Crystal structure of N,N-di-ethyl-benzene-1,4-diaminium dinitrate.

In the structure of the title mol-ecular salt, C10H18N2 (2+)·2NO3 (-), the dinitrate salt of 4-(N,N-di-ethyl-amino)-aniline, the two ethyl groups lie almost perpendicular to the plane of the benzene ring [the ring-to-ethyl C-C-N-C torsion angles are -59.5 (2) and 67.5 (3)°]. The aminium groups of the cation form inter-species N-H⋯O hydrogen bonds with the nitro O-atom acceptors of both anions, giving rise to chain substructures lying along c. The chains are linked via further N-H⋯O hydrogen bonds, forming two-dimensional networks lying parallel to (010). These sheets are linked by C-H⋯O hydrogen bonds, forming a three-dimensional structure.

Related literature

For the structures of metal complex structures with dicationic 4-[N,N-di­ethyl­amino)­aniline or 4-[N,N-di­ethyl­amino)-2-methyl­aniline species as counter-ions, see: Dobrzycki & Woźniak (2008 ▶); Bringley et al. (2005 ▶). For the structure of similar dicationic benzene-1,4-diaminium species, see: Chandrasekaran (1969 ▶); Anderson et al. (2006 ▶).

Experimental

Crystal data

C10H18N2 2+·2NO3 −

M = 290.28

Orthorhombic,

a = 38.821 (5) Å

b = 20.900 (5) Å

c = 7.172 (5) Å

V = 5819 (4) Å3

Z = 16

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.30 × 0.18 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.950, T max = 0.988

7645 measured reflections

3156 independent reflections

2522 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.111

S = 1.03

3156 reflections

193 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: APEX2 and SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 2012 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814022946/su5003sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814022946/su5003Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814022946/su5003Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814022946/su5003fig1.tif

The mol­ecular structure of the title salt, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

Click here for additional data file.

a . DOI: 10.1107/S1600536814022946/su5003fig2.tif

A partial extension of the cation–anion chain substructure in the title salt in the unit cell viewed along a. Non-associative H-atoms are omitted and formal hydrogen-bonding associations are shown as dashed lines (see Table 1 for details; for symmetry codes see Table 1).

Click here for additional data file.

c . DOI: 10.1107/S1600536814022946/su5003fig3.tif

The crystal packing of the title salt viewed along c, illustrating the three-dimensional structure. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1029930

Additional supporting information: crystallographic information; 3D view; checkCIF report

C10H18N22+·2NO3−	F(000) = 2464
Mr = 290.28	Dx = 1.325 Mg m−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 6123 reflections
a = 38.821 (5) Å	θ = 2.4–30.4°
b = 20.900 (5) Å	µ = 0.11 mm−1
c = 7.172 (5) Å	T = 293 K
V = 5819 (4) Å3	Plate, brown
Z = 16	0.30 × 0.18 × 0.09 mm

Bruker APEXII CCD diffractometer	3156 independent reflections
Radiation source: fine-focus sealed tube	2522 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ω–2θ scans	θmax = 27.4°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −50→42
Tmin = 0.950, Tmax = 0.988	k = −21→26
7645 measured reflections	l = −8→9

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0471P)2 + 2.0648P] where P = (Fo2 + 2Fc2)/3
3156 reflections	(Δ/σ)max = 0.001
193 parameters	Δρmax = 0.17 e Å−3
5 restraints	Δρmin = −0.19 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

	x	y	z	Uiso*/Ueq
N1	0.49457 (4)	0.17907 (9)	0.4684 (3)	0.0325 (5)
N2	0.59991 (4)	0.03665 (8)	0.1133 (3)	0.0347 (5)
C1	0.52168 (4)	0.14297 (9)	0.3774 (3)	0.0279 (5)
C2	0.54483 (5)	0.17368 (10)	0.2631 (3)	0.0326 (6)
C3	0.57043 (5)	0.13844 (10)	0.1755 (3)	0.0334 (6)
C4	0.57233 (4)	0.07369 (9)	0.2053 (3)	0.0298 (6)
C5	0.54930 (5)	0.04263 (10)	0.3202 (3)	0.0438 (7)
C6	0.52374 (5)	0.07787 (10)	0.4069 (3)	0.0427 (7)
C7	0.58608 (6)	−0.00904 (11)	−0.0298 (4)	0.0496 (8)
C8	0.62331 (6)	0.00310 (12)	0.2507 (4)	0.0482 (8)
C9	0.56544 (8)	0.02374 (14)	−0.1775 (4)	0.0669 (10)
C10	0.63942 (7)	0.04803 (16)	0.3874 (5)	0.0715 (10)
O1	0.63464 (4)	0.13421 (8)	−0.1120 (3)	0.0636 (6)
O2	0.66914 (4)	0.05414 (9)	−0.1229 (3)	0.0650 (7)
O3	0.68100 (4)	0.13959 (8)	−0.2769 (2)	0.0463 (5)
N4	0.66175 (4)	0.10900 (9)	−0.1699 (2)	0.0370 (5)
O4	0.47981 (6)	0.10514 (10)	0.8776 (4)	0.1004 (10)
O5	0.50571 (4)	0.19404 (7)	0.8419 (2)	0.0464 (5)
O6	0.47157 (5)	0.18295 (13)	1.0743 (3)	0.0839 (8)
N3	0.48499 (5)	0.15919 (11)	0.9348 (3)	0.0503 (7)
H1A	0.4986 (5)	0.1832 (10)	0.591 (2)	0.0390*
H1B	0.4959 (5)	0.2192 (8)	0.428 (3)	0.0390*
H1C	0.4749 (4)	0.1587 (10)	0.448 (3)	0.0390*
H2	0.54330	0.21760	0.24480	0.0390*
H3	0.58620	0.15850	0.09710	0.0400*
H5	0.55090	−0.00130	0.33920	0.0530*
H6	0.50800	0.05770	0.48500	0.0510*
H7A	0.60520	−0.03140	−0.08780	0.0600*
H7B	0.57170	−0.04060	0.03180	0.0600*
H8A	0.61010	−0.02880	0.31810	0.0580*
H8B	0.64140	−0.01890	0.18270	0.0580*
H9A	0.55700	−0.00740	−0.26470	0.1010*
H9B	0.57970	0.05410	−0.24160	0.1010*
H9C	0.54630	0.04560	−0.12110	0.1010*
H10A	0.65400	0.02450	0.47070	0.1070*
H10B	0.62170	0.06920	0.45760	0.1070*
H10C	0.65280	0.07930	0.32170	0.1070*
H21	0.6122 (5)	0.0669 (9)	0.063 (3)	0.0420*

	U11	U22	U33	U12	U13	U23
N1	0.0309 (8)	0.0341 (10)	0.0325 (9)	−0.0016 (7)	0.0053 (7)	−0.0021 (8)
N2	0.0328 (8)	0.0319 (9)	0.0393 (10)	0.0006 (7)	0.0112 (8)	−0.0013 (8)
C1	0.0254 (8)	0.0315 (10)	0.0269 (10)	0.0005 (7)	0.0000 (7)	−0.0008 (9)
C2	0.0324 (9)	0.0246 (10)	0.0407 (11)	−0.0032 (8)	0.0056 (9)	0.0027 (8)
C3	0.0310 (9)	0.0332 (10)	0.0360 (11)	−0.0076 (8)	0.0083 (8)	0.0025 (9)
C4	0.0285 (9)	0.0274 (10)	0.0336 (10)	0.0003 (8)	0.0060 (8)	−0.0021 (9)
C5	0.0471 (12)	0.0260 (11)	0.0582 (14)	0.0007 (9)	0.0193 (11)	0.0061 (10)
C6	0.0411 (11)	0.0346 (12)	0.0523 (14)	−0.0042 (9)	0.0210 (10)	0.0096 (11)
C7	0.0531 (12)	0.0396 (13)	0.0562 (15)	−0.0013 (10)	0.0095 (12)	−0.0171 (12)
C8	0.0400 (11)	0.0537 (15)	0.0510 (13)	0.0125 (10)	0.0069 (11)	0.0077 (12)
C9	0.0802 (17)	0.068 (2)	0.0525 (15)	−0.0061 (15)	−0.0071 (15)	−0.0158 (16)
C10	0.0478 (13)	0.099 (2)	0.0676 (18)	0.0045 (14)	−0.0118 (14)	0.0000 (18)
O1	0.0462 (9)	0.0616 (11)	0.0829 (13)	0.0066 (8)	0.0289 (10)	−0.0033 (11)
O2	0.0620 (10)	0.0481 (10)	0.0850 (14)	0.0088 (8)	0.0077 (11)	0.0312 (11)
O3	0.0395 (8)	0.0460 (9)	0.0534 (10)	0.0014 (7)	0.0143 (7)	0.0140 (8)
N4	0.0318 (8)	0.0412 (10)	0.0380 (10)	−0.0007 (8)	0.0055 (8)	−0.0010 (9)
O4	0.1129 (17)	0.0573 (13)	0.131 (2)	−0.0358 (12)	0.0083 (18)	0.0035 (16)
O5	0.0603 (9)	0.0431 (9)	0.0359 (8)	−0.0042 (7)	0.0010 (8)	−0.0006 (8)
O6	0.0538 (10)	0.156 (2)	0.0418 (10)	0.0075 (12)	0.0096 (9)	−0.0029 (14)
N3	0.0427 (10)	0.0652 (14)	0.0429 (11)	−0.0016 (10)	−0.0053 (9)	0.0083 (11)

O1—N4	1.248 (2)	C4—C5	1.378 (3)
O2—N4	1.229 (3)	C5—C6	1.383 (3)
O3—N4	1.247 (2)	C7—C9	1.495 (4)
O4—N3	1.219 (3)	C8—C10	1.495 (4)
O5—N3	1.273 (3)	C2—H2	0.9300
O6—N3	1.233 (3)	C3—H3	0.9300
N1—C1	1.450 (3)	C5—H5	0.9300
N2—C4	1.477 (3)	C6—H6	0.9300
N2—C8	1.513 (3)	C7—H7A	0.9700
N2—C7	1.501 (3)	C7—H7B	0.9700
N1—H1B	0.889 (17)	C8—H8A	0.9700
N1—H1C	0.886 (17)	C8—H8B	0.9700
N1—H1A	0.897 (15)	C9—H9B	0.9600
N2—H21	0.87 (2)	C9—H9A	0.9600
C1—C2	1.375 (3)	C9—H9C	0.9600
C1—C6	1.379 (3)	C10—H10C	0.9600
C2—C3	1.387 (3)	C10—H10A	0.9600
C3—C4	1.372 (3)	C10—H10B	0.9600
C4—N2—C7	112.31 (15)	C1—C2—H2	120.00
C4—N2—C8	112.79 (19)	C3—C2—H2	120.00
C7—N2—C8	111.43 (17)	C4—C3—H3	120.00
H1A—N1—H1B	102.6 (19)	C2—C3—H3	120.00
H1A—N1—H1C	111.0 (19)	C4—C5—H5	121.00
H1B—N1—H1C	116.7 (18)	C6—C5—H5	120.00
C1—N1—H1B	107.6 (13)	C5—C6—H6	120.00
C1—N1—H1C	107.5 (13)	C1—C6—H6	120.00
C1—N1—H1A	111.4 (13)	C9—C7—H7A	109.00
C4—N2—H21	101.6 (13)	N2—C7—H7A	109.00
C7—N2—H21	112.0 (14)	N2—C7—H7B	109.00
C8—N2—H21	106.1 (13)	C9—C7—H7B	109.00
O2—N4—O3	120.47 (17)	H7A—C7—H7B	108.00
O1—N4—O3	119.57 (18)	N2—C8—H8B	109.00
O1—N4—O2	119.96 (17)	N2—C8—H8A	109.00
O4—N3—O5	117.3 (2)	C10—C8—H8B	109.00
O5—N3—O6	117.5 (2)	H8A—C8—H8B	108.00
O4—N3—O6	125.2 (2)	C10—C8—H8A	109.00
C2—C1—C6	120.92 (18)	H9A—C9—H9B	109.00
N1—C1—C6	119.10 (17)	H9A—C9—H9C	109.00
N1—C1—C2	119.98 (17)	C7—C9—H9A	110.00
C1—C2—C3	119.36 (19)	C7—C9—H9B	109.00
C2—C3—C4	119.44 (19)	C7—C9—H9C	110.00
N2—C4—C3	119.10 (17)	H9B—C9—H9C	109.00
C3—C4—C5	121.52 (18)	H10B—C10—H10C	109.00
N2—C4—C5	119.37 (17)	C8—C10—H10A	109.00
C4—C5—C6	118.90 (19)	C8—C10—H10B	109.00
C1—C6—C5	119.86 (19)	C8—C10—H10C	109.00
N2—C7—C9	112.6 (2)	H10A—C10—H10B	109.00
N2—C8—C10	112.8 (2)	H10A—C10—H10C	110.00
C7—N2—C4—C3	−113.1 (2)	C6—C1—C2—C3	0.5 (3)
C7—N2—C4—C5	67.5 (3)	N1—C1—C6—C5	179.57 (19)
C8—N2—C4—C3	120.0 (2)	C2—C1—C6—C5	−0.3 (3)
C8—N2—C4—C5	−59.5 (2)	C1—C2—C3—C4	−0.4 (3)
C4—N2—C7—C9	57.5 (3)	C2—C3—C4—N2	−179.28 (19)
C8—N2—C7—C9	−174.8 (2)	C2—C3—C4—C5	0.2 (3)
C4—N2—C8—C10	−56.5 (3)	N2—C4—C5—C6	179.47 (19)
C7—N2—C8—C10	176.1 (2)	C3—C4—C5—C6	0.0 (3)
N1—C1—C2—C3	−179.37 (19)	C4—C5—C6—C1	0.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O5	0.90 (2)	1.84 (2)	2.731 (3)	178 (2)
N1—H1B···O5i	0.89 (2)	1.92 (2)	2.803 (3)	175 (2)
N1—H1C···O3ii	0.89 (2)	1.99 (2)	2.855 (3)	165 (2)
N2—H21···O1	0.87 (2)	2.08 (2)	2.930 (3)	167 (2)
N2—H21···O2	0.87 (2)	2.60 (2)	3.198 (3)	127 (2)
C2—H2···O2iii	0.93	2.47	3.216 (4)	137
C3—H3···O1	0.93	2.46	3.236 (4)	141
C5—H5···O3iv	0.93	2.57	3.467 (4)	161
C8—H8A···O3iv	0.97	2.59	3.552 (4)	173

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1AO5	0.90(2)	1.84(2)	2.731(3)	178(2)
N1H1BO5i	0.89(2)	1.92(2)	2.803(3)	175(2)
N1H1CO3ii	0.89(2)	1.99(2)	2.855(3)	165(2)
N2H21O1	0.87(2)	2.08(2)	2.930(3)	167(2)
N2H21O2	0.87(2)	2.60(2)	3.198(3)	127(2)
C2H2O2iii	0.93	2.47	3.216(4)	137
C3H3O1	0.93	2.46	3.236(4)	141
C5H5O3iv	0.93	2.57	3.467(4)	161
C8H8AO3iv	0.97	2.59	3.552(4)	173

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .