N,N-Dimethyl-ethane-1,2-diaminium bis-(3-hy-droxy-benzoate).

In the title compound, C(4)H(14)N(2) (2+)·2C(7)H(5)O(3) (-), both the N,N-dimethyl-ethylenediamine N atoms are protonated and two 3-hy-droxy-benzoate anions act as counter-ions. In the crystal, anions and cations are linked by a network of N-H⋯O and O-H⋯O hydrogen bonds.

Related literature

For bond lengths in fully protonated polyamines, see: Bujak & Angel (2006 ▶); Bujak & Zaleski (2002 ▶); Doran et al. (2003 ▶); Thorn et al. (2005 ▶); Zhang et al. (2007 ▶).

Experimental

Crystal data

C4H14N2 2+·2C7H5O3 −

M = 364.39

Monoclinic,

a = 14.5439 (3) Å

b = 17.5881 (4) Å

c = 7.7104 (2) Å

β = 114.777 (1)°

V = 1790.76 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.49 × 0.12 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: integration (XPREP; Bruker, 2001 ▶) T min = 0.952, T max = 0.997

14114 measured reflections

4292 independent reflections

3635 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.077

S = 0.96

4292 reflections

240 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.20 e Å−3

Absolute structure: Flack (1983 ▶), 2119 Friedel pairs

Flack parameter: 0.00 (7)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL and SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811040578/fj2425sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040578/fj2425Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811040578/fj2425Isup3.cml

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

C4H14N22+·2C7H5O3−	F(000) = 776
Mr = 364.39	Dx = 1.352 Mg m−3Dm = 1.352 Mg m−3Dm measured by not measured
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 4375 reflections
a = 14.5439 (3) Å	θ = 2.3–27.2°
b = 17.5881 (4) Å	µ = 0.10 mm−1
c = 7.7104 (2) Å	T = 293 K
β = 114.777 (1)°	Needle, colourless
V = 1790.76 (7) Å3	0.49 × 0.12 × 0.03 mm
Z = 4

Bruker APEXII CCD diffractometer	4292 independent reflections
Radiation source: fine-focus sealed tube	3635 reflections with I > 2σ(I)
graphite	Rint = 0.048
φ and ω scans	θmax = 28.0°, θmin = 1.9°
Absorption correction: integration (XPREP; Bruker, 2005)	h = −19→19
Tmin = 0.952, Tmax = 0.997	k = −23→23
14114 measured reflections	l = −9→10

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036	H-atom parameters constrained
wR(F2) = 0.077	w = 1/[σ2(Fo2) + (0.037P)2] where P = (Fo2 + 2Fc2)/3
S = 0.96	(Δ/σ)max < 0.001
4292 reflections	Δρmax = 0.18 e Å−3
240 parameters	Δρmin = −0.20 e Å−3
2 restraints	Absolute structure: Flack (1983), 2119 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.00 (7)

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.

	x	y	z	Uiso*/Ueq
O6	−0.04233 (9)	0.58513 (7)	0.31587 (16)	0.0236 (3)
H6	−0.0877	0.6024	0.3410	0.035*
O4	0.24002 (8)	0.70635 (7)	1.07125 (16)	0.0235 (3)
N7	0.41688 (11)	0.92211 (8)	0.40647 (19)	0.0192 (3)
H9A	0.4078	0.9518	0.4914	0.029*
H19B	0.3910	0.9446	0.2926	0.029*
H8C	0.4828	0.9142	0.4427	0.029*
N10	0.19982 (10)	0.78889 (8)	0.3324 (2)	0.0202 (3)
H1	0.2057	0.7653	0.2325	0.024*
C7	0.05796 (12)	0.62591 (9)	0.6407 (2)	0.0174 (3)
H005	0.0023	0.6493	0.6479	0.021*
C1	0.25729 (12)	0.86195 (9)	0.3681 (2)	0.0189 (3)
H3A	0.2578	0.8860	0.4817	0.023*
H2B	0.2238	0.8961	0.2611	0.023*
O5	0.08907 (9)	0.66203 (7)	1.02369 (18)	0.0284 (3)
C6	0.04672 (12)	0.58805 (9)	0.4740 (2)	0.0177 (3)
C8	0.15193 (12)	0.62880 (8)	0.7962 (2)	0.0170 (3)
C4	0.36527 (12)	0.84847 (9)	0.3943 (3)	0.0225 (4)
H6A	0.4014	0.8195	0.5102	0.027*
H5B	0.3652	0.8193	0.2875	0.027*
C19	0.16091 (12)	0.66816 (9)	0.9766 (2)	0.0186 (3)
C9	0.23557 (12)	0.59331 (9)	0.7864 (2)	0.0190 (3)
H012	0.2989	0.5961	0.8888	0.023*
C10	0.22300 (13)	0.55372 (9)	0.6214 (2)	0.0215 (4)
H013	0.2780	0.5287	0.6155	0.026*
C5	0.12971 (12)	0.55123 (9)	0.4663 (2)	0.0206 (4)
H014	0.1224	0.5249	0.3566	0.025*
C15	0.09028 (13)	0.80408 (11)	0.2764 (3)	0.0297 (4)
H18C	0.0823	0.8318	0.3766	0.044*
H16D	0.0544	0.7567	0.2557	0.044*
H17E	0.0636	0.8336	0.1610	0.044*
C11	0.24122 (15)	0.73670 (10)	0.4997 (3)	0.0305 (4)
H13F	0.2456	0.7630	0.6119	0.046*
H14G	0.3075	0.7199	0.5180	0.046*
H12H	0.1973	0.6935	0.4770	0.046*
O1	0.80917 (9)	0.53105 (7)	0.53286 (16)	0.0231 (3)
O2	0.78810 (9)	0.62504 (7)	0.32384 (18)	0.0267 (3)
O3	0.43039 (9)	0.70905 (7)	0.11670 (19)	0.0272 (3)
H3	0.3697	0.7025	0.0857	0.041*
C23	0.60027 (13)	0.52862 (10)	0.4403 (2)	0.0229 (4)
H020	0.6388	0.4881	0.5111	0.027*
C26	0.75606 (12)	0.57987 (9)	0.4128 (2)	0.0192 (3)
C25	0.58608 (13)	0.64466 (10)	0.2662 (2)	0.0199 (4)
H022	0.6158	0.6824	0.2222	0.024*
C24	0.64459 (12)	0.58440 (9)	0.3717 (2)	0.0184 (3)
C22	0.49872 (13)	0.53375 (10)	0.4027 (3)	0.0256 (4)
H024	0.4694	0.4966	0.4493	0.031*
C20	0.48344 (12)	0.64932 (9)	0.2253 (2)	0.0204 (4)
C21	0.43992 (13)	0.59385 (10)	0.2960 (2)	0.0235 (4)
H026	0.3718	0.5969	0.2719	0.028*

	U11	U22	U33	U12	U13	U23
O6	0.0184 (6)	0.0337 (7)	0.0185 (6)	−0.0004 (5)	0.0076 (5)	−0.0060 (5)
O4	0.0171 (6)	0.0275 (7)	0.0248 (7)	−0.0043 (5)	0.0078 (5)	−0.0107 (5)
N7	0.0191 (7)	0.0217 (7)	0.0169 (7)	−0.0024 (6)	0.0077 (6)	−0.0010 (5)
N10	0.0213 (7)	0.0201 (7)	0.0199 (7)	−0.0032 (6)	0.0094 (6)	−0.0044 (6)
C7	0.0177 (8)	0.0160 (8)	0.0207 (8)	0.0001 (6)	0.0103 (7)	−0.0004 (7)
C1	0.0221 (8)	0.0167 (8)	0.0165 (8)	−0.0013 (7)	0.0068 (7)	−0.0007 (7)
O5	0.0234 (6)	0.0402 (8)	0.0262 (7)	−0.0092 (6)	0.0149 (6)	−0.0120 (6)
C6	0.0193 (8)	0.0163 (8)	0.0177 (8)	−0.0025 (6)	0.0081 (7)	0.0016 (6)
C8	0.0204 (8)	0.0130 (8)	0.0193 (8)	−0.0026 (6)	0.0099 (7)	0.0002 (6)
C4	0.0220 (9)	0.0171 (9)	0.0286 (10)	−0.0005 (7)	0.0107 (8)	−0.0008 (7)
C19	0.0180 (8)	0.0188 (8)	0.0168 (8)	0.0033 (7)	0.0051 (7)	0.0010 (7)
C9	0.0161 (8)	0.0180 (8)	0.0199 (8)	−0.0001 (6)	0.0047 (7)	0.0008 (7)
C10	0.0202 (8)	0.0196 (8)	0.0262 (10)	0.0041 (7)	0.0112 (7)	0.0001 (7)
C5	0.0248 (9)	0.0166 (8)	0.0224 (9)	−0.0012 (7)	0.0118 (8)	−0.0039 (7)
C15	0.0216 (9)	0.0359 (11)	0.0332 (11)	−0.0053 (8)	0.0132 (9)	−0.0075 (9)
C11	0.0375 (11)	0.0220 (9)	0.0344 (11)	−0.0023 (8)	0.0173 (10)	0.0045 (8)
O1	0.0219 (6)	0.0241 (6)	0.0191 (6)	0.0058 (5)	0.0046 (5)	0.0003 (5)
O2	0.0213 (6)	0.0294 (7)	0.0322 (7)	0.0044 (5)	0.0139 (6)	0.0091 (6)
O3	0.0149 (6)	0.0242 (6)	0.0393 (8)	0.0024 (5)	0.0081 (6)	0.0063 (6)
C23	0.0261 (9)	0.0210 (9)	0.0197 (9)	0.0017 (7)	0.0078 (7)	0.0026 (7)
C26	0.0190 (8)	0.0213 (9)	0.0151 (8)	0.0007 (7)	0.0050 (7)	−0.0051 (7)
C25	0.0202 (8)	0.0216 (8)	0.0198 (9)	−0.0031 (7)	0.0103 (7)	−0.0013 (7)
C24	0.0197 (8)	0.0196 (8)	0.0143 (8)	−0.0009 (6)	0.0057 (7)	−0.0034 (6)
C22	0.0271 (9)	0.0246 (9)	0.0271 (10)	−0.0066 (8)	0.0134 (8)	0.0003 (8)
C20	0.0194 (8)	0.0203 (9)	0.0187 (9)	0.0000 (7)	0.0053 (7)	−0.0034 (7)
C21	0.0174 (8)	0.0286 (9)	0.0240 (10)	−0.0042 (7)	0.0083 (7)	−0.0043 (7)

O6—C6	1.358 (2)	C10—C5	1.383 (2)
O6—H6	0.8200	C10—H013	0.9300
O4—C19	1.2664 (19)	C5—H014	0.9300
N7—C4	1.480 (2)	C15—H18C	0.9600
N7—H9A	0.8900	C15—H16D	0.9600
N7—H19B	0.8900	C15—H17E	0.9600
N7—H8C	0.8900	C11—H13F	0.9600
N10—C11	1.489 (2)	C11—H14G	0.9600
N10—C15	1.490 (2)	C11—H12H	0.9600
N10—C1	1.494 (2)	O1—C26	1.262 (2)
N10—H1	0.9100	O2—C26	1.260 (2)
C7—C8	1.391 (2)	O3—C20	1.363 (2)
C7—C6	1.395 (2)	O3—H3	0.8200
C7—H005	0.9300	C23—C22	1.384 (2)
C1—C4	1.516 (2)	C23—C24	1.394 (2)
C1—H3A	0.9700	C23—H020	0.9300
C1—H2B	0.9700	C26—C24	1.518 (2)
O5—C19	1.246 (2)	C25—C24	1.389 (2)
C6—C5	1.393 (2)	C25—C20	1.393 (2)
C8—C9	1.397 (2)	C25—H022	0.9300
C8—C19	1.510 (2)	C22—C21	1.391 (2)
C4—H6A	0.9700	C22—H024	0.9300
C4—H5B	0.9700	C20—C21	1.392 (2)
C9—C10	1.393 (2)	C21—H026	0.9300
C9—H012	0.9300
C6—O6—H6	109.5	C5—C10—C9	120.73 (15)
C4—N7—H9A	109.5	C5—C10—H013	119.6
C4—N7—H19B	109.5	C9—C10—H013	119.6
H9A—N7—H19B	109.5	C10—C5—C6	120.13 (15)
C4—N7—H8C	109.5	C10—C5—H014	119.9
H9A—N7—H8C	109.5	C6—C5—H014	119.9
H19B—N7—H8C	109.5	N10—C15—H18C	109.5
C11—N10—C15	110.88 (14)	N10—C15—H16D	109.5
C11—N10—C1	112.24 (13)	H18C—C15—H16D	109.5
C15—N10—C1	110.30 (13)	N10—C15—H17E	109.5
C11—N10—H1	107.7	H18C—C15—H17E	109.5
C15—N10—H1	107.7	H16D—C15—H17E	109.5
C1—N10—H1	107.7	N10—C11—H13F	109.5
C8—C7—C6	120.34 (15)	N10—C11—H14G	109.5
C8—C7—H005	119.8	H13F—C11—H14G	109.5
C6—C7—H005	119.8	N10—C11—H12H	109.5
N10—C1—C4	111.00 (13)	H13F—C11—H12H	109.5
N10—C1—H3A	109.4	H14G—C11—H12H	109.5
C4—C1—H3A	109.4	C20—O3—H3	109.5
N10—C1—H2B	109.4	C22—C23—C24	119.82 (17)
C4—C1—H2B	109.4	C22—C23—H020	120.1
H3A—C1—H2B	108.0	C24—C23—H020	120.1
O6—C6—C5	117.48 (15)	O2—C26—O1	125.20 (15)
O6—C6—C7	123.03 (14)	O2—C26—C24	117.38 (15)
C5—C6—C7	119.49 (15)	O1—C26—C24	117.43 (15)
C7—C8—C9	120.00 (15)	C24—C25—C20	120.85 (16)
C7—C8—C19	119.04 (14)	C24—C25—H022	119.6
C9—C8—C19	120.92 (15)	C20—C25—H022	119.6
N7—C4—C1	109.95 (13)	C25—C24—C23	119.48 (15)
N7—C4—H6A	109.7	C25—C24—C26	120.04 (15)
C1—C4—H6A	109.7	C23—C24—C26	120.47 (15)
N7—C4—H5B	109.7	C23—C22—C21	120.72 (16)
C1—C4—H5B	109.7	C23—C22—H024	119.6
H6A—C4—H5B	108.2	C21—C22—H024	119.6
O5—C19—O4	123.25 (15)	O3—C20—C21	123.19 (15)
O5—C19—C8	118.00 (14)	O3—C20—C25	117.46 (15)
O4—C19—C8	118.74 (14)	C21—C20—C25	119.35 (16)
C10—C9—C8	119.26 (16)	C22—C21—C20	119.76 (16)
C10—C9—H012	120.4	C22—C21—H026	120.1
C8—C9—H012	120.4	C20—C21—H026	120.1
C11—N10—C1—C4	64.80 (17)	C7—C6—C5—C10	−1.4 (2)
C15—N10—C1—C4	−171.02 (14)	C20—C25—C24—C23	−1.1 (2)
C8—C7—C6—O6	−178.08 (14)	C20—C25—C24—C26	179.29 (15)
C8—C7—C6—C5	1.8 (2)	C22—C23—C24—C25	0.0 (3)
C6—C7—C8—C9	−0.4 (2)	C22—C23—C24—C26	179.60 (15)
C6—C7—C8—C19	−178.15 (13)	O2—C26—C24—C25	−10.9 (2)
N10—C1—C4—N7	173.31 (13)	O1—C26—C24—C25	169.32 (15)
C7—C8—C19—O5	36.5 (2)	O2—C26—C24—C23	169.52 (15)
C9—C8—C19—O5	−141.30 (16)	O1—C26—C24—C23	−10.3 (2)
C7—C8—C19—O4	−142.72 (15)	C24—C23—C22—C21	0.4 (3)
C9—C8—C19—O4	39.5 (2)	C24—C25—C20—O3	−178.29 (15)
C7—C8—C9—C10	−1.5 (2)	C24—C25—C20—C21	1.8 (2)
C19—C8—C9—C10	176.23 (14)	C23—C22—C21—C20	0.3 (3)
C8—C9—C10—C5	1.9 (2)	O3—C20—C21—C22	178.71 (16)
C9—C10—C5—C6	−0.4 (3)	C25—C20—C21—C22	−1.3 (3)
O6—C6—C5—C10	178.49 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H8C···O5i	0.89	1.94	2.7169 (18)	145
N7—H9A···O1ii	0.89	2.12	2.8904 (18)	145
N7—H19B···O1iii	0.89	1.90	2.7657 (19)	164
N10—H1···O4iv	0.91	1.84	2.7367 (17)	168
O3—H3···O4iv	0.82	1.84	2.6415 (16)	164.
O6—H6···O2v	0.82	1.80	2.5897 (16)	161.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H8C⋯O5i	0.89	1.94	2.7169 (18)	145
N7—H9A⋯O1ii	0.89	2.12	2.8904 (18)	145
N7—H19B⋯O1iii	0.89	1.90	2.7657 (19)	164
N10—H1⋯O4iv	0.91	1.84	2.7367 (17)	168
O3—H3⋯O4iv	0.82	1.84	2.6415 (16)	164
O6—H6⋯O2v	0.82	1.80	2.5897 (16)	161

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