) | 0.0273 (15) | 0.0322 (14) | 0.0002 (12) | −0.0071 (12) | −0.0017 (12) |
C7 | 0.0331 (15) | 0.0245 (14) | 0.0302 (14) | −0.0007 (11) | 0.0028 (11) | 0.0033 (11) |
N2 | 0.0348 (12) | 0.0163 (11) | 0.0271 (11) | −0.0043 (9) | 0.0133 (9) | −0.0020 (9) |
C8 | 0.0493 (18) | 0.0339 (16) | 0.0372 (15) | −0.0155 (14) | 0.0250 (14) | −0.0087 (13) |
C9 | 0.0347 (14) | 0.0246 (14) | 0.0296 (13) | −0.0062 (11) | 0.0178 (12) | 0.0000 (10) |
C10 | 0.0300 (14) | 0.0327 (16) | 0.0428 (16) | 0.0018 (12) | 0.0149 (13) | 0.0015 (12) |
C11 | 0.0370 (16) | 0.0438 (18) | 0.0325 (14) | −0.0042 (14) | 0.0050 (12) | 0.0028 (13) |
C12 | 0.0550 (19) | 0.0371 (16) | 0.0258 (14) | −0.0031 (14) | 0.0168 (13) | −0.0048 (12) |
C13 | 0.0479 (18) | 0.0335 (16) | 0.0352 (15) | 0.0086 (13) | 0.0204 (13) | 0.0041 (13) |
C14 | 0.0332 (15) | 0.0343 (15) | 0.0272 (13) | −0.0003 (12) | 0.0101 (11) | 0.0048 (12) |
N3 | 0.0255 (11) | 0.0175 (11) | 0.0266 (10) | −0.0030 (9) | −0.0023 (9) | −0.0007 (8) |
C15 | 0.0294 (14) | 0.0231 (14) | 0.0376 (15) | −0.0071 (11) | −0.0067 (12) | 0.0049 (11) |
C16 | 0.0250 (13) | 0.0191 (13) | 0.0261 (12) | −0.0027 (10) | −0.0010 (10) | −0.0021 (10) |
C17 | 0.0242 (13) | 0.0270 (14) | 0.0311 (13) | 0.0011 (11) | 0.0022 (10) | 0.0004 (11) |
C18 | 0.0351 (15) | 0.0287 (15) | 0.0274 (13) | −0.0008 (12) | 0.0011 (11) | 0.0028 (11) |
C19 | 0.0318 (14) | 0.0296 (15) | 0.0355 (15) | 0.0096 (12) | −0.0033 (12) | −0.0008 (12) |
C20 | 0.0264 (14) | 0.0418 (17) | 0.0412 (16) | 0.0083 (12) | 0.0056 (12) | −0.0040 (13) |
C21 | 0.0305 (14) | 0.0352 (16) | 0.0308 (14) | −0.0019 (12) | 0.0056 (11) | 0.0001 (12) |
Geometric parameters (Å, º) top
S1—P1 | 1.9601 (9) | C9—C14 | 1.391 (4) |
P1—N1 | 1.663 (2) | C10—C11 | 1.368 (4) |
P1—N2 | 1.635 (2) | C10—H1C10 | 0.96 |
P1—N3 | 1.651 (2) | C11—C12 | 1.381 (5) |
N1—C1 | 1.477 (3) | C11—H1C11 | 0.96 |
N1—H1N1 | 0.88 (2) | C12—C13 | 1.385 (4) |
C1—C2 | 1.503 (4) | C12—H1C12 | 0.96 |
C1—H1C1 | 0.96 | C13—C14 | 1.384 (4) |
C1—H2C1 | 0.96 | C13—H1C13 | 0.96 |
C2—C3 | 1.389 (4) | C14—H1C14 | 0.96 |
C2—C7 | 1.385 (4) | N3—C15 | 1.473 (3) |
C3—C4 | 1.392 (4) | N3—H1N3 | 0.880 (17) |
C3—H1C3 | 0.96 | C15—C16 | 1.507 (3) |
C4—C5 | 1.383 (5) | C15—H1C15 | 0.96 |
C4—H1C4 | 0.96 | C15—H2C15 | 0.96 |
C5—C6 | 1.380 (5) | C16—C17 | 1.388 (4) |
C5—H1C5 | 0.96 | C16—C21 | 1.390 (4) |
C6—C7 | 1.385 (4) | C17—C18 | 1.384 (4) |
C6—H1C6 | 0.96 | C17—H1C17 | 0.96 |
C7—H1C7 | 0.96 | C18—C19 | 1.386 (4) |
N2—C8 | 1.466 (4) | C18—H1C18 | 0.96 |
N2—H1N2 | 0.880 (6) | C19—C20 | 1.373 (4) |
