Crystal structure of 4-(di-methyl-amino)-pyridinium 4-amino-benzoate dihydrate.

In the title hydrated mol-ecular salt, C7H11N2 (+)·C7H6NO2 (-)·2H2O, the cation is protonated at the pyridine N atom and the dihedral angle between the benzene ring and the CO2 (-) group in the anion is 8.5 (2)°. In the crystal, the cation forms an N-H⋯O hydrogen bond to the anion and the anion forms two N-H⋯O hydrogen bonds to adjacent water mol-ecules. Both water mol-ecules form two O-H⋯O hydrogen bonds to carboxyl-ate O atoms. In combination, these hydrogen bonds generate a three-dimensional network and two weak C-H⋯π inter-actions are also observed.

Related literature

For related structures, see: Dhanabalan et al. (2014 ▸); Lo & Ng (2008 ▸); Pereira Silva et al. (2010 ▸); Sivakumar et al. (2014 ▸).

Experimental

Crystal data

C7H11N2 +·C7H6NO2 −·2H2O

M = 295.34

Triclinic,

a = 9.3402 (7) Å

b = 9.7999 (7) Å

c = 10.2132 (8) Å

α = 65.755 (3)°

β = 69.983 (2)°

γ = 89.212 (3)°

V = 792.08 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 295 K

0.30 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T min = 0.973, T max = 0.982

16983 measured reflections

3337 independent reflections

2141 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.168

S = 1.03

3337 reflections

216 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: SAINT (Bruker, 2004 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989014026310/hb7333sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014026310/hb7333Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989014026310/hb7333Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989014026310/hb7333fig1.tif

The mol­ecular structure of (I), with 30% probability displacement ellipsoids for non-H atoms.

Click here for additional data file.

a . DOI: 10.1107/S2056989014026310/hb7333fig2.tif

The packing of (I), viewed down a axis. Inter­molecular Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

CCDC reference: 1036769

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

C7H11N2+·C7H6NO2−·2H2O	Z = 2
Mr = 295.34	F(000) = 316
Triclinic, P1	Dx = 1.238 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3402 (7) Å	Cell parameters from 1058 reflections
b = 9.7999 (7) Å	θ = 2.3–26.7°
c = 10.2132 (8) Å	µ = 0.09 mm−1
α = 65.755 (3)°	T = 295 K
β = 69.983 (2)°	Block, colourless
γ = 89.212 (3)°	0.30 × 0.24 × 0.20 mm
V = 792.08 (10) Å3

Bruker Kappa APEXII CCD diffractometer	3337 independent reflections
Radiation source: fine-focus sealed tube	2141 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω and φ scan	θmax = 26.7°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.973, Tmax = 0.982	k = −12→12
16983 measured reflections	l = −12→12

