2,2'-Azanediyl-diethanaminium pyridine-2,5-dicarboxyl-ate.

The crystal structure of the title compound, C(4)H(15)N(3) (2+)·C(7)H(3)NO(4) (2-), consists of diethyl-enetriaminium (2,2'-azanediyl-diethanaminium) cations and pyridine-2,5-dicarboxyl-ate anions, which are linked by N-H⋯O, N-H⋯N and C-H⋯O hydrogen bonds. C-H⋯π inter-actions are also observed. In the anion, the carboxyl-ate groups are oriented at dihedral angles of 11.04 (15) and 6.31 (14)° with respect to the pyridine ring.

Related literature

For general background to proton-transfer compounds, see: Sheshmani et al. (2007 ▶); Aghabozorg et al. (2008a ▶,b ▶,c ▶); Derikvand et al. (2009 ▶).

Experimental

Crystal data

C4H15N3 2+·C7H3NO4 2−

M = 270.29

Monoclinic,

a = 10.485 (2) Å

b = 7.7016 (15) Å

c = 17.254 (4) Å

β = 106.67 (3)°

V = 1334.7 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 298 K

0.3 × 0.3 × 0.15 mm

Data collection

Stoe IPDS II diffractometer

Absorption correction: integration (X-RED32; Stoe & Cie, 2005 ▶) T min = 0.967, T max = 0.983

14267 measured reflections

3593 independent reflections

2523 reflections with I > 2σ(I)

R int = 0.099

Refinement

R[F 2 > 2σ(F 2)] = 0.087

wR(F 2) = 0.184

S = 1.18

3593 reflections

200 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.28 e Å−3

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810054413/xu5129sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810054413/xu5129Isup2.hkl

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

C4H15N32+·C7H3NO42−	F(000) = 576.0
Mr = 270.29	Dx = 1.345 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3595 reflections
a = 10.485 (2) Å	θ = 2.5–29.2°
b = 7.7016 (15) Å	µ = 0.10 mm−1
c = 17.254 (4) Å	T = 298 K
β = 106.67 (3)°	Block, yellow
V = 1334.7 (5) Å3	0.3 × 0.3 × 0.15 mm
Z = 4

Stoe IPDS II diffractometer	3593 independent reflections
Radiation source: fine-focus sealed tube	2523 reflections with I > 2σ(I)
graphite	Rint = 0.099
Detector resolution: 0.15 mm pixels mm-1	θmax = 29.2°, θmin = 2.5°
rotation method scans	h = −14→13
Absorption correction: integration (X-RED32; Stoe & Cie, 2005)	k = −10→10
Tmin = 0.967, Tmax = 0.983	l = −23→23
14267 measured reflections

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)] = 0.087	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.184	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ2(Fo2) + (0.0436P)2 + 0.9032P] where P = (Fo2 + 2Fc2)/3
3593 reflections	(Δ/σ)max < 0.001
200 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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
O1	0.6009 (2)	0.1955 (4)	0.15541 (15)	0.0729 (8)
O2	0.60280 (19)	0.3262 (3)	0.04174 (12)	0.0548 (6)
O3	1.29302 (19)	0.1713 (3)	0.26621 (13)	0.0551 (6)
O4	1.28741 (19)	0.3736 (3)	0.17248 (12)	0.0509 (5)
N1	0.8735 (2)	0.3611 (3)	0.09555 (13)	0.0391 (5)
N2	0.4579 (2)	−0.0627 (3)	0.21118 (15)	0.0382 (5)
N3	0.2987 (2)	−0.0099 (3)	0.04917 (15)	0.0460 (6)
N4	0.3271 (3)	0.3560 (4)	0.01663 (16)	0.0443 (6)
C1	0.8097 (2)	0.2669 (3)	0.13871 (15)	0.0327 (5)
C2	0.8779 (3)	0.1723 (4)	0.20632 (17)	0.0436 (6)
H2	0.8315	0.1112	0.2361	0.052*
C3	1.0150 (3)	0.1698 (4)	0.22901 (16)	0.0422 (6)
H3	1.0619	0.1033	0.2729	0.051*
C4	1.0825 (2)	0.2672 (3)	0.18589 (15)	0.0341 (5)
C5	1.0069 (3)	0.3606 (3)	0.12018 (16)	0.0381 (6)
H5	1.0515	0.4273	0.0913	0.046*
C6	0.6586 (2)	0.2626 (3)	0.10991 (16)	0.0381 (6)
C7	1.2334 (3)	0.2704 (4)	0.21038 (16)	0.0401 (6)
C8	0.3824 (3)	−0.2064 (4)	0.16064 (19)	0.0496 (7)
H8A	0.3570	−0.2911	0.1951	0.059*
H8B	0.4386	−0.2640	0.1326	0.059*
C9	0.2599 (3)	−0.1373 (4)	0.09994 (18)	0.0475 (7)
H9A	0.2120	−0.2316	0.0669	0.057*
H9B	0.2015	−0.0841	0.1277	0.057*
C10	0.1898 (3)	0.0876 (4)	−0.00271 (17)	0.0474 (7)
H10A	0.1346	0.1334	0.0290	0.057*
H10B	0.1353	0.0113	−0.0437	0.057*
C11	0.2408 (3)	0.2359 (4)	−0.04313 (17)	0.0525 (8)
H11A	0.2909	0.1892	−0.0777	0.063*
H11B	0.1657	0.3001	−0.0770	0.063*
H2A	0.539 (3)	−0.100 (4)	0.249 (2)	0.058 (9)*
H2B	0.486 (3)	0.011 (4)	0.1790 (18)	0.044 (8)*
H2C	0.405 (4)	0.010 (5)	0.238 (2)	0.069 (10)*
H3A	0.352 (4)	−0.064 (5)	0.018 (2)	0.083 (12)*
H4A	0.417 (4)	0.320 (4)	0.032 (2)	0.059 (9)*
H4B	0.300 (4)	0.365 (5)	0.064 (2)	0.068 (11)*
H4C	0.322 (4)	0.463 (5)	−0.006 (2)	0.078 (12)*

	U11	U22	U33	U12	U13	U23
O1	0.0440 (12)	0.103 (2)	0.0698 (15)	−0.0193 (12)	0.0137 (11)	0.0258 (14)
O2	0.0361 (10)	0.0691 (14)	0.0538 (12)	0.0065 (10)	0.0041 (9)	0.0145 (11)
O3	0.0376 (10)	0.0646 (14)	0.0590 (13)	0.0127 (10)	0.0074 (9)	0.0041 (11)
O4	0.0381 (10)	0.0631 (13)	0.0544 (12)	−0.0137 (9)	0.0176 (9)	−0.0085 (10)
N1	0.0391 (11)	0.0379 (11)	0.0397 (11)	−0.0011 (9)	0.0103 (9)	0.0061 (9)
N2	0.0306 (11)	0.0380 (12)	0.0428 (12)	−0.0004 (9)	0.0055 (10)	0.0057 (10)
N3	0.0443 (13)	0.0444 (13)	0.0448 (13)	0.0052 (10)	0.0055 (10)	0.0025 (11)
N4	0.0377 (12)	0.0476 (14)	0.0454 (14)	0.0005 (11)	0.0084 (10)	0.0097 (11)
C1	0.0326 (11)	0.0284 (11)	0.0369 (12)	0.0018 (9)	0.0096 (10)	0.0012 (10)
C2	0.0364 (13)	0.0458 (15)	0.0480 (15)	−0.0022 (11)	0.0108 (11)	0.0151 (12)
C3	0.0366 (13)	0.0429 (14)	0.0450 (14)	0.0023 (11)	0.0083 (11)	0.0119 (12)
C4	0.0336 (12)	0.0303 (12)	0.0387 (13)	−0.0013 (10)	0.0108 (10)	−0.0055 (10)
C6	0.0323 (12)	0.0391 (13)	0.0414 (14)	−0.0006 (10)	0.0084 (10)	0.0004 (11)
C7	0.0333 (12)	0.0418 (14)	0.0446 (14)	−0.0002 (11)	0.0105 (11)	−0.0114 (12)
C8	0.0522 (17)	0.0348 (14)	0.0556 (17)	−0.0015 (12)	0.0056 (14)	0.0031 (12)
C9	0.0450 (15)	0.0411 (14)	0.0493 (15)	−0.0075 (12)	0.0021 (12)	−0.0018 (13)
C10	0.0462 (15)	0.0427 (15)	0.0451 (15)	0.0017 (12)	0.0000 (12)	−0.0072 (12)
C11	0.0604 (18)	0.0531 (17)	0.0379 (14)	0.0071 (15)	0.0040 (13)	0.0039 (13)
C5	0.0414 (13)	0.0343 (12)	0.0403 (13)	−0.0041 (11)	0.0146 (11)	0.0039 (11)

O1—C6	1.233 (3)	C1—C6	1.519 (3)
O2—C6	1.253 (3)	C2—C3	1.378 (4)
O3—C7	1.248 (3)	C2—H2	0.9300
O4—C7	1.262 (3)	C3—C4	1.385 (4)
N1—C5	1.340 (3)	C3—H3	0.9300
N1—C1	1.347 (3)	C4—C5	1.384 (4)
N2—C8	1.489 (4)	C4—C7	1.516 (3)
N2—H2A	0.96 (3)	C8—C9	1.503 (4)
N2—H2B	0.90 (3)	C8—H8A	0.9700
N2—H2C	1.00 (4)	C8—H8B	0.9700
N3—C10	1.444 (4)	C9—H9A	0.9700
N3—C9	1.450 (4)	C9—H9B	0.9700
N3—H3A	0.98 (4)	C10—C11	1.514 (4)
N4—C11	1.484 (4)	C10—H10A	0.9700
N4—H4A	0.94 (4)	C10—H10B	0.9700
N4—H4B	0.95 (4)	C11—H11A	0.9700
N4—H4C	0.91 (4)	C11—H11B	0.9700
C1—C2	1.387 (3)	C5—H5	0.9300
C5—N1—C1	117.5 (2)	O3—C7—O4	125.9 (2)
C8—N2—H2A	113.6 (19)	O3—C7—C4	117.2 (2)
C8—N2—H2B	108.7 (19)	O4—C7—C4	117.0 (2)
H2A—N2—H2B	103 (3)	N2—C8—C9	110.5 (2)
C8—N2—H2C	115 (2)	N2—C8—H8A	109.6
H2A—N2—H2C	111 (3)	C9—C8—H8A	109.6
H2B—N2—H2C	105 (3)	N2—C8—H8B	109.6
C10—N3—C9	114.7 (2)	C9—C8—H8B	109.6
C10—N3—H3A	111 (2)	H8A—C8—H8B	108.1
C9—N3—H3A	111 (2)	N3—C9—C8	109.2 (2)
C11—N4—H4A	112 (2)	N3—C9—H9A	109.8
C11—N4—H4B	112 (2)	C8—C9—H9A	109.8
H4A—N4—H4B	107 (3)	N3—C9—H9B	109.8
C11—N4—H4C	108 (2)	C8—C9—H9B	109.8
H4A—N4—H4C	109 (3)	H9A—C9—H9B	108.3
H4B—N4—H4C	108 (3)	N3—C10—C11	110.9 (2)
N1—C1—C2	122.0 (2)	N3—C10—H10A	109.5
N1—C1—C6	117.9 (2)	C11—C10—H10A	109.5
C2—C1—C6	120.1 (2)	N3—C10—H10B	109.5
C3—C2—C1	119.4 (2)	C11—C10—H10B	109.5
C3—C2—H2	120.3	H10A—C10—H10B	108.0
C1—C2—H2	120.3	N4—C11—C10	112.1 (2)
C2—C3—C4	119.5 (2)	N4—C11—H11A	109.2
C2—C3—H3	120.3	C10—C11—H11A	109.2
C4—C3—H3	120.3	N4—C11—H11B	109.2
C5—C4—C3	117.4 (2)	C10—C11—H11B	109.2
C5—C4—C7	121.8 (2)	H11A—C11—H11B	107.9
C3—C4—C7	120.8 (2)	N1—C5—C4	124.2 (2)
O1—C6—O2	125.4 (2)	N1—C5—H5	117.9
O1—C6—C1	117.2 (2)	C4—C5—H5	117.9
O2—C6—C1	117.4 (2)
C5—N1—C1—C2	0.1 (4)	C5—C4—C7—O3	−174.3 (2)
C5—N1—C1—C6	−178.4 (2)	C3—C4—C7—O3	5.8 (4)
N1—C1—C2—C3	−2.0 (4)	C5—C4—C7—O4	5.8 (4)
C6—C1—C2—C3	176.4 (3)	C3—C4—C7—O4	−174.1 (2)
C1—C2—C3—C4	2.6 (4)	C10—N3—C9—C8	−170.1 (2)
C2—C3—C4—C5	−1.3 (4)	N2—C8—C9—N3	58.8 (3)
C2—C3—C4—C7	178.6 (3)	C9—N3—C10—C11	170.9 (2)
N1—C1—C6—O1	−170.7 (3)	N3—C10—C11—N4	−58.1 (3)
C2—C1—C6—O1	10.9 (4)	C1—N1—C5—C4	1.3 (4)
N1—C1—C6—O2	9.9 (4)	C3—C4—C5—N1	−0.7 (4)
C2—C1—C6—O2	−168.6 (3)	C7—C4—C5—N1	179.4 (2)

Cg is the centroid of the pyridine ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3i	0.96 (3)	2.56 (3)	3.254 (3)	130 (2)
N2—H2A···O4i	0.96 (3)	1.94 (3)	2.886 (3)	169 (3)
N2—H2B···O1	0.90 (3)	1.98 (3)	2.821 (4)	155 (3)
N2—H2C···O3ii	0.99 (4)	1.87 (4)	2.843 (3)	167 (3)
N3—H3A···O2iii	0.97 (4)	2.38 (4)	3.223 (3)	145 (3)
N4—H4A···O2	0.95 (4)	1.91 (4)	2.807 (4)	158 (3)
N4—H4B···O4ii	0.94 (4)	1.92 (3)	2.840 (3)	167 (4)
N4—H4C···O2iv	0.91 (4)	1.98 (4)	2.823 (4)	154 (4)
N4—H4C···N1iv	0.91 (4)	2.57 (4)	3.253 (4)	133 (3)
C8—H8A···O1v	0.97	2.49	3.218 (4)	132
C3—H3···Cgi	0.93	2.83	3.588 (3)	139
C10—H10B···Cgiii	0.97	2.91	3.846 (3)	161

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3i	0.96 (3)	2.56 (3)	3.254 (3)	130 (2)
N2—H2A⋯O4i	0.96 (3)	1.94 (3)	2.886 (3)	169 (3)
N2—H2B⋯O1	0.90 (3)	1.98 (3)	2.821 (4)	155 (3)
N2—H2C⋯O3ii	0.99 (4)	1.87 (4)	2.843 (3)	167 (3)
N3—H3A⋯O2iii	0.97 (4)	2.38 (4)	3.223 (3)	145 (3)
N4—H4A⋯O2	0.95 (4)	1.91 (4)	2.807 (4)	158 (3)
N4—H4B⋯O4ii	0.94 (4)	1.92 (3)	2.840 (3)	167 (4)
N4—H4C⋯O2iv	0.91 (4)	1.98 (4)	2.823 (4)	154 (4)
N4—H4C⋯N1iv	0.91 (4)	2.57 (4)	3.253 (4)	133 (3)
C8—H8A⋯O1v	0.97	2.49	3.218 (4)	132
C3—H3⋯Cgi	0.93	2.83	3.588 (3)	139
C10—H10B⋯Cgiii	0.97	2.91	3.846 (3)	161

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