A cocrystal of diethyl­ammonium chloride and di­phenyl­amine

The title compound, diethyl­ammonium chloride–di­phenyl­amine (1/1), C₄H₁₂N⁺·Cl⁻·C₁₂H₁₁N, consists of discrete diethyl­ammonium cations, chloride anions and di­phenyl­amine mol­ecules linked together by several N—H...Cl hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.027
• wR factor = 0.070
• Data-to-parameter ratio = 20.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The silylation of diphenylamine with 2-chloro-2,6-dimethyl-2,6-disilaheptane in pentane in the presence of diethylamine was attempted. Light yellow crystals of the title compound, (I), were obtained from the crude product mixture.

Compound (I) consists of discrete diethylammonium cations, chloride anions and diphenylamine molecules. Each chloride anion forms three hydrogen bonds (Table 2). The dihedral angle between the two aromatic rings of the diphenylamine is 37.91 (4)°.

S2. Experimental

An equimolar mixture (9 mmol) of 2-chloro-2,6-dimethyl-2,6-disilaheptane diphenylamine and diethylamine in 150 ml of pentane was heated to 309 K for 2 h. After filtration and removal of the solvent a yellow oil was obtained. Light yellow crystals of (H₅C₂)₂NH₂⁺·Cl⁻. (H₅C₆)₂NH was obtained directly from the crude reaction product upon standing for 21 d.

S3. Refinement

H atoms bonded to C atoms were refined with fixed individual displacement parameters [U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl)], using a riding model with aromatic C—H = 0.95 Å, methylene C—H = 0.99 Å or methyl C—H = 0.98 Å. H atoms bonded to N atoms were refined independently with isotropic displacement parameters.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991).

Figures

Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) 1/2 − x, 1/2 + y, 3/2 − z.]

(I)

Crystal data

C4H12N^+·Cl^−·C12H11N	F(000) = 600
Mr = 278.81	Dx = 1.148 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 19430 reflections
a = 9.0679 (6) Å	θ = 2.4–27.5°
b = 10.0077 (6) Å	µ = 0.23 mm^−1
c = 17.8386 (13) Å	T = 100 K
β = 94.726 (6)°	Block, light yellow
V = 1613.33 (19) Å^3	0.26 × 0.24 × 0.15 mm
Z = 4

Data collection

Stoe IPDS II two-circle diffractometer	3833 independent reflections
Radiation source: fine-focus sealed tube	3087 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 27.9°, θmin = 2.4°
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995)	h = −11→11
Tmin = 0.955, Tmax = 0.968	k = −13→13
27910 measured reflections	l = −23→23

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.070	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0466P)^2] where P = (Fo^2 + 2Fc^2)/3
3833 reflections	(Δ/σ)max = 0.001
184 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.40033 (12)	0.48481 (12)	0.63545 (6)	0.0338 (2)
H1A	0.4634	0.4436	0.5999	0.051*
H1B	0.3841	0.5790	0.6223	0.051*
H1C	0.3050	0.4382	0.6332	0.051*
C2	0.47500 (11)	0.47493 (11)	0.71409 (6)	0.0269 (2)
H2A	0.4922	0.3798	0.7272	0.032*
H2B	0.5723	0.5202	0.7160	0.032*
N3	0.38264 (9)	0.53766 (9)	0.76999 (5)	0.02447 (18)
H3A	0.3703 (14)	0.6254 (15)	0.7583 (7)	0.034 (3)*
H3B	0.2926 (16)	0.4963 (15)	0.7659 (7)	0.037 (3)*
C4	0.44610 (12)	0.52422 (12)	0.84949 (6)	0.0307 (2)
H4A	0.5479	0.5607	0.8545	0.037*
H4B	0.4511	0.4286	0.8637	0.037*
C5	0.35150 (16)	0.59856 (14)	0.90146 (7)	0.0442 (3)
H5A	0.3949	0.5900	0.9534	0.066*
H5B	0.2515	0.5607	0.8974	0.066*
H5C	0.3467	0.6932	0.8873	0.066*
Cl1	0.38089 (2)	0.84251 (2)	0.724177 (15)	0.02832 (8)
N1	0.73130 (9)	0.75457 (9)	0.74821 (5)	0.02451 (18)
H1	0.6484 (15)	0.7948 (14)	0.7426 (7)	0.032 (3)*
C11	0.77637 (10)	0.72692 (10)	0.82350 (5)	0.02177 (19)
C12	0.72848 (11)	0.81509 (10)	0.87765 (6)	0.0250 (2)
H12	0.6731	0.8922	0.8621	0.030*
C13	0.76118 (11)	0.79075 (11)	0.95344 (6)	0.0291 (2)
H13	0.7273	0.8509	0.9895	0.035*
C14	0.84321 (12)	0.67899 (12)	0.97758 (6)	0.0328 (2)
H14	0.8660	0.6624	1.0297	0.039*
C15	0.89117 (13)	0.59205 (12)	0.92385 (6)	0.0344 (2)
H15	0.9474	0.5155	0.9397	0.041*
C16	0.85866 (11)	0.61467 (10)	0.84744 (6)	0.0274 (2)
H16	0.8923	0.5540	0.8116	0.033*
C21	0.79040 (10)	0.71156 (9)	0.68263 (5)	0.02151 (18)
C22	0.93418 (10)	0.66203 (10)	0.67961 (6)	0.02491 (19)
H22	0.9968	0.6510	0.7246	0.030*
C23	0.98511 (11)	0.62898 (10)	0.61048 (6)	0.0285 (2)
H23	1.0830	0.5958	0.6089	0.034*
C24	0.89636 (12)	0.64337 (11)	0.54398 (6)	0.0303 (2)
H24	0.9325	0.6203	0.4972	0.036*
C25	0.75338 (12)	0.69221 (11)	0.54701 (6)	0.0295 (2)
H25	0.6913	0.7026	0.5018	0.035*
C26	0.70081 (10)	0.72573 (10)	0.61511 (6)	0.0252 (2)
H26	0.6028	0.7588	0.6162	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0301 (5)	0.0385 (6)	0.0328 (6)	−0.0009 (4)	0.0033 (4)	−0.0039 (5)
C2	0.0230 (4)	0.0264 (5)	0.0319 (5)	0.0024 (4)	0.0070 (4)	−0.0007 (4)
N3	0.0220 (4)	0.0204 (4)	0.0315 (5)	−0.0020 (3)	0.0057 (3)	−0.0013 (3)
C4	0.0323 (5)	0.0305 (5)	0.0295 (5)	−0.0063 (4)	0.0036 (4)	−0.0020 (4)
C5	0.0581 (8)	0.0387 (7)	0.0375 (6)	−0.0029 (6)	0.0146 (6)	−0.0081 (5)
Cl1	0.02135 (11)	0.02205 (12)	0.04200 (14)	0.00366 (8)	0.00532 (9)	0.00230 (10)
N1	0.0207 (4)	0.0290 (4)	0.0238 (4)	0.0070 (3)	0.0015 (3)	−0.0004 (3)
C11	0.0195 (4)	0.0223 (5)	0.0235 (5)	−0.0014 (3)	0.0020 (3)	0.0001 (4)
C12	0.0246 (4)	0.0236 (5)	0.0273 (5)	0.0031 (3)	0.0052 (4)	−0.0002 (4)
C13	0.0306 (5)	0.0313 (5)	0.0259 (5)	0.0011 (4)	0.0055 (4)	−0.0036 (4)
C14	0.0359 (5)	0.0382 (6)	0.0237 (5)	0.0037 (4)	−0.0009 (4)	0.0012 (4)
C15	0.0399 (6)	0.0320 (6)	0.0302 (6)	0.0103 (5)	−0.0036 (4)	0.0020 (4)
C16	0.0300 (5)	0.0244 (5)	0.0275 (5)	0.0047 (4)	0.0003 (4)	−0.0031 (4)
C21	0.0227 (4)	0.0179 (4)	0.0243 (5)	−0.0010 (3)	0.0041 (3)	−0.0001 (3)
C22	0.0223 (4)	0.0234 (5)	0.0290 (5)	0.0011 (4)	0.0017 (4)	−0.0013 (4)
C23	0.0262 (5)	0.0247 (5)	0.0357 (6)	0.0032 (4)	0.0092 (4)	0.0000 (4)
C24	0.0374 (5)	0.0276 (5)	0.0274 (5)	0.0023 (4)	0.0123 (4)	−0.0001 (4)
C25	0.0341 (5)	0.0315 (6)	0.0232 (5)	0.0007 (4)	0.0033 (4)	0.0026 (4)
C26	0.0228 (4)	0.0262 (5)	0.0266 (5)	0.0016 (4)	0.0030 (4)	0.0031 (4)

Geometric parameters (Å, º)

C1—C2	1.5098 (15)	C12—C13	1.3818 (14)
C1—H1A	0.9800	C12—H12	0.9500
C1—H1B	0.9800	C13—C14	1.3917 (16)
C1—H1C	0.9800	C13—H13	0.9500
C2—N3	1.4924 (13)	C14—C15	1.3904 (16)
C2—H2A	0.9900	C14—H14	0.9500
C2—H2B	0.9900	C15—C16	1.3892 (15)
N3—C4	1.4919 (14)	C15—H15	0.9500
N3—H3A	0.908 (15)	C16—H16	0.9500
N3—H3B	0.913 (15)	C21—C22	1.4000 (13)
C4—C5	1.5100 (16)	C21—C26	1.4035 (13)
C4—H4A	0.9900	C22—C23	1.3917 (14)
C4—H4B	0.9900	C22—H22	0.9500
C5—H5A	0.9800	C23—C24	1.3850 (15)
C5—H5B	0.9800	C23—H23	0.9500
C5—H5C	0.9800	C24—C25	1.3908 (15)
N1—C21	1.3944 (12)	C24—H24	0.9500
N1—C11	1.3989 (13)	C25—C26	1.3824 (14)
N1—H1	0.851 (14)	C25—H25	0.9500
C11—C16	1.3960 (14)	C26—H26	0.9500
C11—C12	1.4033 (13)
C2—C1—H1A	109.5	N1—C11—C12	117.00 (9)
C2—C1—H1B	109.5	C13—C12—C11	120.60 (9)
H1A—C1—H1B	109.5	C13—C12—H12	119.7
C2—C1—H1C	109.5	C11—C12—H12	119.7
H1A—C1—H1C	109.5	C12—C13—C14	120.70 (10)
H1B—C1—H1C	109.5	C12—C13—H13	119.6
N3—C2—C1	111.09 (8)	C14—C13—H13	119.6
N3—C2—H2A	109.4	C15—C14—C13	118.63 (10)
C1—C2—H2A	109.4	C15—C14—H14	120.7
N3—C2—H2B	109.4	C13—C14—H14	120.7
C1—C2—H2B	109.4	C16—C15—C14	121.42 (10)
H2A—C2—H2B	108.0	C16—C15—H15	119.3
C4—N3—C2	113.79 (8)	C14—C15—H15	119.3
C4—N3—H3A	109.7 (8)	C15—C16—C11	119.75 (10)
C2—N3—H3A	108.6 (8)	C15—C16—H16	120.1
C4—N3—H3B	107.9 (8)	C11—C16—H16	120.1
C2—N3—H3B	107.7 (9)	N1—C21—C22	124.42 (9)
H3A—N3—H3B	109.1 (12)	N1—C21—C26	116.97 (8)
N3—C4—C5	110.19 (10)	C22—C21—C26	118.54 (9)
N3—C4—H4A	109.6	C23—C22—C21	119.76 (9)
C5—C4—H4A	109.6	C23—C22—H22	120.1
N3—C4—H4B	109.6	C21—C22—H22	120.1
C5—C4—H4B	109.6	C24—C23—C22	121.49 (9)
H4A—C4—H4B	108.1	C24—C23—H23	119.3
C4—C5—H5A	109.5	C22—C23—H23	119.3
C4—C5—H5B	109.5	C23—C24—C25	118.75 (9)
H5A—C5—H5B	109.5	C23—C24—H24	120.6
C4—C5—H5C	109.5	C25—C24—H24	120.6
H5A—C5—H5C	109.5	C26—C25—C24	120.63 (10)
H5B—C5—H5C	109.5	C26—C25—H25	119.7
C21—N1—C11	129.96 (8)	C24—C25—H25	119.7
C21—N1—H1	116.4 (9)	C25—C26—C21	120.83 (9)
C11—N1—H1	113.1 (9)	C25—C26—H26	119.6
C16—C11—N1	124.02 (9)	C21—C26—H26	119.6
C16—C11—C12	118.90 (9)
C1—C2—N3—C4	176.60 (9)	C12—C11—C16—C15	0.19 (15)
C2—N3—C4—C5	176.01 (9)	C11—N1—C21—C22	−19.68 (17)
C21—N1—C11—C16	−23.23 (16)	C11—N1—C21—C26	163.61 (10)
C21—N1—C11—C12	160.09 (10)	N1—C21—C22—C23	−176.28 (10)
C16—C11—C12—C13	−0.50 (15)	C26—C21—C22—C23	0.39 (15)
N1—C11—C12—C13	176.35 (9)	C21—C22—C23—C24	−0.28 (16)
C11—C12—C13—C14	0.52 (16)	C22—C23—C24—C25	0.10 (16)
C12—C13—C14—C15	−0.22 (17)	C23—C24—C25—C26	−0.02 (16)
C13—C14—C15—C16	−0.10 (18)	C24—C25—C26—C21	0.14 (16)
C14—C15—C16—C11	0.11 (17)	N1—C21—C26—C25	176.59 (10)
N1—C11—C16—C15	−176.43 (10)	C22—C21—C26—C25	−0.32 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl1	0.908 (15)	2.260 (15)	3.1581 (9)	170.0 (12)
N3—H3B···Cl1^i	0.913 (15)	2.218 (15)	3.0946 (9)	160.7 (12)
N1—H1···Cl1	0.851 (14)	2.467 (14)	3.2909 (9)	162.9 (12)

Symmetry code: (i) −x+1/2, y−1/2, −z+3/2.