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0709P)2 + 0.2681P] where P = (Fo2 + 2Fc2)/3
3337 reflections	(Δ/σ)max < 0.001
216 parameters	Δρmax = 0.29 e Å−3
7 restraints	Δρmin = −0.23 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.2531 (2)	0.4227 (2)	0.2980 (2)	0.0514 (5)
C2	0.3081 (2)	0.4846 (2)	0.1370 (2)	0.0542 (5)
H2	0.3434	0.4230	0.0871	0.065*
C3	0.3104 (2)	0.6362 (2)	0.0517 (2)	0.0531 (5)
H3	0.3492	0.6757	−0.0556	0.064*
C4	0.2567 (2)	0.7315 (2)	0.1210 (2)	0.0491 (4)
C5	0.2008 (2)	0.6690 (2)	0.2806 (2)	0.0568 (5)
H5	0.1630	0.7305	0.3302	0.068*
C6	0.1998 (2)	0.5183 (2)	0.3680 (2)	0.0581 (5)
H6	0.1631	0.4799	0.4751	0.070*
C7	0.2563 (2)	0.8938 (2)	0.0265 (3)	0.0577 (5)
C8	0.1012 (3)	0.3280 (2)	0.9041 (3)	0.0708 (6)
H8	0.0065	0.2666	0.9669	0.085*
C9	0.1039 (3)	0.4747 (2)	0.8167 (3)	0.0655 (6)
H9	0.0118	0.5130	0.8197	0.079*
C10	0.2434 (3)	0.5707 (2)	0.7214 (3)	0.0622 (6)
C11	0.3751 (3)	0.5037 (3)	0.7234 (3)	0.0903 (9)
H11	0.4716	0.5621	0.6622	0.108*
C12	0.3649 (3)	0.3550 (3)	0.8129 (3)	0.0892 (8)
H12	0.4546	0.3123	0.8114	0.107*
C13	0.3933 (4)	0.8197 (4)	0.5480 (5)	0.159 (2)
H13A	0.4464	0.8139	0.6153	0.238*
H13B	0.3738	0.9215	0.5003	0.238*
H13C	0.4557	0.7910	0.4695	0.238*
C14	0.1109 (4)	0.7869 (3)	0.6311 (4)	0.1021 (10)
H14A	0.0473	0.7295	0.6093	0.153*
H14B	0.1394	0.8888	0.5515	0.153*
H14C	0.0548	0.7877	0.7290	0.153*
N1	0.2553 (2)	0.2736 (2)	0.3824 (2)	0.0707 (5)
H1A	0.218 (3)	0.236 (3)	0.4832 (12)	0.078 (8)*
H1B	0.282 (3)	0.218 (3)	0.331 (3)	0.082 (8)*
N2	0.2282 (2)	0.2677 (2)	0.9039 (2)	0.0694 (5)
H2A	0.218 (3)	0.1687 (12)	0.961 (2)	0.079 (7)*
N3	0.2487 (3)	0.7185 (2)	0.6365 (3)	0.0864 (7)
O1	0.18777 (18)	0.97118 (16)	0.09587 (19)	0.0718 (5)
O2	0.3219 (2)	0.94822 (18)	−0.1168 (2)	0.0820 (5)
O3	0.8669 (2)	0.9002 (3)	0.2848 (2)	0.0923 (6)
H3A	0.816 (4)	0.948 (4)	0.233 (4)	0.138*
H3B	0.9578 (17)	0.921 (4)	0.225 (4)	0.138*
O4	0.6374 (2)	0.9148 (2)	0.7810 (3)	0.0908 (6)
H4A	0.5475 (17)	0.930 (4)	0.810 (4)	0.136*
H4B	0.693 (4)	0.960 (4)	0.803 (4)	0.136*

	U11	U22	U33	U12	U13	U23
C1	0.0425 (10)	0.0498 (10)	0.0531 (11)	0.0097 (8)	−0.0151 (8)	−0.0161 (9)
C2	0.0508 (11)	0.0528 (11)	0.0534 (11)	0.0106 (8)	−0.0121 (9)	−0.0236 (9)
C3	0.0493 (11)	0.0562 (11)	0.0442 (10)	0.0081 (8)	−0.0124 (8)	−0.0168 (9)
C4	0.0419 (10)	0.0491 (10)	0.0529 (11)	0.0087 (8)	−0.0171 (8)	−0.0194 (9)
C5	0.0549 (11)	0.0607 (12)	0.0589 (12)	0.0174 (9)	−0.0196 (9)	−0.0310 (10)
C6	0.0560 (12)	0.0667 (13)	0.0444 (11)	0.0145 (9)	−0.0153 (9)	−0.0202 (9)
C7	0.0482 (11)	0.0525 (11)	0.0687 (14)	0.0109 (9)	−0.0246 (10)	−0.0206 (10)
C8	0.0618 (13)	0.0555 (12)	0.0919 (17)	0.0015 (10)	−0.0354 (12)	−0.0230 (12)
C9	0.0616 (13)	0.0575 (12)	0.0797 (15)	0.0095 (10)	−0.0316 (11)	−0.0273 (11)
C10	0.0718 (14)	0.0553 (12)	0.0667 (13)	0.0014 (10)	−0.0410 (11)	−0.0202 (10)
C11	0.0593 (14)	0.0892 (18)	0.0937 (19)	−0.0039 (13)	−0.0376 (14)	−0.0048 (15)
C12	0.0643 (15)	0.0915 (19)	0.103 (2)	0.0203 (14)	−0.0437 (15)	−0.0234 (16)
C13	0.131 (3)	0.092 (2)	0.177 (4)	−0.044 (2)	−0.096 (3)	0.046 (2)
C14	0.130 (3)	0.0622 (15)	0.120 (3)	0.0295 (16)	−0.064 (2)	−0.0303 (16)
N1	0.0811 (13)	0.0549 (11)	0.0565 (12)	0.0159 (9)	−0.0167 (10)	−0.0130 (9)
N2	0.0796 (14)	0.0520 (10)	0.0877 (14)	0.0123 (10)	−0.0473 (11)	−0.0274 (10)
N3	0.0961 (16)	0.0599 (12)	0.0969 (16)	−0.0098 (11)	−0.0602 (13)	−0.0074 (11)
O1	0.0744 (10)	0.0538 (8)	0.0866 (11)	0.0189 (7)	−0.0286 (9)	−0.0308 (8)
O2	0.0879 (12)	0.0644 (10)	0.0658 (11)	0.0250 (8)	−0.0198 (9)	−0.0095 (8)
O3	0.0898 (13)	0.1101 (15)	0.0598 (11)	0.0207 (12)	−0.0261 (9)	−0.0222 (10)
O4	0.0835 (13)	0.1013 (14)	0.1038 (14)	0.0223 (11)	−0.0322 (12)	−0.0615 (12)

C1—N1	1.362 (3)	C10—C11	1.389 (3)
C1—C6	1.389 (3)	C11—C12	1.348 (4)
C1—C2	1.395 (3)	C11—H11	0.9300
C2—C3	1.375 (3)	C12—N2	1.338 (3)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.383 (3)	C13—N3	1.446 (4)
C3—H3	0.9300	C13—H13A	0.9600
C4—C5	1.383 (3)	C13—H13B	0.9600
C4—C7	1.484 (3)	C13—H13C	0.9600
C5—C6	1.375 (3)	C14—N3	1.451 (4)
C5—H5	0.9300	C14—H14A	0.9600
C6—H6	0.9300	C14—H14B	0.9600
C7—O2	1.248 (3)	C14—H14C	0.9600
C7—O1	1.267 (3)	N1—H1A	0.874 (10)
C8—N2	1.318 (3)	N1—H1B	0.885 (10)
C8—C9	1.341 (3)	N2—H2A	0.890 (10)
C8—H8	0.9300	O3—H3A	0.826 (10)
C9—C10	1.394 (3)	O3—H3B	0.825 (10)
C9—H9	0.9300	O4—H4A	0.823 (10)
C10—N3	1.339 (3)	O4—H4B	0.821 (10)
N1—C1—C6	121.60 (19)	C12—C11—C10	120.8 (2)
N1—C1—C2	120.45 (18)	C12—C11—H11	119.6
C6—C1—C2	117.94 (17)	C10—C11—H11	119.6
C3—C2—C1	120.44 (18)	N2—C12—C11	121.3 (2)
C3—C2—H2	119.8	N2—C12—H12	119.3
C1—C2—H2	119.8	C11—C12—H12	119.3
C2—C3—C4	121.77 (18)	N3—C13—H13A	109.5
C2—C3—H3	119.1	N3—C13—H13B	109.5
C4—C3—H3	119.1	H13A—C13—H13B	109.5
C3—C4—C5	117.50 (17)	N3—C13—H13C	109.5
C3—C4—C7	120.77 (18)	H13A—C13—H13C	109.5
C5—C4—C7	121.72 (18)	H13B—C13—H13C	109.5
C6—C5—C4	121.59 (19)	N3—C14—H14A	109.5
C6—C5—H5	119.2	N3—C14—H14B	109.5
C4—C5—H5	119.2	H14A—C14—H14B	109.5
C5—C6—C1	120.75 (18)	N3—C14—H14C	109.5
C5—C6—H6	119.6	H14A—C14—H14C	109.5
C1—C6—H6	119.6	H14B—C14—H14C	109.5
O2—C7—O1	122.73 (19)	C1—N1—H1A	119.5 (17)
O2—C7—C4	119.24 (19)	C1—N1—H1B	116.5 (17)
O1—C7—C4	118.02 (19)	H1A—N1—H1B	123 (2)
N2—C8—C9	122.2 (2)	C8—N2—C12	119.2 (2)
N2—C8—H8	118.9	C8—N2—H2A	117.7 (16)
C9—C8—H8	118.9	C12—N2—H2A	123.0 (16)
C8—C9—C10	120.7 (2)	C10—N3—C13	121.4 (2)
C8—C9—H9	119.7	C10—N3—C14	122.4 (2)
C10—C9—H9	119.7	C13—N3—C14	116.2 (2)
N3—C10—C11	122.6 (2)	H3A—O3—H3B	107 (4)
N3—C10—C9	121.7 (2)	H4A—O4—H4B	112 (4)
C11—C10—C9	115.7 (2)
N1—C1—C2—C3	−177.90 (19)	C5—C4—C7—O1	−7.6 (3)
C6—C1—C2—C3	0.7 (3)	N2—C8—C9—C10	−0.3 (4)
C1—C2—C3—C4	−1.1 (3)	C8—C9—C10—N3	−178.1 (2)
C2—C3—C4—C5	0.4 (3)	C8—C9—C10—C11	0.5 (4)
C2—C3—C4—C7	−178.23 (18)	N3—C10—C11—C12	178.6 (3)
C3—C4—C5—C6	0.7 (3)	C9—C10—C11—C12	0.1 (4)
C7—C4—C5—C6	179.30 (18)	C10—C11—C12—N2	−0.8 (5)
C4—C5—C6—C1	−1.1 (3)	C9—C8—N2—C12	−0.5 (4)
N1—C1—C6—C5	178.9 (2)	C11—C12—N2—C8	1.0 (4)
C2—C1—C6—C5	0.4 (3)	C11—C10—N3—C13	−3.7 (4)
C3—C4—C7—O2	−8.6 (3)	C9—C10—N3—C13	174.7 (3)
C5—C4—C7—O2	172.8 (2)	C11—C10—N3—C14	178.0 (3)
C3—C4—C7—O1	171.01 (18)	C9—C10—N3—C14	−3.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3i	0.87 (1)	2.04 (1)	2.898 (3)	167 (2)
N1—H1B···O4i	0.89 (1)	2.04 (1)	2.921 (3)	174 (2)
N2—H2A···O1ii	0.89 (1)	1.81 (1)	2.697 (2)	174 (2)
O3—H3A···O2iii	0.83 (1)	2.03 (1)	2.858 (3)	175 (4)
O3—H3B···O1iv	0.83 (1)	2.04 (1)	2.861 (3)	174 (4)
O4—H4A···O2v	0.82 (1)	2.01 (1)	2.834 (3)	175 (4)
O4—H4B···O1vi	0.82 (1)	2.04 (1)	2.847 (3)	167 (4)
C9—H9···Cg2vii	0.93	2.80	3.510 (3)	134
C12—H12···Cg2i	0.93	2.84	3.535 (3)	132

Table 1

Hydrogen-bond geometry (, )

Cg2 is the centroid of the C1C6 benzene ring.

DHA	DH	HA	D A	DHA
N1H1AO3i	0.87(1)	2.04(1)	2.898(3)	167(2)
N1H1BO4i	0.89(1)	2.04(1)	2.921(3)	174(2)
N2H2AO1ii	0.89(1)	1.81(1)	2.697(2)	174(2)
O3H3AO2iii	0.83(1)	2.03(1)	2.858(3)	175(4)
O3H3BO1iv	0.83(1)	2.04(1)	2.861(3)	174(4)
O4H4AO2v	0.82(1)	2.01(1)	2.834(3)	175(4)
O4H4BO1vi	0.82(1)	2.04(1)	2.847(3)	167(4)
C9H9Cg2vii	0.93	2.80	3.510(3)	134
C12H12Cg2i	0.93	2.84	3.535(3)	132

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .