N1,N1-Dimethyl­propane-1,2-diaminium bis­(6-carb­oxy­pyridine-2-carboxyl­ate) monohydrate

Aghabozorg, H.; Foroughian, M.; Foroumadi, A.; Bruno, G.; Amiri Rudbari, H.

doi:10.1107/S1600536811009287

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages o932-o933

doi:10.1107/S1600536811009287

Open

access

N¹,N¹-Dimethylpropane-1,2-diaminium bis(6-carboxypyridine-2-carboxylate) monohydrate

Hossein Aghabozorg,^a ^* Mahsa Foroughian,^a Alireza Foroumadi,^b Giuseppe Bruno ^c and Hadi Amiri Rudbari ^c

^aFaculty of Chemistry, Islamic Azad University, North Tehran Branch, Tehran, Iran, ^bDrug Design and Development Research Center, Tehran University of Medical Sciences, Tehran, Iran, and ^cDipartimento di Chimica Inorganica, Vill. S. Agata, Salita Sperone 31, Universita di Messina, 98166 Messina, Italy
^*Correspondence e-mail: haghabozorg@yahoo.com

(Received 17 February 2011; accepted 10 March 2011; online 19 March 2011)

The asymmetric unit of the title proton-transfer compound, C₅H₁₆N₂²⁺·2C₇H₄NO₄⁻·H₂O, consists of two mono-deprotonated pyridine-2,6-dicarboxylic acid molecules as anions, viz. (py-2,6-dcH)⁻, one diprotonated N¹,N¹-dimethylpropane-1,2-diamine molecule as a cation, viz. (dmpdaH₂)²⁺, and one water molecule. The crystal packing shows extensive O—H⋯O, N—H⋯O, N—H⋯N and O—H⋯N and weak intermolecular C—H⋯O hydrogen bonds. These interactions link the (dmpdaH₂)²⁺ cation, the (py-2,6-dcH)⁻ anions and water molecule and play an important role in the stabilization of crystal packing.

Related literature

For background to proton-transfer compounds, see: Aghabozorg et al. (2008 ). For related structures, see: Aghabozorg, Bayan et al. (2011 ); Aghabozorg, Mofidi Rouchi et al. (2011 ); Aghabozorg, Saemi et al. (2011 ); Sharif et al. (2010 ).

Experimental

Crystal data

C₅H₁₆N₂²⁺·2C₇H₄NO₄⁻·H₂O
M_r = 454.44
Orthorhombic, P 2₁ 2₁ 2₁
a = 11.826 (8) Å
b = 13.376 (8) Å
c = 13.479 (8) Å
V = 2132 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.42 × 0.38 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.708, T_max = 0.746
70173 measured reflections
4650 independent reflections
4509 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.084
S = 1.07
4650 reflections
298 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O9	0.91	1.82	2.711 (2)	165
N2—H1A⋯O9	0.89	2.55	3.392 (3)	158
N2—H1A⋯N3	0.89	2.40	2.988 (2)	124
N2—H2A⋯O5ⁱ	0.89	2.25	2.948 (2)	135
N2—H2A⋯N4ⁱ	0.89	2.32	3.123 (3)	151
O3—H3⋯O5	0.82	1.68	2.473 (2)	162
N2—H3A⋯O2ⁱⁱ	0.89	2.05	2.845 (2)	148
N2—H3A⋯O7ⁱ	0.89	2.30	2.902 (2)	125
O7—H7⋯O1ⁱⁱⁱ	0.82	1.75	2.535 (2)	159
O9—H9A⋯O1	0.80 (2)	2.30 (2)	2.900 (2)	132 (2)
O9—H9A⋯N3	0.80 (2)	2.38 (2)	3.107 (3)	152 (2)
O9—H9B⋯O3	0.83 (2)	2.33 (3)	2.958 (3)	133 (3)
O9—H9B⋯O6	0.83 (2)	2.16 (2)	2.844 (2)	139 (3)
C3—H3B⋯O6^iv	0.97	2.58	3.541 (3)	172
C3—H3C⋯O2ⁱⁱ	0.97	2.20	3.057 (3)	147
C4—H4⋯O4ⁱ	0.98	2.45	3.349 (3)	152
C15—H15⋯O8^v	0.93	2.48	3.166 (3)	131
C2—H20A⋯O4ⁱ	0.96	2.57	3.443 (3)	152
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x, y+1, z; (iv) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (v) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009287/vm2081sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811009287/vm2081Isup2.hkl

checkCIF report

Comment top

Proton transfer is very important in chemistry, biochemistry and medicinal chemistry. In order to synthesize new types of proton transfer compounds our research group focusses on forming new compounds from pyridine dicarboxcylic acids (Aghabozorg et al. 2008) and different organic bases with nitrogen donor sites such as propane-1,3-diamine (Aghabozorg, Bayan et al., 2011), diethylenetriamine (Aghabozorg, Saemi et al., 2011) and 2-amino-4-methylpyridine (Aghabozorg, Mofidi Rouchi et al., 2011; Sharif et al., 2010).

The asymmetric unit of the title compound consists of two mono deprotonated pyridine-2,6-dicarboxylic acid as anion, one diprotonated N,N'-dimethyl-1,2-propanediamine as cation, and one water molecule (Fig. 1). In the crystal packing there are extensive O—H···O, N—H···O, N—H···N, O—H···N and weak intermolecular C—H···O hydrogen bonds (Table 1, Fig. 2, Fig. 3). The N,N'-dimethyl-1,2-propanediaminium (dmpdaH₂)²⁺ cation is linked to the water molecule by N—H···O hydrogen bonds. This water molecule also connects the cationic part to the anionic part by N—H···O, O—H···N and O—H···O hydrogen bonds. These hydrogen bonds play an important role in the stabilization of the crystal packing.

Related literature top

For background to proton-transfer compounds, see: Aghabozorg et al. (2008). For related structures, see: Aghabozorg, Bayan et al. (2011); Aghabozorg, Mofidi Rouchi et al. (2011); Aghabozorg, Saemi et al. (2011); Sharif et al. (2010).

Experimental top

The solution of pyridine-2,6-dicarboxylic acid (0.334 g, 2 mmol) in 15 ml water was reacted with a solution of N,N'-dimethyl-1,2-propanediamine (0.258 ml, 2 mmol) in 7 ml water in 1:1 molar ratios. The reaction mixture was stirred for 2hrs at 298 K. The colorless crystals of the title compound appeared after slow evaporation of solvent at room temperature in darkness (m.p:177°C).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. The packing diagram of the title compound showing hydrogen bonding interactions in the asymmetric unit as blue dashed lines.
	Fig. 3. The packing diagram of the title compound showing all hydrogen bonding interactions as blue dashed lines. Symmetry codes: (i) -x+1, y-1/2, -z+3/2; (ii) -x+1, y+1/2, -z+3/2; (iii) x, y+1, z; (iv) -x+3/2, -y+1, z-1/2; (v) -x+2, y-1/2, -z+3/2.

N¹,N¹-Dimethylpropane-1,2-diaminium bis(6-carboxypyridine-2-carboxylate) monohydrate top

Crystal data top

C₅H₁₆N₂²⁺·2C₇H₄NO₄⁻·H₂O	F(000) = 960
M_r = 454.44	D_x = 1.416 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 296(2) reflections
a = 11.826 (8) Å	θ = 2.2–27.0°
b = 13.376 (8) Å	µ = 0.11 mm⁻¹
c = 13.479 (8) Å	T = 293 K
V = 2132 (2) Å³	Irregular, colorless
Z = 4	0.42 × 0.38 × 0.22 mm

Data collection top

Bruker APEXII CCD diffractometer	4650 independent reflections
Radiation source: fine-focus sealed tube	4509 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→15
T_min = 0.708, T_max = 0.746	k = −17→17
70173 measured reflections	l = −17→17

Refinement top

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)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0516P)² + 0.2616P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
4650 reflections	Δρ_max = 0.23 e Å⁻³
298 parameters	Δρ_min = −0.18 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0064 (13)

Crystal data top

C₅H₁₆N₂²⁺·2C₇H₄NO₄⁻·H₂O	V = 2132 (2) Å³
M_r = 454.44	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 11.826 (8) Å	µ = 0.11 mm⁻¹
b = 13.376 (8) Å	T = 293 K
c = 13.479 (8) Å	0.42 × 0.38 × 0.22 mm

Data collection top

Bruker APEXII CCD diffractometer	4650 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	4509 reflections with I > 2σ(I)
T_min = 0.708, T_max = 0.746	R_int = 0.025
70173 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	3 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.23 e Å⁻³
4650 reflections	Δρ_min = −0.18 e Å⁻³
298 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.82378 (16)	0.49387 (15)	0.59189 (15)	0.0608 (4)
H10A	0.7917	0.5578	0.6078	0.091*
H10B	0.8457	0.4929	0.5233	0.091*
H10C	0.8890	0.4823	0.6328	0.091*
C2	0.78465 (16)	0.31373 (12)	0.58604 (14)	0.0589 (4)
H20A	0.7278	0.2639	0.5979	0.088*
H20B	0.8493	0.3005	0.6271	0.088*
H20C	0.8067	0.3119	0.5175	0.088*
C3	0.63379 (12)	0.43601 (10)	0.55191 (10)	0.0410 (3)
H3B	0.6481	0.4194	0.4830	0.049*
H3C	0.6194	0.5073	0.5552	0.049*
C4	0.52821 (12)	0.38176 (9)	0.58465 (9)	0.0352 (3)
H4	0.5460	0.3112	0.5963	0.042*
C5	0.44060 (16)	0.38990 (14)	0.50382 (12)	0.0557 (4)
H5A	0.3731	0.3555	0.5239	0.084*
H5B	0.4694	0.3603	0.4440	0.084*
H5C	0.4235	0.4591	0.4921	0.084*
C6	0.51400 (11)	0.21400 (9)	0.86340 (10)	0.0361 (3)
C7	0.44510 (11)	0.29707 (9)	0.91060 (9)	0.0323 (2)
C8	0.34944 (14)	0.27536 (10)	0.96579 (11)	0.0469 (3)
H8	0.3263	0.2095	0.9746	0.056*
C9	0.28930 (15)	0.35256 (12)	1.00737 (13)	0.0547 (4)
H9	0.2244	0.3398	1.0442	0.066*
C10	0.32657 (12)	0.44927 (11)	0.99364 (11)	0.0433 (3)
H10	0.2881	0.5029	1.0218	0.052*
C11	0.42230 (10)	0.46459 (9)	0.93714 (9)	0.0309 (2)
C12	0.46436 (11)	0.56979 (9)	0.91995 (9)	0.0347 (3)
C13	0.74414 (11)	0.71223 (9)	0.80029 (10)	0.0360 (3)
C14	0.81762 (10)	0.79792 (9)	0.76580 (10)	0.0327 (2)
C15	0.92660 (12)	0.77789 (11)	0.73243 (12)	0.0446 (3)
H15	0.9531	0.7125	0.7291	0.054*
C16	0.99431 (12)	0.85656 (12)	0.70449 (13)	0.0490 (4)
H16	1.0672	0.8452	0.6812	0.059*
C17	0.95259 (11)	0.95225 (11)	0.71152 (10)	0.0402 (3)
H17	0.9975	1.0069	0.6951	0.048*
C18	0.84204 (10)	0.96563 (9)	0.74366 (9)	0.0315 (2)
C19	0.79612 (10)	1.07016 (9)	0.75010 (9)	0.0330 (2)
N1	0.73847 (10)	0.41412 (9)	0.61018 (8)	0.0399 (3)
H1	0.7203	0.4150	0.6758	0.048*
N2	0.47949 (9)	0.42609 (8)	0.67685 (8)	0.0340 (2)
H1A	0.5298	0.4217	0.7258	0.051*
H2A	0.4171	0.3930	0.6936	0.051*
H3A	0.4626	0.4900	0.6661	0.051*
N3	0.48126 (8)	0.39046 (7)	0.89568 (7)	0.0291 (2)
N4	0.77430 (8)	0.89011 (7)	0.76994 (7)	0.0295 (2)
O1	0.59431 (8)	0.23905 (6)	0.80781 (8)	0.0420 (2)
O2	0.48705 (13)	0.12753 (7)	0.88430 (10)	0.0636 (4)
O3	0.54684 (9)	0.57393 (7)	0.85809 (8)	0.0454 (2)
H3	0.5668	0.6322	0.8511	0.068*
O4	0.42263 (12)	0.63994 (8)	0.96310 (10)	0.0592 (3)
O5	0.64280 (8)	0.73404 (6)	0.82184 (8)	0.0417 (2)
O6	0.78683 (10)	0.62868 (7)	0.80691 (11)	0.0570 (3)
O7	0.68767 (8)	1.07388 (7)	0.76530 (8)	0.0428 (2)
H7	0.6673	1.1324	0.7681	0.064*
O8	0.85621 (10)	1.14190 (8)	0.74214 (11)	0.0578 (3)
O9	0.72243 (10)	0.42389 (9)	0.81056 (8)	0.0489 (3)
H9A	0.6703 (19)	0.3950 (18)	0.835 (2)	0.099 (9)*
H9B	0.711 (3)	0.4830 (14)	0.827 (2)	0.115 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0545 (9)	0.0633 (10)	0.0645 (10)	−0.0123 (8)	0.0124 (8)	−0.0003 (8)
C2	0.0586 (10)	0.0474 (9)	0.0706 (10)	0.0237 (8)	0.0006 (8)	−0.0045 (8)
C3	0.0424 (7)	0.0358 (6)	0.0446 (7)	0.0094 (6)	0.0129 (5)	0.0066 (6)
C4	0.0431 (7)	0.0256 (5)	0.0370 (6)	0.0036 (5)	0.0063 (5)	−0.0008 (5)
C5	0.0664 (10)	0.0583 (9)	0.0423 (7)	−0.0145 (8)	−0.0085 (7)	−0.0005 (7)
C6	0.0419 (6)	0.0232 (5)	0.0431 (6)	0.0004 (5)	0.0016 (5)	0.0027 (5)
C7	0.0382 (6)	0.0248 (5)	0.0340 (5)	−0.0014 (5)	0.0030 (5)	0.0020 (4)
C8	0.0547 (8)	0.0329 (7)	0.0529 (8)	−0.0130 (6)	0.0179 (7)	−0.0007 (6)
C9	0.0528 (9)	0.0525 (8)	0.0587 (9)	−0.0150 (7)	0.0298 (8)	−0.0087 (7)
C10	0.0406 (7)	0.0406 (7)	0.0489 (7)	0.0015 (5)	0.0156 (6)	−0.0094 (6)
C11	0.0322 (6)	0.0276 (5)	0.0327 (5)	0.0004 (5)	0.0011 (5)	−0.0007 (4)
C12	0.0375 (6)	0.0256 (5)	0.0411 (6)	0.0034 (5)	−0.0008 (5)	−0.0004 (5)
C13	0.0369 (6)	0.0256 (5)	0.0455 (7)	0.0014 (5)	−0.0014 (5)	−0.0007 (5)
C14	0.0296 (6)	0.0273 (5)	0.0412 (6)	0.0026 (4)	0.0001 (5)	0.0010 (5)
C15	0.0341 (6)	0.0351 (6)	0.0647 (9)	0.0091 (5)	0.0054 (6)	0.0012 (6)
C16	0.0283 (6)	0.0533 (8)	0.0654 (9)	0.0069 (6)	0.0112 (6)	0.0066 (7)
C17	0.0292 (6)	0.0420 (7)	0.0495 (7)	−0.0043 (5)	0.0044 (5)	0.0083 (6)
C18	0.0294 (5)	0.0295 (6)	0.0357 (6)	−0.0009 (4)	−0.0008 (5)	0.0046 (4)
C19	0.0317 (5)	0.0283 (5)	0.0391 (6)	−0.0024 (5)	0.0002 (5)	0.0053 (5)
N1	0.0420 (6)	0.0376 (6)	0.0400 (5)	0.0045 (5)	0.0107 (5)	−0.0022 (4)
N2	0.0305 (5)	0.0362 (5)	0.0353 (5)	−0.0017 (4)	0.0039 (4)	−0.0012 (4)
N3	0.0299 (5)	0.0238 (4)	0.0335 (5)	0.0005 (4)	0.0034 (4)	0.0018 (4)
N4	0.0267 (4)	0.0255 (4)	0.0363 (5)	0.0006 (4)	0.0008 (4)	0.0017 (4)
O1	0.0368 (4)	0.0260 (4)	0.0632 (6)	0.0017 (4)	0.0110 (4)	−0.0009 (4)
O2	0.0880 (9)	0.0216 (4)	0.0814 (8)	0.0001 (5)	0.0362 (7)	0.0061 (5)
O3	0.0495 (5)	0.0229 (4)	0.0637 (6)	−0.0027 (4)	0.0157 (5)	0.0024 (4)
O4	0.0746 (8)	0.0288 (5)	0.0742 (8)	0.0032 (5)	0.0236 (7)	−0.0083 (5)
O5	0.0334 (4)	0.0256 (4)	0.0660 (6)	−0.0011 (4)	0.0090 (4)	0.0041 (4)
O6	0.0486 (6)	0.0267 (5)	0.0956 (9)	0.0067 (4)	0.0086 (6)	0.0069 (5)
O7	0.0325 (4)	0.0244 (4)	0.0714 (6)	0.0015 (3)	0.0023 (4)	−0.0022 (4)
O8	0.0448 (6)	0.0313 (5)	0.0973 (9)	−0.0083 (4)	0.0141 (6)	0.0070 (5)
O9	0.0454 (6)	0.0497 (6)	0.0516 (6)	0.0039 (5)	0.0127 (5)	−0.0008 (5)

Geometric parameters (Å, º) top

C1—N1	1.489 (2)	C10—H10	0.9300
C1—H10A	0.9600	C11—N3	1.3347 (15)
C1—H10B	0.9600	C11—C12	1.5104 (16)
C1—H10C	0.9600	C12—O4	1.2094 (16)
C2—N1	1.4857 (18)	C12—O3	1.2843 (16)
C2—H20A	0.9600	C13—O6	1.2296 (16)
C2—H20B	0.9600	C13—O5	1.2672 (16)
C2—H20C	0.9600	C13—C14	1.5117 (17)
C3—N1	1.4950 (19)	C14—N4	1.3364 (15)
C3—C4	1.5101 (18)	C14—C15	1.3910 (18)
C3—H3B	0.9700	C15—C16	1.375 (2)
C3—H3C	0.9700	C15—H15	0.9300
C4—N2	1.4926 (15)	C16—C17	1.375 (2)
C4—C5	1.507 (2)	C16—H16	0.9300
C4—H4	0.9800	C17—C18	1.3889 (17)
C5—H5A	0.9600	C17—H17	0.9300
C5—H5B	0.9600	C18—N4	1.3371 (15)
C5—H5C	0.9600	C18—C19	1.5025 (16)
C6—O2	1.2323 (16)	C19—O8	1.1988 (16)
C6—O1	1.2553 (16)	C19—O7	1.2996 (15)
C6—C7	1.5177 (17)	N1—H1	0.9100
C7—N3	1.3356 (15)	N2—H1A	0.8900
C7—C8	1.3848 (18)	N2—H2A	0.8900
C8—C9	1.373 (2)	N2—H3A	0.8900
C8—H8	0.9300	O3—H3	0.8200
C9—C10	1.379 (2)	O7—H7	0.8200
C9—H9	0.9300	O9—H9A	0.799 (17)
C10—C11	1.3798 (18)	O9—H9B	0.830 (17)

N1—C1—H10A	109.5	N3—C11—C10	123.33 (11)
N1—C1—H10B	109.5	N3—C11—C12	117.12 (10)
H10A—C1—H10B	109.5	C10—C11—C12	119.55 (11)
N1—C1—H10C	109.5	O4—C12—O3	126.07 (13)
H10A—C1—H10C	109.5	O4—C12—C11	120.98 (12)
H10B—C1—H10C	109.5	O3—C12—C11	112.94 (10)
N1—C2—H20A	109.5	O6—C13—O5	125.52 (13)
N1—C2—H20B	109.5	O6—C13—C14	118.39 (12)
H20A—C2—H20B	109.5	O5—C13—C14	116.08 (11)
N1—C2—H20C	109.5	N4—C14—C15	123.12 (12)
H20A—C2—H20C	109.5	N4—C14—C13	117.80 (11)
H20B—C2—H20C	109.5	C15—C14—C13	119.08 (11)
N1—C3—C4	115.91 (11)	C16—C15—C14	118.73 (13)
N1—C3—H3B	108.3	C16—C15—H15	120.6
C4—C3—H3B	108.3	C14—C15—H15	120.6
N1—C3—H3C	108.3	C15—C16—C17	118.99 (13)
C4—C3—H3C	108.3	C15—C16—H16	120.5
H3B—C3—H3C	107.4	C17—C16—H16	120.5
N2—C4—C5	107.93 (12)	C16—C17—C18	118.63 (12)
N2—C4—C3	111.82 (11)	C16—C17—H17	120.7
C5—C4—C3	108.80 (11)	C18—C17—H17	120.7
N2—C4—H4	109.4	N4—C18—C17	123.32 (12)
C5—C4—H4	109.4	N4—C18—C19	118.11 (10)
C3—C4—H4	109.4	C17—C18—C19	118.57 (11)
C4—C5—H5A	109.5	O8—C19—O7	124.64 (12)
C4—C5—H5B	109.5	O8—C19—C18	121.69 (11)
H5A—C5—H5B	109.5	O7—C19—C18	113.67 (10)
C4—C5—H5C	109.5	C2—N1—C1	111.23 (13)
H5A—C5—H5C	109.5	C2—N1—C3	111.49 (12)
H5B—C5—H5C	109.5	C1—N1—C3	109.50 (12)
O2—C6—O1	125.64 (13)	C2—N1—H1	108.2
O2—C6—C7	116.91 (12)	C1—N1—H1	108.2
O1—C6—C7	117.45 (10)	C3—N1—H1	108.2
N3—C7—C8	122.59 (12)	C4—N2—H1A	109.5
N3—C7—C6	116.73 (11)	C4—N2—H2A	109.5
C8—C7—C6	120.68 (11)	H1A—N2—H2A	109.5
C9—C8—C7	118.99 (12)	C4—N2—H3A	109.5
C9—C8—H8	120.5	H1A—N2—H3A	109.5
C7—C8—H8	120.5	H2A—N2—H3A	109.5
C8—C9—C10	119.01 (13)	C11—N3—C7	117.68 (10)
C8—C9—H9	120.5	C14—N4—C18	117.15 (10)
C10—C9—H9	120.5	C12—O3—H3	109.5
C9—C10—C11	118.40 (12)	C19—O7—H7	109.5
C9—C10—H10	120.8	H9A—O9—H9B	103 (3)
C11—C10—H10	120.8

N1—C3—C4—N2	75.97 (14)	N4—C14—C15—C16	1.6 (2)
N1—C3—C4—C5	−164.91 (12)	C13—C14—C15—C16	−177.73 (14)
O2—C6—C7—N3	173.61 (14)	C14—C15—C16—C17	0.7 (2)
O1—C6—C7—N3	−5.34 (18)	C15—C16—C17—C18	−2.0 (2)
O2—C6—C7—C8	−6.7 (2)	C16—C17—C18—N4	1.2 (2)
O1—C6—C7—C8	174.39 (14)	C16—C17—C18—C19	−179.26 (13)
N3—C7—C8—C9	−0.3 (2)	N4—C18—C19—O8	168.74 (14)
C6—C7—C8—C9	179.99 (14)	C17—C18—C19—O8	−10.81 (19)
C7—C8—C9—C10	−0.6 (3)	N4—C18—C19—O7	−10.92 (16)
C8—C9—C10—C11	1.0 (3)	C17—C18—C19—O7	169.53 (12)
C9—C10—C11—N3	−0.5 (2)	C4—C3—N1—C2	74.31 (15)
C9—C10—C11—C12	179.35 (14)	C4—C3—N1—C1	−162.17 (12)
N3—C11—C12—O4	−172.38 (13)	C10—C11—N3—C7	−0.30 (18)
C10—C11—C12—O4	7.7 (2)	C12—C11—N3—C7	179.80 (11)
N3—C11—C12—O3	6.62 (16)	C8—C7—N3—C11	0.73 (19)
C10—C11—C12—O3	−173.29 (12)	C6—C7—N3—C11	−179.55 (11)
O6—C13—C14—N4	−172.34 (13)	C15—C14—N4—C18	−2.43 (19)
O5—C13—C14—N4	6.38 (18)	C13—C14—N4—C18	176.91 (11)
O6—C13—C14—C15	7.0 (2)	C17—C18—N4—C14	1.00 (18)
O5—C13—C14—C15	−174.25 (13)	C19—C18—N4—C14	−178.52 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O9	0.91	1.82	2.711 (2)	165
N2—H1A···O9	0.89	2.55	3.392 (3)	158
N2—H1A···N3	0.89	2.40	2.988 (2)	124
N2—H2A···O5ⁱ	0.89	2.25	2.948 (2)	135
N2—H2A···N4ⁱ	0.89	2.32	3.123 (3)	151
O3—H3···O5	0.82	1.68	2.473 (2)	162
N2—H3A···O2ⁱⁱ	0.89	2.05	2.845 (2)	148
N2—H3A···O7ⁱ	0.89	2.30	2.902 (2)	125
O7—H7···O1ⁱⁱⁱ	0.82	1.75	2.535 (2)	159
O9—H9A···O1	0.80 (2)	2.30 (2)	2.900 (2)	132 (2)
O9—H9A···N3	0.80 (2)	2.38 (2)	3.107 (3)	152 (2)
O9—H9B···O3	0.83 (2)	2.33 (3)	2.958 (3)	133 (3)
O9—H9B···O6	0.83 (2)	2.16 (2)	2.844 (2)	139 (3)
C3—H3B···O6^iv	0.97	2.58	3.541 (3)	172
C3—H3C···O2ⁱⁱ	0.97	2.20	3.057 (3)	147
C4—H4···O4ⁱ	0.98	2.45	3.349 (3)	152
C15—H15···O8^v	0.93	2.48	3.166 (3)	131
C2—H20A···O4ⁱ	0.96	2.57	3.443 (3)	152

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x, y+1, z; (iv) −x+3/2, −y+1, z−1/2; (v) −x+2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₅H₁₆N₂²⁺·2C₇H₄NO₄⁻·H₂O
M_r	454.44
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	11.826 (8), 13.376 (8), 13.479 (8)
V (Å³)	2132 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.42 × 0.38 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.708, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	70173, 4650, 4509
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.084, 1.07
No. of reflections	4650
No. of parameters	298
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.18

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O9	0.9100	1.8200	2.711 (2)	165
N2—H1A···O9	0.8900	2.5500	3.392 (3)	158
N2—H1A···N3	0.8900	2.4000	2.988 (2)	124
N2—H2A···O5ⁱ	0.8900	2.2500	2.948 (2)	135
N2—H2A···N4ⁱ	0.8900	2.3200	3.123 (3)	151
O3—H3···O5	0.8200	1.6800	2.473 (2)	162
N2—H3A···O2ⁱⁱ	0.8900	2.0500	2.845 (2)	148
N2—H3A···O7ⁱ	0.8900	2.3000	2.902 (2)	125
O7—H7···O1ⁱⁱⁱ	0.8200	1.7500	2.535 (2)	159
O9—H9A···O1	0.80 (2)	2.30 (2)	2.900 (2)	132 (2)
O9—H9A···N3	0.80 (2)	2.38 (2)	3.107 (3)	152 (2)
O9—H9B···O3	0.83 (2)	2.33 (3)	2.958 (3)	133 (3)
O9—H9B···O6	0.83 (2)	2.16 (2)	2.844 (2)	139 (3)
C3—H3B···O6^iv	0.9700	2.5800	3.541 (3)	172.00
C3—H3C···O2ⁱⁱ	0.9700	2.2000	3.057 (3)	147.00
C4—H4···O4ⁱ	0.9800	2.4500	3.349 (3)	152.00
C15—H15···O8^v	0.9300	2.4800	3.166 (3)	131.00
C2—H20A···O4ⁱ	0.9600	2.5700	3.443 (3)	152.00

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x, y+1, z; (iv) −x+3/2, −y+1, z−1/2; (v) −x+2, y−1/2, −z+3/2.

Acknowledgements

The authors are grateful to the Islamic Azad University, North Tehran Branch, for financial support.

References

Aghabozorg, H., Bayan, M., Mirzaei, M. & Notash, B. (2011). Acta Cryst. E67, o610. Web of Science CSD CrossRef IUCr Journals Google Scholar
Aghabozorg, H., Manteghi, F. & Sheshmani, S. (2008). J. Iran. Chem. Soc, 5, 184–227. CrossRef CAS Google Scholar
Aghabozorg, H., Mofidi Rouchi, A., Mirzaei, M. & Notash, B. (2011). Acta Cryst. E67, o54. Web of Science CrossRef IUCr Journals Google Scholar
Aghabozorg, H., Saemi, M., Khazaei, Z., Amani, V. & Notash, B. (2011). Acta Cryst. E67, o292. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sharif, M. A., Tabatabaee, M., Adinehloo, M. & Aghabozorg, H. (2010). Acta Cryst. E66, o3232. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.