Crystal structure of 2,5-di-methyl-anilinium hydrogen maleate.

The crystal structure of the title salt, C8H12N(+)·C4H3O4 (-), consists of a 2,5-di-methyl-anilinium cation and an hydrogen maleate anion. In the anion, a strong intra-molecular O-H⋯O hydrogen bond is observed, leading to an S(7) graph-set motif. In the crystal, the cations and anions pack in alternating layers parallel to (001). The ammonium group undergoes inter-molecular N-H⋯O hydrogen-bonding inter-actions with the O atoms of three different hydrogen maleate anions. This results in the formation of ribbons extending parallel to [010] with hydrogen-bonding motifs of the types R (4) 4(12) and R (4) 4(18).

Related literature

For active pharmaceutical ingredients (API), see: Kelley et al. (2013 ▶). An example of the modification of API properties through the change of one of the mol­ecular components is the substitution of the saccharinate anion in the anti-HIV active lamivudine saccharinate by maleate (Martins et al., 2009 ▶). For 2,5-di­methyl­anilinium cations in combination with other anions, see: Smirani & Rzaigui (2009 ▶).

Experimental

Crystal data

C8H12N+·C4H3O4 −

M = 237.25

Triclinic,

a = 6.7983 (17) Å

b = 8.515 (2) Å

c = 11.012 (3) Å

α = 108.784 (8)°

β = 98.026 (7)°

γ = 98.742 (7)°

V = 584.3 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 173 K

0.45 × 0.26 × 0.19 mm

Data collection

Rigaku XtaLAB mini diffractometer

Absorption correction: multi-scan (REQAB; Rigaku, 1998 ▶) T min = 0.833, T max = 0.981

6136 measured reflections

2667 independent reflections

2222 reflections with F 2 > 2.0σ(F 2)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.108

S = 1.06

2667 reflections

172 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.28 e Å−3

Data collection: CrystalClear (Rigaku, 2011 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2011 ▶); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S160053681402282X/wm5077sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681402282X/wm5077Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S160053681402282X/wm5077fig1.tif

View of the mol­ecular components of 2,5-di­methyl­anilinium hydrogenmaleate with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.

Click here for additional data file.

. DOI: 10.1107/S160053681402282X/wm5077fig2.tif

View of the mol­ecular arrangement of the title compound along [100]. Hydrogen bonds are shown as dashed lines.

Click here for additional data file.

. DOI: 10.1107/S160053681402282X/wm5077fig3.tif

Graph-set description of ring-type hydrogen bonding. Hydrogen bonds are shown as dashed lines.

CCDC reference: 1029719

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

C8H12N+·C4H3O4−	Z = 2
Mr = 237.25	F(000) = 252.00
Triclinic, P1	Dx = 1.348 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 6.7983 (17) Å	Cell parameters from 5478 reflections
b = 8.515 (2) Å	θ = 3.1–27.7°
c = 11.012 (3) Å	µ = 0.10 mm−1
α = 108.784 (8)°	T = 173 K
β = 98.026 (7)°	Prism, colorless
γ = 98.742 (7)°	0.45 × 0.26 × 0.19 mm
V = 584.3 (3) Å3

Rigaku XtaLAB mini diffractometer	2222 reflections with F2 > 2.0σ(F2)
Detector resolution: 6.849 pixels mm-1	Rint = 0.021
ω scans	θmax = 27.5°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −8→8
Tmin = 0.833, Tmax = 0.981	k = −11→11
6136 measured reflections	l = −14→14
2667 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0485P)2 + 0.1991P] where P = (Fo2 + 2Fc2)/3
2667 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.28 e Å−3
Primary atom site location: structure-invariant direct methods

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

	x	y	z	Uiso*/Ueq
O1	0.28044 (17)	1.15154 (14)	0.58091 (10)	0.0323 (3)
O2	0.37703 (18)	1.31701 (13)	0.47170 (11)	0.0355 (3)
O3	0.19359 (18)	0.84302 (14)	0.53298 (10)	0.0329 (3)
O4	0.11116 (16)	0.60871 (13)	0.35616 (11)	0.0330 (3)
N1	0.25093 (19)	0.58663 (15)	0.64194 (11)	0.0215 (3)
C1	0.34834 (19)	0.65824 (16)	0.78115 (12)	0.0196 (3)
C2	0.2577 (2)	0.77054 (16)	0.86650 (13)	0.0215 (3)
C3	0.3508 (3)	0.83054 (18)	0.99864 (13)	0.0267 (3)
C4	0.5245 (3)	0.78132 (19)	1.04275 (14)	0.0295 (4)
C5	0.6148 (2)	0.67116 (18)	0.95572 (15)	0.0264 (3)
C6	0.5240 (2)	0.60942 (17)	0.82285 (14)	0.0231 (3)
C7	0.0705 (3)	0.82651 (19)	0.81904 (14)	0.0279 (3)
C8	0.8045 (3)	0.6188 (3)	1.00350 (18)	0.0371 (4)
C9	0.3196 (2)	1.17476 (17)	0.47453 (14)	0.0240 (3)
C10	0.2959 (3)	1.02714 (18)	0.35196 (14)	0.0261 (3)
C11	0.2359 (3)	0.86040 (17)	0.32482 (13)	0.0253 (3)
C12	0.1743 (2)	0.76436 (17)	0.41028 (14)	0.0236 (3)
H1	0.240 (4)	1.025 (4)	0.564 (3)	0.070 (8)*
H1A	0.237 (3)	0.671 (3)	0.6082 (18)	0.033 (5)*
H3	0.2938	0.9073	1.0602	0.0320*
H4	0.5826	0.8235	1.1337	0.0354*
H1C	0.124 (3)	0.523 (3)	0.6319 (19)	0.041 (5)*
H6	0.5823	0.5341	0.7611	0.0277*
H7A	−0.0376	0.7266	0.7696	0.0334*
H7B	0.1026	0.8909	0.7623	0.0334*
H7C	0.0251	0.8984	0.8943	0.0334*
H8A	0.7767	0.5596	1.0642	0.0445*
H8B	0.9130	0.7198	1.0486	0.0445*
H8C	0.8472	0.5430	0.9287	0.0445*
H1B	0.321 (3)	0.511 (3)	0.5915 (19)	0.036 (5)*
H10	0.3294	1.0566	0.2801	0.0313*
H11	0.2317	0.7919	0.2369	0.0304*

	U11	U22	U33	U12	U13	U23
O1	0.0469 (7)	0.0269 (6)	0.0224 (6)	0.0110 (5)	0.0078 (5)	0.0058 (5)
O2	0.0427 (7)	0.0205 (6)	0.0417 (7)	0.0047 (5)	0.0167 (6)	0.0062 (5)
O3	0.0478 (7)	0.0312 (6)	0.0248 (6)	0.0102 (5)	0.0101 (5)	0.0148 (5)
O4	0.0339 (6)	0.0226 (6)	0.0416 (7)	0.0012 (5)	0.0088 (5)	0.0118 (5)
N1	0.0251 (6)	0.0209 (6)	0.0179 (6)	0.0041 (5)	0.0043 (5)	0.0064 (5)
C1	0.0217 (7)	0.0179 (6)	0.0191 (7)	0.0000 (5)	0.0043 (5)	0.0082 (5)
C2	0.0233 (7)	0.0208 (7)	0.0214 (7)	0.0037 (5)	0.0059 (6)	0.0088 (6)
C3	0.0329 (8)	0.0264 (7)	0.0195 (7)	0.0053 (6)	0.0071 (6)	0.0060 (6)
C4	0.0320 (8)	0.0317 (8)	0.0209 (7)	−0.0020 (6)	−0.0014 (6)	0.0108 (6)
C5	0.0214 (7)	0.0279 (7)	0.0322 (8)	−0.0001 (6)	0.0016 (6)	0.0174 (7)
C6	0.0227 (7)	0.0223 (7)	0.0268 (7)	0.0044 (5)	0.0071 (6)	0.0111 (6)
C7	0.0294 (8)	0.0313 (8)	0.0269 (8)	0.0129 (6)	0.0088 (6)	0.0112 (6)
C8	0.0251 (8)	0.0449 (10)	0.0471 (10)	0.0044 (7)	0.0004 (7)	0.0281 (8)
C9	0.0216 (7)	0.0225 (7)	0.0263 (7)	0.0069 (6)	0.0047 (6)	0.0056 (6)
C10	0.0326 (8)	0.0250 (7)	0.0217 (7)	0.0046 (6)	0.0071 (6)	0.0095 (6)
C11	0.0308 (8)	0.0229 (7)	0.0195 (7)	0.0034 (6)	0.0043 (6)	0.0051 (6)
C12	0.0210 (7)	0.0239 (7)	0.0276 (8)	0.0060 (5)	0.0042 (6)	0.0110 (6)

O1—C9	1.305 (2)	C4—C5	1.391 (3)
O1—H1	1.02 (3)	C4—H4	0.9500
O2—C9	1.227 (2)	C5—C6	1.397 (2)
O3—C12	1.2777 (18)	C5—C8	1.509 (3)
O4—C12	1.2422 (17)	C6—H6	0.9500
N1—C1	1.4671 (17)	C7—H7A	0.9800
N1—H1A	0.922 (19)	C7—H7B	0.9800
N1—H1C	0.92 (2)	C7—H7C	0.9800
N1—H1B	0.941 (19)	C8—H8A	0.9800
C1—C2	1.3926 (19)	C8—H8B	0.9800
C1—C6	1.389 (2)	C8—H8C	0.9800
C2—C3	1.3946 (19)	C9—C10	1.4876 (19)
C2—C7	1.510 (3)	C10—C11	1.337 (2)
C3—C4	1.388 (3)	C11—C12	1.494 (3)
C3—H3	0.9500
C9—O1—H1	109.8 (14)	C5—C6—H6	120.0
C12—O3—H1	111.1 (9)	C2—C7—H7A	109.5
C1—N1—H1A	111.0 (11)	C2—C7—H7B	109.5
C1—N1—H1C	109.7 (12)	H7A—C7—H7B	109.5
H1A—N1—H1C	108.3 (16)	C2—C7—H7C	109.5
C1—N1—H1B	112.6 (11)	H7A—C7—H7C	109.5
H1A—N1—H1B	109.7 (15)	H7B—C7—H7C	109.5
H1C—N1—H1B	105.3 (16)	C5—C8—H8A	109.5
C6—C1—C2	122.76 (12)	C5—C8—H8B	109.5
C6—C1—N1	119.04 (12)	H8A—C8—H8B	109.5
C2—C1—N1	118.19 (12)	C5—C8—H8C	109.5
C1—C2—C3	116.33 (12)	H8A—C8—H8C	109.5
C1—C2—C7	122.09 (12)	H8B—C8—H8C	109.5
C3—C2—C7	121.57 (12)	O2—C9—O1	121.78 (13)
C4—C3—C2	121.87 (13)	O2—C9—C10	117.86 (13)
C4—C3—H3	119.1	O1—C9—C10	120.36 (12)
C2—C3—H3	119.1	C11—C10—C9	131.55 (13)
C3—C4—C5	120.95 (13)	C11—C10—H10	114.2
C3—C4—H4	119.5	C9—C10—H10	114.2
C5—C4—H4	119.5	C10—C11—C12	130.50 (13)
C4—C5—C6	118.13 (13)	C10—C11—H11	114.8
C4—C5—C8	120.96 (14)	C12—C11—H11	114.8
C6—C5—C8	120.91 (14)	O4—C12—O3	123.77 (13)
C1—C6—C5	119.94 (13)	O4—C12—C11	116.61 (13)
C1—C6—H6	120.0	O3—C12—C11	119.59 (12)
C6—C1—C2—C3	−1.19 (19)	C2—C1—C6—C5	1.2 (2)
N1—C1—C2—C3	177.61 (12)	N1—C1—C6—C5	−177.58 (12)
C6—C1—C2—C7	178.07 (12)	C4—C5—C6—C1	−0.11 (19)
N1—C1—C2—C7	−3.14 (18)	C8—C5—C6—C1	179.49 (12)
C1—C2—C3—C4	0.1 (2)	O2—C9—C10—C11	−179.46 (15)
C7—C2—C3—C4	−179.14 (13)	O1—C9—C10—C11	0.7 (2)
C2—C3—C4—C5	0.9 (2)	C9—C10—C11—C12	−1.0 (3)
C3—C4—C5—C6	−0.9 (2)	C10—C11—C12—O4	175.04 (15)
C3—C4—C5—C8	179.48 (13)	C10—C11—C12—O3	−6.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3	1.02 (3)	1.45 (3)	2.4651 (16)	175 (2)
N1—H1A···O3	0.92 (3)	1.94 (3)	2.859 (2)	177.2 (15)
N1—H1C···O4i	0.92 (2)	1.86 (2)	2.7602 (18)	168 (2)
N1—H1B···O2ii	0.94 (2)	1.88 (2)	2.7920 (17)	161.4 (16)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1H1O3	1.02(3)	1.45(3)	2.4651(16)	175(2)
N1H1AO3	0.92(3)	1.94(3)	2.859(2)	177.2(15)
N1H1CO4i	0.92(2)	1.86(2)	2.7602(18)	168(2)
N1H1BO2ii	0.94(2)	1.88(2)	2.7920(17)	161.4(16)

Symmetry codes: (i) ; (ii) .