C8—C9 | 1.507 (4) | C19—H1C19 | 0.96 |
C8—H1C8 | 0.96 | C20—C21 | 1.381 (4) |
C8—H2C8 | 0.96 | C20—H1C20 | 0.96 |
C9—C10 | 1.394 (4) | C21—H1C21 | 0.96 |
S1—P1—N1 | 117.01 (8) | C10—C9—C14 | 118.2 (2) |
S1—P1—N2 | 108.98 (8) | C9—C10—C11 | 121.0 (3) |
S1—P1—N3 | 116.47 (9) | C9—C10—H1C10 | 119.51 |
N1—P1—N2 | 106.69 (12) | C11—C10—H1C10 | 119.51 |
N1—P1—N3 | 99.76 (10) | C10—C11—C12 | 120.5 (3) |
N2—P1—N3 | 107.02 (11) | C10—C11—H1C11 | 119.75 |
P1—N1—C1 | 116.45 (16) | C12—C11—H1C11 | 119.75 |
P1—N1—H1N1 | 115.3 (17) | C11—C12—C13 | 119.6 (3) |
C1—N1—H1N1 | 110.0 (16) | C11—C12—H1C12 | 120.2 |
N1—C1—C2 | 110.8 (2) | C13—C12—H1C12 | 120.2 |
N1—C1—H1C1 | 109.47 | C12—C13—C14 | 119.9 (3) |
N1—C1—H2C1 | 109.47 | C12—C13—H1C13 | 120.05 |
C2—C1—H1C1 | 109.47 | C14—C13—H1C13 | 120.05 |
C2—C1—H2C1 | 109.47 | C9—C14—C13 | 120.8 (2) |
H1C1—C1—H2C1 | 108.11 | C9—C14—H1C14 | 119.61 |
C1—C2—C3 | 121.1 (2) | C13—C14—H1C14 | 119.61 |
C1—C2—C7 | 120.6 (3) | P1—N3—C15 | 117.98 (17) |
C3—C2—C7 | 118.3 (2) | P1—N3—H1N3 | 113.8 (16) |
C2—C3—C4 | 120.7 (3) | C15—N3—H1N3 | 115 (2) |
C2—C3—H1C3 | 119.65 | N3—C15—C16 | 110.9 (2) |
C4—C3—H1C3 | 119.65 | N3—C15—H1C15 | 109.47 |
C3—C4—C5 | 120.1 (3) | N3—C15—H2C15 | 109.47 |
C3—C4—H1C4 | 119.96 | C16—C15—H1C15 | 109.47 |
C5—C4—H1C4 | 119.96 | C16—C15—H2C15 | 109.47 |
C4—C5—C6 | 119.6 (3) | H1C15—C15—H2C15 | 108.01 |
C4—C5—H1C5 | 120.2 | C15—C16—C17 | 121.3 (2) |
C6—C5—H1C5 | 120.2 | C15—C16—C21 | 120.1 (2) |
C5—C6—C7 | 120.1 (3) | C17—C16—C21 | 118.6 (2) |
C5—C6—H1C6 | 119.96 | C16—C17—C18 | 120.8 (3) |
C7—C6—H1C6 | 119.96 | C16—C17—H1C17 | 119.61 |
C2—C7—C6 | 121.2 (3) | C18—C17—H1C17 | 119.61 |
C2—C7—H1C7 | 119.4 | C17—C18—C19 | 119.9 (3) |
C6—C7—H1C7 | 119.4 | C17—C18—H1C18 | 120.06 |
P1—N2—C8 | 122.66 (18) | C19—C18—H1C18 | 120.06 |
P1—N2—H1N2 | 120 (2) | C18—C19—C20 | 119.7 (3) |
C8—N2—H1N2 | 116 (2) | C18—C19—H1C19 | 120.17 |
N2—C8—C9 | 110.8 (2) | C20—C19—H1C19 | 120.17 |
N2—C8—H1C8 | 109.47 | C19—C20—C21 | 120.6 (3) |
N2—C8—H2C8 | 109.47 | C19—C20—H1C20 | 119.71 |
C9—C8—H1C8 | 109.47 | C21—C20—H1C20 | 119.71 |
C9—C8—H2C8 | 109.47 | C16—C21—C20 | 120.5 (3) |
H1C8—C8—H2C8 | 108.07 | C16—C21—H1C21 | 119.74 |
C8—C9—C10 | 120.9 (3) | C20—C21—H1C21 | 119.74 |
C8—C9—C14 | 120.9 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···S1i | 0.88 (2) | 2.49 (2) | 3.337 (2) | 161 (2) |
N2—H1N2···N1ii | 0.880 (6) | 2.668 (17) | 3.450 (3) | 149 (2) |
N3—H1N3···S1i | 0.880 (17) | 2.67 (2) | 3.510 (2) | 159 (2) |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z. |