2-[(Di-methyl-phenyl-phosphanyl-idene)aza-nium-yl]-5-methyl-benzene-sulfonate benzene monosolvate.

The title compound, C15H18NO3PS·C6H6, is a rare example of a crystallographically characterized exocyclic phosphiniminium-arene-sulfonate zwitterion, which crystallises as its benzene solvate. The crystal structure shows that the N atom is protonated and that the iminium H atom forms both intra- and inter-molecular hydrogen bonds to the single-bonded sulfonate O atom in an R 2 (2)(4) graph-set motif. The dihedral angle between the aromatic rings in the main molecule is 89.49 (8)°.

Related literature

For background to this class of compound, see: Brown et al. (2007 ▶); Bruneau & Achard (2012 ▶); Drent et al. (2002 ▶); Lee & Hoveyda (2009 ▶); Lee et al. (2008 ▶, 2009 ▶); Nakamura et al. (2009 ▶). For related structures, see: Burns et al. (2012 ▶); Liu et al. (1995 ▶); Perrotin et al. (2011 ▶); Spencer et al. (2003 ▶); Wallis et al. (2009 ▶, 2010 ▶); Zhang et al. (2006 ▶); Zhou & Jordan (2011 ▶). For hydrogen-bonding details, see: Desiraju (1995 ▶).

Experimental

Crystal data

C15H18NO3PS·C6H6

M = 401.44

Triclinic,

a = 9.3696 (2) Å

b = 10.3141 (2) Å

c = 11.7579 (3) Å

α = 68.665 (2)°

β = 78.180 (2)°

γ = 70.630 (2)°

V = 993.89 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.27 mm−1

T = 100 K

0.41 × 0.31 × 0.25 mm

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.939, T max = 1.000

22626 measured reflections

5263 independent reflections

4918 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.096

S = 1.05

5263 reflections

251 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.40 e Å−3

Δρmin = −0.42 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813013755/pk2483sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813013755/pk2483Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813013755/pk2483Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H18NO3PS·C6H6	Z = 2
Mr = 401.44	F(000) = 424
Triclinic, P1	Dx = 1.341 Mg m−3
Hall symbol: -P 1	Melting point: 490 K
a = 9.3696 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3141 (2) Å	Cell parameters from 16324 reflections
c = 11.7579 (3) Å	θ = 3.3–29.0°
α = 68.665 (2)°	µ = 0.27 mm−1
β = 78.180 (2)°	T = 100 K
γ = 70.630 (2)°	Prism, colorless
V = 993.89 (4) Å3	0.41 × 0.31 × 0.25 mm

Agilent Xcalibur (Ruby, Gemini) diffractometer	5263 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4918 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
Detector resolution: 10.2836 pixels mm-1	θmax = 29.1°, θmin = 3.3°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −13→13
Tmin = 0.939, Tmax = 1.000	l = −16→16
22626 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0264P)2 + 1.4298P] where P = (Fo2 + 2Fc2)/3
5263 reflections	(Δ/σ)max = 0.001
251 parameters	Δρmax = 1.40 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

	x	y	z	Uiso*/Ueq
S1	0.24462 (4)	0.76594 (4)	0.45953 (3)	0.01262 (9)
P1	0.71909 (4)	0.68470 (4)	0.55802 (3)	0.01128 (9)
O1	0.28714 (14)	0.88299 (13)	0.35938 (11)	0.0211 (2)
O2	0.34682 (13)	0.62271 (12)	0.46153 (11)	0.0181 (2)
O3	0.08543 (12)	0.77151 (14)	0.47013 (11)	0.0200 (2)
N1	0.54554 (14)	0.67514 (14)	0.56918 (12)	0.0135 (2)
H1N	0.530 (3)	0.632 (3)	0.531 (2)	0.027 (6)*
C1	0.27173 (16)	0.78953 (15)	0.59586 (13)	0.0119 (3)
C2	0.14789 (16)	0.86274 (16)	0.65917 (14)	0.0139 (3)
H2	0.0516	0.8904	0.6336	0.017*
C3	0.16470 (17)	0.89556 (16)	0.75995 (14)	0.0155 (3)
C4	0.30965 (18)	0.84905 (17)	0.79818 (14)	0.0171 (3)
H4	0.3235	0.8684	0.8658	0.021*
C5	0.43403 (17)	0.77421 (17)	0.73725 (14)	0.0156 (3)
H5	0.5294	0.7428	0.7655	0.019*
C6	0.41761 (16)	0.74565 (15)	0.63435 (13)	0.0125 (3)
C7	0.03151 (19)	0.98321 (19)	0.82218 (16)	0.0221 (3)
H7A	0.0137	0.9262	0.9060	0.033*
H7B	−0.0573	1.0103	0.7806	0.033*
H7C	0.0532	1.0690	0.8195	0.033*
C8	0.81146 (16)	0.56744 (16)	0.69318 (13)	0.0140 (3)
C9	0.92555 (18)	0.6000 (2)	0.72847 (15)	0.0210 (3)
H9	0.9523	0.6850	0.6835	0.025*
C10	0.9990 (2)	0.5043 (2)	0.83147 (17)	0.0296 (4)
H10	1.0755	0.5250	0.8552	0.036*
C11	0.9585 (2)	0.3787 (2)	0.89842 (18)	0.0329 (4)
H11	1.0074	0.3155	0.9676	0.040*
C12	0.8455 (2)	0.34585 (19)	0.86339 (17)	0.0286 (4)
H12	0.8190	0.2609	0.9090	0.034*
C13	0.77174 (19)	0.43981 (17)	0.76011 (15)	0.0191 (3)
H13	0.6966	0.4177	0.7360	0.023*
C14	0.82093 (17)	0.63095 (17)	0.42977 (14)	0.0169 (3)
H14A	0.8261	0.5318	0.4443	0.025*
H14B	0.9220	0.6403	0.4181	0.025*
H14C	0.7698	0.6918	0.3577	0.025*
C15	0.71858 (18)	0.86602 (16)	0.53121 (16)	0.0186 (3)
H15A	0.6603	0.9301	0.4637	0.028*
H15B	0.8210	0.8728	0.5121	0.028*
H15C	0.6741	0.8931	0.6034	0.028*
C16	0.6085 (3)	0.8347 (2)	0.14006 (19)	0.0392 (5)
H16	0.5942	0.8883	0.1923	0.047*
C17	0.6651 (3)	0.8839 (3)	0.0207 (2)	0.0363 (5)
H17	0.6838	0.9741	−0.0092	0.044*
C18	0.6951 (2)	0.8019 (2)	−0.05696 (18)	0.0318 (4)
H18	0.7352	0.8361	−0.1377	0.038*
C19	0.6647 (2)	0.6685 (2)	−0.01315 (18)	0.0296 (4)
H19	0.6886	0.6115	−0.0639	0.035*
C20	0.6011 (2)	0.6207 (2)	0.1021 (2)	0.0319 (4)
H20	0.5761	0.5336	0.1287	0.038*
C21	0.5720 (2)	0.7022 (2)	0.18328 (18)	0.0311 (4)
H21	0.5297	0.6686	0.2634	0.037*

	U11	U22	U33	U12	U13	U23
S1	0.01064 (16)	0.01423 (17)	0.01497 (16)	−0.00342 (12)	−0.00207 (12)	−0.00656 (13)
P1	0.00971 (16)	0.01120 (16)	0.01365 (17)	−0.00251 (12)	−0.00188 (12)	−0.00481 (13)
O1	0.0269 (6)	0.0214 (6)	0.0159 (5)	−0.0104 (5)	−0.0009 (4)	−0.0045 (4)
O2	0.0163 (5)	0.0174 (5)	0.0248 (6)	−0.0016 (4)	−0.0054 (4)	−0.0125 (4)
O3	0.0117 (5)	0.0294 (6)	0.0234 (6)	−0.0056 (4)	−0.0028 (4)	−0.0131 (5)
N1	0.0098 (5)	0.0159 (6)	0.0188 (6)	−0.0028 (4)	−0.0019 (4)	−0.0107 (5)
C1	0.0122 (6)	0.0112 (6)	0.0137 (6)	−0.0043 (5)	−0.0013 (5)	−0.0045 (5)
C2	0.0118 (6)	0.0129 (6)	0.0169 (7)	−0.0039 (5)	−0.0005 (5)	−0.0047 (5)
C3	0.0155 (7)	0.0143 (6)	0.0158 (7)	−0.0035 (5)	0.0012 (5)	−0.0059 (5)
C4	0.0198 (7)	0.0183 (7)	0.0154 (7)	−0.0044 (6)	−0.0017 (6)	−0.0085 (6)
C5	0.0134 (6)	0.0173 (7)	0.0174 (7)	−0.0027 (5)	−0.0039 (5)	−0.0072 (6)
C6	0.0115 (6)	0.0107 (6)	0.0156 (6)	−0.0031 (5)	−0.0008 (5)	−0.0048 (5)
C7	0.0186 (7)	0.0250 (8)	0.0221 (8)	−0.0009 (6)	0.0012 (6)	−0.0130 (6)
C8	0.0119 (6)	0.0151 (7)	0.0144 (6)	−0.0008 (5)	−0.0021 (5)	−0.0065 (5)
C9	0.0152 (7)	0.0303 (9)	0.0206 (7)	−0.0075 (6)	−0.0026 (6)	−0.0102 (7)
C10	0.0191 (8)	0.0455 (11)	0.0260 (9)	−0.0008 (7)	−0.0100 (7)	−0.0166 (8)
C11	0.0346 (10)	0.0329 (10)	0.0227 (9)	0.0095 (8)	−0.0151 (7)	−0.0094 (7)
C12	0.0417 (11)	0.0169 (8)	0.0206 (8)	0.0001 (7)	−0.0079 (7)	−0.0033 (6)
C13	0.0234 (8)	0.0155 (7)	0.0184 (7)	−0.0037 (6)	−0.0037 (6)	−0.0061 (6)
C14	0.0146 (7)	0.0204 (7)	0.0159 (7)	−0.0039 (6)	0.0004 (5)	−0.0078 (6)
C15	0.0174 (7)	0.0121 (7)	0.0266 (8)	−0.0046 (5)	−0.0031 (6)	−0.0058 (6)
C16	0.0531 (13)	0.0367 (11)	0.0249 (9)	−0.0015 (10)	−0.0034 (9)	−0.0168 (8)
C17	0.0350 (11)	0.0372 (11)	0.0396 (11)	−0.0124 (9)	−0.0016 (9)	−0.0145 (9)
C18	0.0265 (9)	0.0423 (11)	0.0248 (9)	−0.0089 (8)	−0.0007 (7)	−0.0104 (8)
C19	0.0248 (9)	0.0381 (10)	0.0286 (9)	−0.0033 (8)	−0.0065 (7)	−0.0167 (8)
C20	0.0221 (9)	0.0338 (10)	0.0443 (11)	−0.0117 (7)	0.0074 (8)	−0.0199 (9)
C21	0.0268 (9)	0.0488 (12)	0.0215 (8)	−0.0143 (8)	0.0017 (7)	−0.0144 (8)

S1—O1	1.4474 (12)	C9—H9	0.9300
S1—O3	1.4547 (11)	C10—C11	1.380 (3)
S1—O2	1.4648 (11)	C10—H10	0.9300
S1—O2	1.4648 (11)	C11—C12	1.387 (3)
S1—C1	1.7845 (15)	C11—H11	0.9300
P1—N1	1.6373 (13)	C12—C13	1.391 (2)
P1—C14	1.7776 (15)	C12—H12	0.9300
P1—C15	1.7783 (16)	C13—H13	0.9300
P1—C8	1.7911 (15)	C14—H14A	0.9600
N1—C6	1.4155 (18)	C14—H14B	0.9600
N1—H1N	0.80 (2)	C14—H14C	0.9600
C1—C2	1.395 (2)	C15—H15A	0.9600
C1—C6	1.4043 (19)	C15—H15B	0.9600
C2—C3	1.395 (2)	C15—H15C	0.9600
C2—H2	0.9300	C16—C17	1.365 (3)
C3—C4	1.392 (2)	C16—C21	1.406 (3)
C3—C7	1.506 (2)	C16—H16	0.9300
C4—C5	1.390 (2)	C17—C18	1.388 (3)
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.393 (2)	C18—C19	1.386 (3)
C5—H5	0.9300	C18—H18	0.9300
C7—H7A	0.9600	C19—C20	1.346 (3)
C7—H7B	0.9600	C19—H19	0.9300
C7—H7C	0.9600	C20—C21	1.421 (3)
C8—C13	1.394 (2)	C20—H20	0.9300
C8—C9	1.396 (2)	C21—H21	0.9300
C9—C10	1.391 (2)
O1—S1—O3	114.14 (7)	C10—C9—C8	119.49 (17)
O1—S1—O2	112.97 (7)	C10—C9—H9	120.3
O3—S1—O2	112.35 (7)	C8—C9—H9	120.3
O1—S1—O2	112.97 (7)	C11—C10—C9	120.11 (17)
O3—S1—O2	112.35 (7)	C11—C10—H10	119.9
O1—S1—C1	105.48 (7)	C9—C10—H10	119.9
O3—S1—C1	106.09 (7)	C10—C11—C12	120.53 (17)
O2—S1—C1	104.84 (7)	C10—C11—H11	119.7
O2—S1—C1	104.84 (7)	C12—C11—H11	119.7
N1—P1—C14	107.43 (7)	C11—C12—C13	120.10 (18)
N1—P1—C15	110.52 (7)	C11—C12—H12	120.0
C14—P1—C15	108.36 (8)	C13—C12—H12	120.0
N1—P1—C8	111.53 (7)	C12—C13—C8	119.40 (16)
C14—P1—C8	109.37 (7)	C12—C13—H13	120.3
C15—P1—C8	109.55 (7)	C8—C13—H13	120.3
C6—N1—P1	125.47 (10)	P1—C14—H14A	109.5
C6—N1—H1N	116.5 (17)	P1—C14—H14B	109.5
P1—N1—H1N	117.9 (17)	H14A—C14—H14B	109.5
C2—C1—C6	119.74 (13)	P1—C14—H14C	109.5
C2—C1—S1	119.26 (11)	H14A—C14—H14C	109.5
C6—C1—S1	120.80 (11)	H14B—C14—H14C	109.5
C1—C2—C3	121.75 (14)	P1—C15—H15A	109.5
C1—C2—H2	119.1	P1—C15—H15B	109.5
C3—C2—H2	119.1	H15A—C15—H15B	109.5
C4—C3—C2	117.74 (14)	P1—C15—H15C	109.5
C4—C3—C7	121.16 (14)	H15A—C15—H15C	109.5
C2—C3—C7	121.05 (14)	H15B—C15—H15C	109.5
C5—C4—C3	121.29 (14)	C17—C16—C21	119.3 (2)
C5—C4—H4	119.4	C17—C16—H16	120.3
C3—C4—H4	119.4	C21—C16—H16	120.3
C4—C5—C6	120.79 (14)	C16—C17—C18	121.3 (2)
C4—C5—H5	119.6	C16—C17—H17	119.4
C6—C5—H5	119.6	C18—C17—H17	119.4
C5—C6—C1	118.64 (13)	C19—C18—C17	119.44 (19)
C5—C6—N1	120.69 (13)	C19—C18—H18	120.3
C1—C6—N1	120.67 (13)	C17—C18—H18	120.3
C3—C7—H7A	109.5	C20—C19—C18	120.70 (19)
C3—C7—H7B	109.5	C20—C19—H19	119.7
H7A—C7—H7B	109.5	C18—C19—H19	119.7
C3—C7—H7C	109.5	C19—C20—C21	120.49 (19)
H7A—C7—H7C	109.5	C19—C20—H20	119.8
H7B—C7—H7C	109.5	C21—C20—H20	119.8
C13—C8—C9	120.36 (15)	C16—C21—C20	118.63 (18)
C13—C8—P1	118.82 (12)	C16—C21—H21	120.7
C9—C8—P1	120.78 (12)	C20—C21—H21	120.7
O1—S1—O2—O2	0.00 (7)	C2—C1—C6—N1	−178.06 (13)
O3—S1—O2—O2	0.00 (4)	S1—C1—C6—N1	−3.16 (19)
C1—S1—O2—O2	0.00 (6)	P1—N1—C6—C5	−29.7 (2)
C14—P1—N1—C6	−160.95 (12)	P1—N1—C6—C1	149.70 (12)
C15—P1—N1—C6	−42.91 (15)	N1—P1—C8—C13	30.59 (14)
C8—P1—N1—C6	79.22 (14)	C14—P1—C8—C13	−88.10 (13)
O1—S1—C1—C2	96.24 (13)	C15—P1—C8—C13	153.27 (12)
O3—S1—C1—C2	−25.20 (13)	N1—P1—C8—C9	−151.94 (12)
O2—S1—C1—C2	−144.27 (12)	C14—P1—C8—C9	89.38 (14)
O2—S1—C1—C2	−144.27 (12)	C15—P1—C8—C9	−29.26 (15)
O1—S1—C1—C6	−78.68 (13)	C13—C8—C9—C10	−0.3 (2)
O3—S1—C1—C6	159.88 (12)	P1—C8—C9—C10	−177.74 (13)
O2—S1—C1—C6	40.81 (13)	C8—C9—C10—C11	−0.4 (3)
O2—S1—C1—C6	40.81 (13)	C9—C10—C11—C12	0.5 (3)
C6—C1—C2—C3	0.7 (2)	C10—C11—C12—C13	−0.1 (3)
S1—C1—C2—C3	−174.27 (11)	C11—C12—C13—C8	−0.6 (3)
C1—C2—C3—C4	−1.8 (2)	C9—C8—C13—C12	0.8 (2)
C1—C2—C3—C7	175.96 (14)	P1—C8—C13—C12	178.27 (13)
C2—C3—C4—C5	0.9 (2)	C21—C16—C17—C18	−3.6 (4)
C7—C3—C4—C5	−176.87 (15)	C16—C17—C18—C19	1.1 (3)
C3—C4—C5—C6	1.1 (2)	C17—C18—C19—C20	2.6 (3)
C4—C5—C6—C1	−2.2 (2)	C18—C19—C20—C21	−3.7 (3)
C4—C5—C6—N1	177.15 (14)	C17—C16—C21—C20	2.5 (3)
C2—C1—C6—C5	1.3 (2)	C19—C20—C21—C16	1.1 (3)
S1—C1—C6—C5	176.21 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.80 (2)	2.09 (2)	2.7374 (17)	139 (2)
N1—H1N···O2i	0.80 (2)	2.47 (2)	3.0311 (17)	128 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2	0.80 (2)	2.09 (2)	2.7374 (17)	139 (2)
N1—H1N⋯O2i	0.80 (2)	2.47 (2)	3.0311 (17)	128 (2)

Symmetry code: (i) .