Download citation
Download citation
link to html
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—H...S hydrogen bond as an H-atom donor, and in an N—H...N hydrogen bond as an acceptor, is a novel feature of the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615004453/fn3190sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615004453/fn3190Isup2.hkl
Contains datablock I

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
C21H24N3PSF(000) = 808
Mr = 381.5Dx = 1.273 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybcCell parameters from 4793 reflections
a = 19.1669 (10) Åθ = 4.2–66.9°
b = 4.9965 (2) ŵ = 2.26 mm1
c = 21.2416 (11) ÅT = 120 K
β = 101.946 (4)°Prism, colourless
V = 1990.20 (17) Å30.42 × 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 tube2891 reflections with I > 3σ(I)
Mirror monochromatorRint = 0.049
Detector resolution: 5.1892 pixels mm-1θmax = 67.0°, θmin = 4.3°
ω scansh = 2222
Absorption correction: analytical
(CrysAlis PRO; Agilent, 2014)
k = 54
Tmin = 0.536, Tmax = 0.682l = 2417
6594 measured reflections
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
R[F > 3σ(F)] = 0.055Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0016I2]
wR(F) = 0.138(Δ/σ)max = 0.012
S = 1.85Δρmax = 0.46 e Å3
3443 reflectionsΔρmin = 0.40 e Å3
245 parametersExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974a,b)
3 restraintsExtinction coefficient: 1400 (300)
87 constraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.19132 (3)0.37255 (12)0.07551 (3)0.0232 (2)
P10.22306 (3)0.61578 (12)0.01467 (3)0.0188 (2)
N10.28463 (11)0.8412 (4)0.04528 (10)0.0219 (6)
C10.34904 (14)0.7389 (5)0.08933 (13)0.0298 (8)
C20.40189 (13)0.9603 (5)0.11005 (12)0.0246 (8)
C30.44503 (15)1.0533 (6)0.06967 (15)0.0345 (9)
C40.49425 (15)1.2569 (6)0.08949 (17)0.0406 (10)
C50.50043 (15)1.3698 (5)0.14982 (16)0.0363 (9)
C60.45723 (16)1.2806 (6)0.18998 (14)0.0354 (9)
C70.40819 (15)1.0786 (5)0.16994 (13)0.0298 (8)
N20.25592 (12)0.4394 (4)0.03717 (10)0.0251 (7)
C80.29064 (17)0.5619 (6)0.08539 (14)0.0378 (10)
C90.28320 (15)0.3861 (5)0.14406 (13)0.0280 (9)
C100.22378 (16)0.4065 (6)0.19432 (14)0.0341 (9)
C110.21634 (16)0.2440 (6)0.24715 (14)0.0381 (10)
C120.26748 (18)0.0542 (6)0.25150 (13)0.0381 (10)
C130.32698 (17)0.0300 (6)0.20216 (14)0.0371 (10)
C140.33483 (15)0.1960 (6)0.14900 (13)0.0310 (9)
N30.16183 (11)0.8151 (4)0.02715 (10)0.0243 (7)
C150.09230 (14)0.6978 (5)0.05676 (13)0.0320 (9)
C160.04654 (14)0.8978 (5)0.09974 (12)0.0243 (8)
C170.07197 (14)1.0349 (5)0.14721 (13)0.0279 (8)
C180.02926 (15)1.2168 (6)0.18673 (13)0.0312 (9)
C190.03972 (15)1.2638 (6)0.17896 (13)0.0338 (9)
C200.06537 (16)1.1280 (6)0.13231 (14)0.0367 (10)
C210.02288 (15)0.9466 (6)0.09281 (13)0.0323 (9)
H1C10.3706030.601860.0680390.0357*
H2C10.3358550.6611160.1265090.0357*
H1C30.4408630.9762890.027650.0414*
H1C40.5239321.3189740.0612380.0487*
H1C50.5345791.5093470.1636870.0435*
H1C60.4611731.358750.2318620.0425*
H1C70.3780081.0195160.1980530.0357*
H1C80.3402740.5894640.0671620.0454*
H2C80.2694220.7331880.0976330.0454*
H1C100.1875450.5363490.1918240.041*
H1C110.1752570.2621720.2814540.0457*
H1C120.2618290.0603890.2884960.0457*
H1C130.3627160.1017170.2048310.0446*
H1C140.3764050.1798350.1151360.0372*
H1C150.0682970.6409220.0236340.0384*
H2C150.099540.5433370.081520.0384*
H1C170.1197551.0032230.1527010.0335*
H1C180.0473831.3101420.2194540.0374*
H1C190.0694191.390670.2060580.0406*
H1C200.1132581.1595470.1271110.044*
H1C210.0414230.8533960.0602980.0388*
H1N10.2686 (15)0.984 (3)0.0619 (12)0.0263*
H1N20.2607 (16)0.2649 (9)0.0327 (14)0.0301*
H1N30.1599 (16)0.974 (3)0.0096 (13)0.0292*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0278 (3)0.0191 (4)0.0243 (3)0.0017 (2)0.0091 (2)0.0015 (2)
P10.0205 (3)0.0153 (4)0.0206 (3)0.0006 (2)0.0040 (2)0.0009 (2)
N10.0231 (11)0.0143 (10)0.0267 (10)0.0010 (8)0.0012 (9)0.0016 (8)
C10.0255 (13)0.0222 (14)0.0374 (14)0.0007 (11)0.0034 (11)0.0004 (11)
C20.0185 (12)0.0184 (13)0.0339 (13)0.0036 (10)0.0013 (10)0.0003 (11)
C30.0309 (14)0.0331 (15)0.0415 (16)0.0013 (12)0.0123 (12)0.0082 (13)
C40.0272 (14)0.0351 (17)0.063 (2)0.0024 (12)0.0185 (14)0.0014 (15)
C50.0225 (13)0.0246 (15)0.0555 (18)0.0004 (11)0.0060 (13)0.0022 (13)
C60.0404 (16)0.0273 (15)0.0322 (14)0.0002 (12)0.0071 (12)0.0017 (12)
C70.0331 (15)0.0245 (14)0.0302 (14)0.0007 (11)0.0028 (11)0.0033 (11)
N20.0348 (12)0.0163 (11)0.0271 (11)0.0043 (9)0.0133 (9)0.0020 (9)
C80.0493 (18)0.0339 (16)0.0372 (15)0.0155 (14)0.0250 (14)0.0087 (13)
C90.0347 (14)0.0246 (14)0.0296 (13)0.0062 (11)0.0178 (12)0.0000 (10)
C100.0300 (14)0.0327 (16)0.0428 (16)0.0018 (12)0.0149 (13)0.0015 (12)
C110.0370 (16)0.0438 (18)0.0325 (14)0.0042 (14)0.0050 (12)0.0028 (13)
C120.0550 (19)0.0371 (16)0.0258 (14)0.0031 (14)0.0168 (13)0.0048 (12)
C130.0479 (18)0.0335 (16)0.0352 (15)0.0086 (13)0.0204 (13)0.0041 (13)
C140.0332 (15)0.0343 (15)0.0272 (13)0.0003 (12)0.0101 (11)0.0048 (12)
N30.0255 (11)0.0175 (11)0.0266 (10)0.0030 (9)0.0023 (9)0.0007 (8)
C150.0294 (14)0.0231 (14)0.0376 (15)0.0071 (11)0.0067 (12)0.0049 (11)
C160.0250 (13)0.0191 (13)0.0261 (12)0.0027 (10)0.0010 (10)0.0021 (10)
C170.0242 (13)0.0270 (14)0.0311 (13)0.0011 (11)0.0022 (10)0.0004 (11)
C180.0351 (15)0.0287 (15)0.0274 (13)0.0008 (12)0.0011 (11)0.0028 (11)
C190.0318 (14)0.0296 (15)0.0355 (15)0.0096 (12)0.0033 (12)0.0008 (12)
C200.0264 (14)0.0418 (17)0.0412 (16)0.0083 (12)0.0056 (12)0.0040 (13)
C210.0305 (14)0.0352 (16)0.0308 (14)0.0019 (12)0.0056 (11)0.0001 (12)
Geometric parameters (Å, º) top
S1—P11.9601 (9)C9—C141.391 (4)
P1—N11.663 (2)C10—C111.368 (4)
P1—N21.635 (2)C10—H1C100.96
P1—N31.651 (2)C11—C121.381 (5)
N1—C11.477 (3)C11—H1C110.96
N1—H1N10.88 (2)C12—C131.385 (4)
C1—C21.503 (4)C12—H1C120.96
C1—H1C10.96C13—C141.384 (4)
C1—H2C10.96C13—H1C130.96
C2—C31.389 (4)C14—H1C140.96
C2—C71.385 (4)N3—C151.473 (3)
C3—C41.392 (4)N3—H1N30.880 (17)
C3—H1C30.96C15—C161.507 (3)
C4—C51.383 (5)C15—H1C150.96
C4—H1C40.96C15—H2C150.96
C5—C61.380 (5)C16—C171.388 (4)
C5—H1C50.96C16—C211.390 (4)
C6—C71.385 (4)C17—C181.384 (4)
C6—H1C60.96C17—H1C170.96
C7—H1C70.96C18—C191.386 (4)
N2—C81.466 (4)C18—H1C180.96
N2—H1N20.880 (6)C19—C201.373 (4)
C8—C91.507 (4)C19—H1C190.96
C8—H1C80.96C20—C211.381 (4)
C8—H2C80.96C20—H1C200.96
C9—C101.394 (4)C21—H1C210.96
S1—P1—N1117.01 (8)C10—C9—C14118.2 (2)
S1—P1—N2108.98 (8)C9—C10—C11121.0 (3)
S1—P1—N3116.47 (9)C9—C10—H1C10119.51
N1—P1—N2106.69 (12)C11—C10—H1C10119.51
N1—P1—N399.76 (10)C10—C11—C12120.5 (3)
N2—P1—N3107.02 (11)C10—C11—H1C11119.75
P1—N1—C1116.45 (16)C12—C11—H1C11119.75
P1—N1—H1N1115.3 (17)C11—C12—C13119.6 (3)
C1—N1—H1N1110.0 (16)C11—C12—H1C12120.2
N1—C1—C2110.8 (2)C13—C12—H1C12120.2
N1—C1—H1C1109.47C12—C13—C14119.9 (3)
N1—C1—H2C1109.47C12—C13—H1C13120.05
C2—C1—H1C1109.47C14—C13—H1C13120.05
C2—C1—H2C1109.47C9—C14—C13120.8 (2)
H1C1—C1—H2C1108.11C9—C14—H1C14119.61
C1—C2—C3121.1 (2)C13—C14—H1C14119.61
C1—C2—C7120.6 (3)P1—N3—C15117.98 (17)
C3—C2—C7118.3 (2)P1—N3—H1N3113.8 (16)
C2—C3—C4120.7 (3)C15—N3—H1N3115 (2)
C2—C3—H1C3119.65N3—C15—C16110.9 (2)
C4—C3—H1C3119.65N3—C15—H1C15109.47
C3—C4—C5120.1 (3)N3—C15—H2C15109.47
C3—C4—H1C4119.96C16—C15—H1C15109.47
C5—C4—H1C4119.96C16—C15—H2C15109.47
C4—C5—C6119.6 (3)H1C15—C15—H2C15108.01
C4—C5—H1C5120.2C15—C16—C17121.3 (2)
C6—C5—H1C5120.2C15—C16—C21120.1 (2)
C5—C6—C7120.1 (3)C17—C16—C21118.6 (2)
C5—C6—H1C6119.96C16—C17—C18120.8 (3)
C7—C6—H1C6119.96C16—C17—H1C17119.61
C2—C7—C6121.2 (3)C18—C17—H1C17119.61
C2—C7—H1C7119.4C17—C18—C19119.9 (3)
C6—C7—H1C7119.4C17—C18—H1C18120.06
P1—N2—C8122.66 (18)C19—C18—H1C18120.06
P1—N2—H1N2120 (2)C18—C19—C20119.7 (3)
C8—N2—H1N2116 (2)C18—C19—H1C19120.17
N2—C8—C9110.8 (2)C20—C19—H1C19120.17
N2—C8—H1C8109.47C19—C20—C21120.6 (3)
N2—C8—H2C8109.47C19—C20—H1C20119.71
C9—C8—H1C8109.47C21—C20—H1C20119.71
C9—C8—H2C8109.47C16—C21—C20120.5 (3)
H1C8—C8—H2C8108.07C16—C21—H1C21119.74
C8—C9—C10120.9 (3)C20—C21—H1C21119.74
C8—C9—C14120.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···S1i0.88 (2)2.49 (2)3.337 (2)161 (2)
N2—H1N2···N1ii0.880 (6)2.668 (17)3.450 (3)149 (2)
N3—H1N3···S1i0.880 (17)2.67 (2)3.510 (2)159 (2)
Symmetry codes: (i) x, y+1, z; (ii) x, y1, z.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds