Ethane-1,2-di­ammonium bis(4-nitro­benzoate) dihydrate

Lynch, D.E.; Healy, P.C.

doi:10.1107/S1600536803014144

Ethane-1,2-diammonium bis(4-nitrobenzoate) dihydrate

The structure of the title compound, C₂H₁₀N₂²⁺·2C₇H₄NO₄^-·2H₂O, comprises interdigitated two-dimensional hydrogen-bonded networks derived from a repeat unit that contains the bisammonium, two benzoates and two water molecules.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803014144/cv6203sup1.cif Contains datablocks I, default
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803014144/cv6203Isup2.hkl Contains datablock I

CCDC reference: 217618

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Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.004 Å
R factor = 0.044
wR factor = 0.150
Data-to-parameter ratio = 11.8

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No syntax errors found

ADDSYM reports no extra symmetry

Comment top

A search of the Cambridge Structural Database (Allen, 2002) reveals that there are 39 reported organic salt structures containing ethane-1,2-diamine and a carboxylate group. Of these, 11 contain a metal and can be considered as coordination complexes. The remainder can be separated into the 19 that contain an alkyl carboxylate whereas the rest (nine) contain benzoates. Interestingly, the majority (five) of these are nitrobenzoates, mainly 4-nitroanthranilate (Smith, Wermuth & White, 2002), 3,5-dinitrobenzoate (Nethaji et al., 1992; Lynch et al., 1994; Burchell et al., 2001) and 3,5-dinitrosalicylate (Smith, Wermuth, Bott et al., 2002). Here we report the 1:2 organic salt dihydrate of ethane-1,2-diammonium with 4-nitrobenzoate, (I) (Fig. 1).

The solid-state packing of (I) involves two symmetrically unique two-dimensional hydrogen-bonded networks individually derived from the repeat unit represented in Fig. 2 by molecules A–C, O1w and O2w. Both networks, comprising of molecules A–C, O1w and O2w, and D–F, O3w andO 4w, respectively, are essentially identical with the symmetry between the groupings being broken by the interdigitation of the 4-NBA molecules. Crosslinking through the associations of the water molecules to adjacent carboxylate O atoms creates the second dimension in the network. Hydrogen-bonding interactions are listed in Table 1.

Experimental top

1:2 molar amounts of ethane-1,2-diamine and 4-nitrobenzoic acid were refluxed in ethanol for 20 min. Total evaporation of the solvent gave colourless needles (m.p. 465 K).

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The molecular configuration and atom-numbering scheme for the title compound, showing 50% probability ellipsoids.
	Fig. 2. Hydrogen-bonded unit that extends to form the two-dimensional networks of (I). [Symmetry code: (i) −x + 1, −y + 1, −z + 1.]

Ethane-1,2-diammonium bis(4-nitrobenzoate) bishydrate top

Crystal data top

C₂H₁₀N₂²⁺·2C₇H₄NO₄⁻·2H₂O	F(000) = 904
M_r = 430.38	D_x = 1.486 Mg m⁻³
Triclinic, P1	Melting point: 465 K K
a = 12.213 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 22.317 (2) Å	Cell parameters from 25 reflections
c = 7.091 (5) Å	θ = 13.0–19.2°
α = 89.47 (2)°	µ = 0.13 mm⁻¹
β = 89.17 (2)°	T = 298 K
γ = 84.72 (8)°	Needle, colourless
V = 1924.2 (14) Å³	0.40 × 0.20 × 0.10 mm
Z = 4

Data collection top

Rigaku AFC7-R diffractometer	R_int = 0.000
Radiation source: Rigaku rotating anode	θ_max = 25.4°, θ_min = 2.6°
Graphite monochromator	h = 0→14
ω–2θ scans	k = −26→26
6810 measured reflections	l = −8→8
6810 independent reflections	3 standard reflections every 150 reflections
3360 reflections with I > 2σ(I)	intensity decay: 0.4%

Refinement top

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0767P)²] where P = (F_o² + 2F_c²)/3
6810 reflections	(Δ/σ)_max < 0.001
577 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₂H₁₀N₂²⁺·2C₇H₄NO₄⁻·2H₂O	γ = 84.72 (8)°
M_r = 430.38	V = 1924.2 (14) Å³
Triclinic, P1	Z = 4
a = 12.213 (2) Å	Mo Kα radiation
b = 22.317 (2) Å	µ = 0.13 mm⁻¹
c = 7.091 (5) Å	T = 298 K
α = 89.47 (2)°	0.40 × 0.20 × 0.10 mm
β = 89.17 (2)°

Data collection top

Rigaku AFC7-R diffractometer	R_int = 0.000
6810 measured reflections	3 standard reflections every 150 reflections
6810 independent reflections	intensity decay: 0.4%
3360 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.150	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.21 e Å⁻³
6810 reflections	Δρ_min = −0.30 e Å⁻³
577 parameters

Special details top

Experimental. The scan width was (1.37 + 0.35tanθ)° with an ω scan speed of 0° per minute (up to 5 scans to achieve I/σ(I) > 15). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1.

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

	x	y	z	U_iso*/U_eq
N1A	0.23216 (19)	0.54109 (10)	0.5570 (3)	0.0426 (6)
H11A	0.2902	0.5203	0.6083	0.053*
H12A	0.1824	0.5514	0.6466	0.053*
H13A	0.2532	0.5741	0.5013	0.053*
C2A	0.1823 (3)	0.50264 (14)	0.4122 (4)	0.0508 (8)
H21A	0.1451	0.4717	0.4773	0.064*
H22A	0.1275	0.5276	0.3421	0.064*
C3A	0.2647 (3)	0.47324 (13)	0.2766 (4)	0.0501 (8)
H31A	0.3260	0.4539	0.3469	0.063*
H32A	0.2312	0.4422	0.2094	0.063*
N4A	0.30677 (19)	0.51532 (10)	0.1391 (3)	0.0419 (6)
H41A	0.2506	0.5360	0.0825	0.052*
H42A	0.3485	0.4948	0.0533	0.052*
H43A	0.3467	0.5406	0.1982	0.052*
C1B	0.5510 (2)	0.30216 (12)	0.6369 (3)	0.0332 (6)
C11B	0.6082 (2)	0.35913 (13)	0.6421 (4)	0.0399 (7)
O10B	0.55370 (17)	0.40763 (10)	0.6822 (4)	0.0641 (7)
O11B	0.70769 (17)	0.35512 (9)	0.6090 (4)	0.0650 (7)
C2B	0.4414 (2)	0.30245 (12)	0.5804 (4)	0.0375 (7)
H2B	0.4017	0.3387	0.5498	0.047*
C3B	0.3915 (2)	0.24917 (13)	0.5696 (4)	0.0381 (7)
H3B	0.3195	0.2490	0.5286	0.048*
C4B	0.4518 (2)	0.19635 (12)	0.6215 (4)	0.0384 (7)
N41B	0.3984 (2)	0.13999 (12)	0.6152 (4)	0.0513 (7)
O41B	0.3031 (2)	0.14151 (11)	0.5588 (4)	0.0746 (7)
O42B	0.4509 (2)	0.09368 (11)	0.6659 (4)	0.0750 (7)
C5B	0.5598 (2)	0.19450 (13)	0.6796 (4)	0.0412 (7)
H5B	0.5982	0.1583	0.7145	0.051*
C6B	0.6094 (2)	0.24795 (12)	0.6847 (4)	0.0370 (7)
H6B	0.6825	0.2475	0.7205	0.046*
C1C	0.0584 (2)	0.31712 (12)	0.8603 (4)	0.0349 (6)
C11C	0.1147 (2)	0.37438 (13)	0.8531 (4)	0.0427 (7)
O10C	0.20968 (17)	0.37066 (10)	0.7932 (4)	0.0689 (7)
O11C	0.06181 (19)	0.42206 (10)	0.9060 (4)	0.0724 (8)
C2C	0.1165 (2)	0.26292 (12)	0.8119 (4)	0.0360 (6)
H2C	0.1896	0.2627	0.7732	0.045*
C3C	0.0684 (2)	0.20914 (12)	0.8196 (4)	0.0381 (7)
H3C	0.1077	0.1730	0.7866	0.048*
C4C	−0.0391 (2)	0.21130 (12)	0.8777 (4)	0.0357 (6)
N41C	−0.0913 (2)	0.15434 (11)	0.8885 (3)	0.0487 (6)
O41C	−0.0347 (2)	0.10731 (10)	0.8572 (4)	0.0763 (8)
O42C	−0.1883 (2)	0.15646 (10)	0.9308 (4)	0.0708 (7)
C5C	−0.1000 (2)	0.26391 (12)	0.9253 (4)	0.0380 (7)
H5C	−0.1733	0.2637	0.9627	0.047*
C6C	−0.0508 (2)	0.31696 (12)	0.9169 (4)	0.0372 (7)
H6C	−0.0909	0.3529	0.9493	0.047*
N1D	0.31709 (19)	0.01744 (10)	0.3166 (3)	0.0422 (6)
H11D	0.3579	−0.0031	0.4026	0.053*
H12D	0.2586	0.0368	0.3726	0.053*
H13D	0.3568	0.0440	0.2595	0.053*
C2D	0.2798 (3)	−0.02539 (12)	0.1725 (4)	0.0461 (7)
H21D	0.2485	−0.0582	0.2382	0.058*
H22D	0.3436	−0.0424	0.1015	0.058*
C3D	0.1956 (2)	0.00314 (13)	0.0350 (4)	0.0463 (8)
H31D	0.1620	−0.0285	−0.0295	0.058*
H32D	0.1382	0.0266	0.1054	0.058*
N4D	0.24285 (19)	0.04236 (10)	−0.1063 (3)	0.0426 (6)
H41D	0.2636	0.0749	−0.0500	0.053*
H42D	0.1926	0.0535	−0.1925	0.053*
H43D	0.3009	0.0225	−0.1619	0.053*
C1E	0.4494 (2)	0.20569 (12)	0.1205 (3)	0.0336 (6)
C11E	0.3959 (2)	0.14704 (12)	0.1124 (4)	0.0374 (7)
O10E	0.30232 (16)	0.14802 (9)	0.0421 (3)	0.0519 (5)
O11E	0.44859 (16)	0.10078 (9)	0.1802 (3)	0.0554 (6)
C2E	0.3873 (2)	0.25904 (12)	0.0739 (4)	0.0354 (6)
H2E	0.3147	0.2581	0.0373	0.044*
C3E	0.4326 (2)	0.31335 (12)	0.0816 (4)	0.0393 (7)
H3E	0.3910	0.3492	0.0526	0.049*
C4E	0.5415 (2)	0.31327 (12)	0.1335 (4)	0.0374 (7)
N41E	0.5910 (2)	0.37068 (12)	0.1401 (3)	0.0519 (7)
O41E	0.5309 (2)	0.41736 (11)	0.1533 (4)	0.0830 (8)
O42E	0.6909 (2)	0.36982 (11)	0.1331 (4)	0.0767 (8)
C5E	0.6062 (2)	0.26158 (13)	0.1794 (4)	0.0387 (7)
H5E	0.6792	0.2630	0.2133	0.048*
C6E	0.5595 (2)	0.20742 (13)	0.1738 (4)	0.0380 (7)
H6E	0.6013	0.1719	0.2055	0.047*
C1F	0.9342 (2)	0.17594 (12)	0.3766 (4)	0.0343 (6)
C11F	0.8784 (2)	0.11876 (13)	0.3850 (4)	0.0401 (7)
O10F	0.77933 (17)	0.12319 (10)	0.4250 (4)	0.0663 (7)
O11F	0.93598 (17)	0.07002 (9)	0.3498 (3)	0.0532 (6)
C2F	0.8773 (2)	0.23024 (12)	0.4279 (4)	0.0373 (7)
H2F	0.8041	0.2306	0.4663	0.047*
C3F	0.9259 (2)	0.28348 (12)	0.4235 (4)	0.0402 (7)
H3F	0.8871	0.3195	0.4591	0.050*
C4F	1.0336 (2)	0.28150 (12)	0.3647 (4)	0.0366 (7)
N41F	1.0868 (2)	0.33846 (11)	0.3596 (4)	0.0495 (7)
O41F	1.0315 (2)	0.38479 (10)	0.4007 (4)	0.0734 (7)
O42F	1.1829 (2)	0.33641 (11)	0.3158 (4)	0.0740 (7)
C5F	1.0935 (2)	0.22884 (12)	0.3109 (4)	0.0355 (6)
H5F	1.1663	0.2290	0.2711	0.044*
C6F	1.0430 (2)	0.17582 (12)	0.3172 (4)	0.0358 (6)
H6F	1.0822	0.1399	0.2814	0.045*
O1W	0.11838 (18)	0.53425 (11)	0.8988 (3)	0.0493 (6)
H11	0.062 (3)	0.5558 (16)	0.945 (5)	0.077 (12)*
H12	0.106 (2)	0.4949 (16)	0.884 (4)	0.059 (10)*
O2W	0.35040 (19)	0.45444 (9)	0.7890 (3)	0.0484 (6)
H21	0.297 (3)	0.4269 (19)	0.780 (6)	0.102 (15)*
H22	0.410 (3)	0.4349 (15)	0.754 (5)	0.068 (11)*
O3W	0.12918 (18)	0.03580 (11)	0.5424 (3)	0.0472 (5)
H31	0.074 (3)	0.0501 (14)	0.492 (4)	0.056 (11)*
H32	0.109 (2)	−0.0040 (15)	0.577 (4)	0.061 (10)*
O4W	0.63636 (19)	0.04438 (9)	0.3369 (3)	0.0476 (5)
H41	0.578 (3)	0.0638 (16)	0.289 (5)	0.078 (13)*
H42	0.689 (3)	0.0755 (17)	0.368 (5)	0.086 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0460 (14)	0.0391 (14)	0.0435 (14)	−0.0098 (11)	0.0137 (11)	−0.0021 (11)
C2A	0.0536 (19)	0.0520 (19)	0.0498 (19)	−0.0220 (16)	0.0105 (15)	−0.0002 (15)
C3A	0.065 (2)	0.0394 (17)	0.0475 (19)	−0.0181 (15)	0.0135 (16)	−0.0031 (14)
N4A	0.0467 (14)	0.0382 (14)	0.0421 (14)	−0.0112 (11)	0.0100 (11)	−0.0047 (10)
C1B	0.0358 (15)	0.0393 (16)	0.0248 (14)	−0.0058 (13)	0.0091 (11)	−0.0026 (11)
C11B	0.0380 (17)	0.0429 (18)	0.0388 (17)	−0.0056 (14)	0.0093 (13)	−0.0005 (13)
O10B	0.0438 (13)	0.0436 (13)	0.1059 (19)	−0.0110 (10)	0.0189 (12)	−0.0218 (12)
O11B	0.0423 (13)	0.0437 (13)	0.109 (2)	−0.0095 (10)	0.0236 (12)	0.0093 (12)
C2B	0.0405 (17)	0.0390 (16)	0.0325 (15)	−0.0016 (13)	0.0063 (12)	−0.0027 (12)
C3B	0.0348 (15)	0.0490 (18)	0.0315 (15)	−0.0095 (14)	0.0031 (12)	−0.0086 (13)
C4B	0.0458 (18)	0.0439 (17)	0.0276 (15)	−0.0158 (14)	0.0083 (13)	−0.0042 (12)
N41B	0.0610 (19)	0.0481 (17)	0.0475 (16)	−0.0218 (15)	0.0128 (13)	−0.0073 (13)
O41B	0.0642 (17)	0.0748 (17)	0.0904 (19)	−0.0353 (14)	−0.0017 (14)	−0.0126 (14)
O42B	0.0865 (19)	0.0475 (15)	0.093 (2)	−0.0189 (14)	0.0127 (15)	0.0059 (13)
C5B	0.0488 (18)	0.0402 (17)	0.0341 (16)	−0.0036 (14)	0.0058 (13)	0.0070 (12)
C6B	0.0312 (15)	0.0454 (17)	0.0345 (16)	−0.0053 (13)	0.0039 (12)	0.0019 (12)
C1C	0.0364 (15)	0.0384 (16)	0.0302 (15)	−0.0058 (13)	0.0031 (12)	−0.0007 (12)
C11C	0.0398 (17)	0.0402 (17)	0.0489 (18)	−0.0092 (14)	0.0087 (14)	−0.0043 (14)
O10C	0.0444 (13)	0.0514 (14)	0.112 (2)	−0.0161 (11)	0.0264 (13)	−0.0032 (13)
O11C	0.0675 (15)	0.0399 (13)	0.111 (2)	−0.0183 (12)	0.0438 (14)	−0.0192 (12)
C2C	0.0328 (15)	0.0415 (17)	0.0334 (15)	−0.0028 (13)	0.0041 (12)	0.0008 (12)
C3C	0.0405 (16)	0.0352 (16)	0.0373 (16)	0.0033 (13)	−0.0005 (13)	0.0008 (12)
C4C	0.0425 (17)	0.0355 (16)	0.0305 (15)	−0.0115 (13)	−0.0036 (12)	0.0019 (12)
N41C	0.0614 (18)	0.0394 (16)	0.0472 (16)	−0.0143 (14)	−0.0008 (13)	0.0015 (12)
O41C	0.0916 (19)	0.0352 (13)	0.102 (2)	−0.0118 (13)	0.0213 (15)	−0.0014 (12)
O42C	0.0616 (16)	0.0569 (15)	0.098 (2)	−0.0293 (13)	0.0033 (14)	0.0005 (13)
C5C	0.0334 (15)	0.0423 (17)	0.0392 (17)	−0.0094 (13)	0.0031 (12)	−0.0008 (13)
C6C	0.0348 (16)	0.0356 (16)	0.0409 (16)	−0.0019 (12)	0.0054 (12)	−0.0055 (12)
N1D	0.0457 (14)	0.0402 (14)	0.0417 (14)	−0.0102 (11)	−0.0039 (11)	0.0080 (11)
C2D	0.059 (2)	0.0352 (16)	0.0456 (18)	−0.0131 (14)	−0.0024 (15)	0.0032 (13)
C3D	0.0520 (19)	0.0447 (18)	0.0456 (18)	−0.0213 (15)	−0.0045 (14)	0.0022 (14)
N4D	0.0472 (14)	0.0393 (14)	0.0418 (14)	−0.0058 (11)	−0.0055 (11)	0.0033 (11)
C1E	0.0362 (15)	0.0412 (16)	0.0241 (14)	−0.0073 (13)	0.0027 (11)	0.0010 (11)
C11E	0.0370 (17)	0.0380 (17)	0.0377 (16)	−0.0073 (13)	0.0014 (13)	0.0017 (13)
O10E	0.0407 (12)	0.0446 (12)	0.0721 (15)	−0.0101 (10)	−0.0154 (11)	−0.0017 (10)
O11E	0.0458 (12)	0.0442 (13)	0.0778 (16)	−0.0130 (10)	−0.0106 (11)	0.0206 (11)
C2E	0.0338 (15)	0.0414 (17)	0.0314 (15)	−0.0053 (13)	−0.0008 (12)	0.0006 (12)
C3E	0.0474 (18)	0.0372 (16)	0.0326 (15)	−0.0011 (14)	0.0035 (13)	0.0041 (12)
C4E	0.0463 (17)	0.0390 (16)	0.0289 (15)	−0.0151 (14)	0.0029 (12)	0.0031 (12)
N41E	0.0640 (19)	0.0482 (17)	0.0463 (16)	−0.0216 (15)	0.0051 (13)	−0.0001 (12)
O41E	0.091 (2)	0.0445 (15)	0.115 (2)	−0.0194 (14)	0.0112 (17)	−0.0072 (14)
O42E	0.0630 (17)	0.0728 (17)	0.100 (2)	−0.0364 (14)	−0.0006 (14)	0.0079 (14)
C5E	0.0347 (15)	0.0523 (19)	0.0314 (15)	−0.0169 (14)	−0.0001 (12)	0.0039 (13)
C6E	0.0375 (16)	0.0423 (17)	0.0336 (15)	−0.0024 (13)	0.0007 (12)	0.0075 (12)
C1F	0.0357 (15)	0.0390 (16)	0.0291 (14)	−0.0085 (13)	−0.0036 (12)	0.0052 (11)
C11F	0.0364 (17)	0.0412 (18)	0.0439 (18)	−0.0088 (14)	−0.0075 (13)	0.0088 (13)
O10F	0.0420 (13)	0.0591 (15)	0.1002 (19)	−0.0191 (11)	0.0105 (12)	0.0015 (13)
O11F	0.0496 (13)	0.0390 (12)	0.0721 (15)	−0.0100 (10)	−0.0077 (11)	0.0085 (10)
C2F	0.0311 (15)	0.0456 (17)	0.0347 (16)	−0.0026 (13)	0.0016 (12)	0.0028 (12)
C3F	0.0426 (17)	0.0338 (16)	0.0433 (17)	0.0013 (13)	0.0003 (13)	−0.0011 (12)
C4F	0.0426 (17)	0.0340 (15)	0.0341 (16)	−0.0087 (13)	−0.0036 (12)	0.0057 (12)
N41F	0.0610 (19)	0.0350 (15)	0.0542 (17)	−0.0130 (14)	−0.0079 (14)	0.0038 (12)
O41F	0.0772 (17)	0.0350 (14)	0.109 (2)	−0.0090 (13)	−0.0056 (15)	0.0018 (13)
O42F	0.0583 (16)	0.0611 (16)	0.107 (2)	−0.0291 (13)	0.0104 (14)	0.0049 (14)
C5F	0.0323 (15)	0.0401 (17)	0.0342 (15)	−0.0050 (13)	0.0015 (12)	0.0041 (12)
C6F	0.0353 (15)	0.0324 (15)	0.0394 (16)	−0.0020 (12)	0.0004 (12)	−0.0015 (12)
O1W	0.0437 (13)	0.0387 (13)	0.0655 (15)	−0.0073 (11)	0.0181 (11)	−0.0025 (10)
O2W	0.0396 (13)	0.0412 (13)	0.0644 (15)	−0.0051 (11)	0.0081 (11)	−0.0078 (10)
O3W	0.0388 (13)	0.0424 (13)	0.0617 (15)	−0.0109 (11)	−0.0039 (11)	0.0073 (10)
O4W	0.0429 (13)	0.0392 (12)	0.0613 (14)	−0.0072 (11)	−0.0047 (11)	0.0077 (10)

Geometric parameters (Å, º) top

N1A—C2A	1.514 (4)	C2D—C3D	1.520 (4)
N1A—H11A	0.89	C2D—H21D	0.97
N1A—H12A	0.89	C2D—H22D	0.97
N1A—H13A	0.89	C3D—N4D	1.471 (3)
C2A—C3A	1.493 (4)	C3D—H31D	0.97
C2A—H21A	0.97	C3D—H32D	0.97
C2A—H22A	0.97	N4D—H41D	0.89
C3A—N4A	1.467 (3)	N4D—H42D	0.89
C3A—H31A	0.97	N4D—H43D	0.89
C3A—H32A	0.97	C1E—C2E	1.391 (4)
N4A—H41A	0.89	C1E—C6E	1.406 (4)
N4A—H42A	0.89	C1E—C11E	1.517 (4)
N4A—H43A	0.89	C11E—O10E	1.252 (3)
C1B—C6B	1.388 (4)	C11E—O11E	1.260 (3)
C1B—C2B	1.403 (4)	C2E—C3E	1.380 (4)
C1B—C11B	1.507 (4)	C2E—H2E	0.93
C11B—O11B	1.229 (3)	C3E—C4E	1.385 (4)
C11B—O10B	1.250 (3)	C3E—H3E	0.93
C2B—C3B	1.388 (4)	C4E—C5E	1.376 (4)
C2B—H2B	0.93	C4E—N41E	1.467 (4)
C3B—C4B	1.381 (4)	N41E—O42E	1.219 (3)
C3B—H3B	0.93	N41E—O41E	1.221 (3)
C4B—C5B	1.384 (4)	C5E—C6E	1.384 (4)
C4B—N41B	1.471 (4)	C5E—H5E	0.93
N41B—O42B	1.219 (3)	C6E—H6E	0.93
N41B—O41B	1.234 (3)	C1F—C6F	1.388 (4)
C5B—C6B	1.388 (4)	C1F—C2F	1.389 (4)
C5B—H5B	0.93	C1F—C11F	1.502 (4)
C6B—H6B	0.93	C11F—O10F	1.234 (3)
C1C—C6C	1.387 (3)	C11F—O11F	1.264 (3)
C1C—C2C	1.388 (4)	C2F—C3F	1.376 (4)
C1C—C11C	1.505 (4)	C2F—H2F	0.93
C11C—O10C	1.226 (3)	C3F—C4F	1.371 (4)
C11C—O11C	1.251 (3)	C3F—H3F	0.93
C2C—C3C	1.384 (4)	C4F—C5F	1.380 (4)
C2C—H2C	0.93	C4F—N41F	1.480 (4)
C3C—C4C	1.367 (4)	N41F—O42F	1.207 (3)
C3C—H3C	0.93	N41F—O41F	1.217 (3)
C4C—C5C	1.373 (4)	C5F—C6F	1.383 (4)
C4C—N41C	1.474 (4)	C5F—H5F	0.93
N41C—O42C	1.215 (3)	C6F—H6F	0.93
N41C—O41C	1.222 (3)	O1W—H11	0.87 (4)
C5C—C6C	1.377 (4)	O1W—H12	0.91 (3)
C5C—H5C	0.93	O2W—H21	0.94 (4)
C6C—H6C	0.93	O2W—H22	0.85 (3)
N1D—C2D	1.509 (4)	O3W—H31	0.80 (3)
N1D—H11D	0.89	O3W—H32	0.97 (3)
N1D—H12D	0.89	O4W—H41	0.87 (4)
N1D—H13D	0.89	O4W—H42	1.02 (4)

C2A—N1A—H11A	109.5	H11D—N1D—H12D	109.5
C2A—N1A—H12A	109.5	C2D—N1D—H13D	109.5
H11A—N1A—H12A	109.5	H11D—N1D—H13D	109.5
C2A—N1A—H13A	109.5	H12D—N1D—H13D	109.5
H11A—N1A—H13A	109.5	N1D—C2D—C3D	114.3 (2)
H12A—N1A—H13A	109.5	N1D—C2D—H21D	108.7
C3A—C2A—N1A	113.5 (2)	C3D—C2D—H21D	108.7
C3A—C2A—H21A	108.9	N1D—C2D—H22D	108.7
N1A—C2A—H21A	108.9	C3D—C2D—H22D	108.7
C3A—C2A—H22A	108.9	H21D—C2D—H22D	107.6
N1A—C2A—H22A	108.9	N4D—C3D—C2D	113.3 (2)
H21A—C2A—H22A	107.7	N4D—C3D—H31D	108.9
N4A—C3A—C2A	113.4 (2)	C2D—C3D—H31D	108.9
N4A—C3A—H31A	108.9	N4D—C3D—H32D	108.9
C2A—C3A—H31A	108.9	C2D—C3D—H32D	108.9
N4A—C3A—H32A	108.9	H31D—C3D—H32D	107.7
C2A—C3A—H32A	108.9	C3D—N4D—H41D	109.5
H31A—C3A—H32A	107.7	C3D—N4D—H42D	109.5
C3A—N4A—H41A	109.5	H41D—N4D—H42D	109.5
C3A—N4A—H42A	109.5	C3D—N4D—H43D	109.5
H41A—N4A—H42A	109.5	H41D—N4D—H43D	109.5
C3A—N4A—H43A	109.5	H42D—N4D—H43D	109.5
H41A—N4A—H43A	109.5	C2E—C1E—C6E	119.4 (3)
H42A—N4A—H43A	109.5	C2E—C1E—C11E	118.8 (2)
C6B—C1B—C2B	119.4 (3)	C6E—C1E—C11E	121.8 (3)
C6B—C1B—C11B	119.0 (2)	O10E—C11E—O11E	124.6 (3)
C2B—C1B—C11B	121.6 (3)	O10E—C11E—C1E	118.1 (3)
O11B—C11B—O10B	123.2 (3)	O11E—C11E—C1E	117.3 (2)
O11B—C11B—C1B	117.6 (3)	C3E—C2E—C1E	120.6 (3)
O10B—C11B—C1B	119.2 (2)	C3E—C2E—H2E	119.7
C3B—C2B—C1B	120.7 (3)	C1E—C2E—H2E	119.7
C3B—C2B—H2B	119.6	C2E—C3E—C4E	118.4 (3)
C1B—C2B—H2B	119.6	C2E—C3E—H3E	120.8
C4B—C3B—C2B	118.1 (3)	C4E—C3E—H3E	120.8
C4B—C3B—H3B	121.0	C5E—C4E—C3E	123.0 (3)
C2B—C3B—H3B	121.0	C5E—C4E—N41E	118.0 (3)
C3B—C4B—C5B	122.7 (3)	C3E—C4E—N41E	119.0 (3)
C3B—C4B—N41B	118.3 (3)	O42E—N41E—O41E	122.5 (3)
C5B—C4B—N41B	119.0 (3)	O42E—N41E—C4E	118.5 (3)
O42B—N41B—O41B	123.0 (3)	O41E—N41E—C4E	119.0 (3)
O42B—N41B—C4B	118.1 (3)	C4E—C5E—C6E	118.1 (3)
O41B—N41B—C4B	118.9 (3)	C4E—C5E—H5E	121.0
C4B—C5B—C6B	118.5 (3)	C6E—C5E—H5E	121.0
C4B—C5B—H5B	120.8	C5E—C6E—C1E	120.5 (3)
C6B—C5B—H5B	120.8	C5E—C6E—H6E	119.7
C1B—C6B—C5B	120.6 (3)	C1E—C6E—H6E	119.7
C1B—C6B—H6B	119.7	C6F—C1F—C2F	118.7 (2)
C5B—C6B—H6B	119.7	C6F—C1F—C11F	121.0 (3)
C6C—C1C—C2C	118.7 (3)	C2F—C1F—C11F	120.3 (2)
C6C—C1C—C11C	121.4 (2)	O10F—C11F—O11F	125.1 (3)
C2C—C1C—C11C	119.9 (2)	O10F—C11F—C1F	117.1 (3)
O10C—C11C—O11C	124.7 (3)	O11F—C11F—C1F	117.8 (2)
O10C—C11C—C1C	116.9 (3)	C3F—C2F—C1F	122.0 (3)
O11C—C11C—C1C	118.4 (2)	C3F—C2F—H2F	119.0
C3C—C2C—C1C	121.7 (2)	C1F—C2F—H2F	119.0
C3C—C2C—H2C	119.1	C4F—C3F—C2F	117.6 (3)
C1C—C2C—H2C	119.1	C4F—C3F—H3F	121.2
C4C—C3C—C2C	117.3 (3)	C2F—C3F—H3F	121.2
C4C—C3C—H3C	121.3	C3F—C4F—C5F	122.6 (3)
C2C—C3C—H3C	121.3	C3F—C4F—N41F	118.1 (3)
C3C—C4C—C5C	123.0 (3)	C5F—C4F—N41F	119.3 (2)
C3C—C4C—N41C	118.0 (3)	O42F—N41F—O41F	123.5 (3)
C5C—C4C—N41C	119.0 (2)	O42F—N41F—C4F	118.2 (3)
O42C—N41C—O41C	123.2 (3)	O41F—N41F—C4F	118.3 (3)
O42C—N41C—C4C	118.2 (3)	C4F—C5F—C6F	118.7 (2)
O41C—N41C—C4C	118.6 (3)	C4F—C5F—H5F	120.6
C4C—C5C—C6C	118.9 (2)	C6F—C5F—H5F	120.6
C4C—C5C—H5C	120.6	C5F—C6F—C1F	120.3 (3)
C6C—C5C—H5C	120.6	C5F—C6F—H6F	119.8
C5C—C6C—C1C	120.4 (3)	C1F—C6F—H6F	119.8
C5C—C6C—H6C	119.8	H11—O1W—H12	113 (3)
C1C—C6C—H6C	119.8	H21—O2W—H22	105 (3)
C2D—N1D—H11D	109.5	H31—O3W—H32	102 (3)
C2D—N1D—H12D	109.5	H41—O4W—H42	107 (3)

N1A—C2A—C3A—N4A	−72.5 (4)	N1D—C2D—C3D—N4D	73.6 (3)
C6B—C1B—C11B—O11B	30.2 (4)	C2E—C1E—C11E—O10E	8.5 (4)
C2B—C1B—C11B—O11B	−148.1 (3)	C6E—C1E—C11E—O10E	−171.5 (2)
C6B—C1B—C11B—O10B	−148.7 (3)	C2E—C1E—C11E—O11E	−170.3 (2)
C2B—C1B—C11B—O10B	33.0 (4)	C6E—C1E—C11E—O11E	9.7 (4)
C6B—C1B—C2B—C3B	−0.8 (4)	C6E—C1E—C2E—C3E	−0.7 (4)
C11B—C1B—C2B—C3B	177.5 (2)	C11E—C1E—C2E—C3E	179.3 (2)
C1B—C2B—C3B—C4B	1.9 (4)	C1E—C2E—C3E—C4E	1.1 (4)
C2B—C3B—C4B—C5B	−1.3 (4)	C2E—C3E—C4E—C5E	−0.6 (4)
C2B—C3B—C4B—N41B	178.4 (2)	C2E—C3E—C4E—N41E	179.3 (2)
C3B—C4B—N41B—O42B	−178.1 (3)	C5E—C4E—N41E—O42E	20.2 (4)
C5B—C4B—N41B—O42B	1.6 (4)	C3E—C4E—N41E—O42E	−159.7 (3)
C3B—C4B—N41B—O41B	2.1 (4)	C5E—C4E—N41E—O41E	−159.4 (3)
C5B—C4B—N41B—O41B	−178.2 (3)	C3E—C4E—N41E—O41E	20.6 (4)
C3B—C4B—C5B—C6B	−0.4 (4)	C3E—C4E—C5E—C6E	−0.2 (4)
N41B—C4B—C5B—C6B	179.9 (2)	N41E—C4E—C5E—C6E	179.8 (2)
C2B—C1B—C6B—C5B	−0.9 (4)	C4E—C5E—C6E—C1E	0.7 (4)
C11B—C1B—C6B—C5B	−179.3 (2)	C2E—C1E—C6E—C5E	−0.2 (4)
C4B—C5B—C6B—C1B	1.6 (4)	C11E—C1E—C6E—C5E	179.8 (2)
C6C—C1C—C11C—O10C	−176.7 (3)	C6F—C1F—C11F—O10F	−174.4 (3)
C2C—C1C—C11C—O10C	4.1 (4)	C2F—C1F—C11F—O10F	5.3 (4)
C6C—C1C—C11C—O11C	2.5 (4)	C6F—C1F—C11F—O11F	5.2 (4)
C2C—C1C—C11C—O11C	−176.7 (3)	C2F—C1F—C11F—O11F	−175.1 (2)
C6C—C1C—C2C—C3C	−0.3 (4)	C6F—C1F—C2F—C3F	−0.8 (4)
C11C—C1C—C2C—C3C	178.9 (3)	C11F—C1F—C2F—C3F	179.5 (2)
C1C—C2C—C3C—C4C	−0.2 (4)	C1F—C2F—C3F—C4F	0.5 (4)
C2C—C3C—C4C—C5C	0.8 (4)	C2F—C3F—C4F—C5F	0.0 (4)
C2C—C3C—C4C—N41C	−179.4 (2)	C2F—C3F—C4F—N41F	−179.9 (2)
C3C—C4C—N41C—O42C	−176.4 (3)	C3F—C4F—N41F—O42F	176.8 (3)
C5C—C4C—N41C—O42C	3.4 (4)	C5F—C4F—N41F—O42F	−3.2 (4)
C3C—C4C—N41C—O41C	4.7 (4)	C3F—C4F—N41F—O41F	−2.8 (4)
C5C—C4C—N41C—O41C	−175.5 (3)	C5F—C4F—N41F—O41F	177.3 (3)
C3C—C4C—C5C—C6C	−0.9 (4)	C3F—C4F—C5F—C6F	−0.3 (4)
N41C—C4C—C5C—C6C	179.4 (2)	N41F—C4F—C5F—C6F	179.7 (2)
C4C—C5C—C6C—C1C	0.3 (4)	C4F—C5F—C6F—C1F	0.0 (4)
C2C—C1C—C6C—C5C	0.3 (4)	C2F—C1F—C6F—C5F	0.5 (4)
C11C—C1C—C6C—C5C	−178.9 (3)	C11F—C1F—C6F—C5F	−179.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O2W	0.89	2.03	2.833 (4)	149
N1A—H12A···O1W	0.89	1.99	2.786 (3)	148
N1A—H13A···O11Bⁱ	0.89	1.85	2.744 (3)	178
N4A—H41A···O1Wⁱⁱ	0.89	2.09	2.881 (3)	147
N4A—H42A···O2Wⁱⁱ	0.89	2.09	2.861 (3)	145
N4A—H43A···O10Bⁱ	0.89	1.96	2.847 (3)	175
N1D—H11D···O4Wⁱⁱⁱ	0.89	2.06	2.846 (3)	147
N1D—H12D···O3W	0.89	1.97	2.781 (3)	150
N1D—H13D···O11E	0.89	1.85	2.728 (3)	171
N4D—H41D···O10E	0.89	1.87	2.753 (3)	173
N4D—H42D···O3Wⁱⁱ	0.89	2.10	2.881 (4)	146
N4D—H43D···O4W^iv	0.89	2.04	2.839 (4)	149
O1W—H11···O11C^v	0.87 (4)	1.86 (4)	2.693 (3)	160 (3)
O1W—H12···O11C	0.91 (3)	1.77 (4)	2.658 (3)	166 (3)
O2W—H21···O10C	0.94 (4)	1.72 (4)	2.653 (3)	171 (4)
O2W—H22···O10B	0.85 (3)	1.87 (4)	2.704 (3)	168 (3)
O3W—H31···O11F^vi	0.80 (3)	1.99 (3)	2.785 (3)	169 (3)
O3W—H32···O11Fⁱⁱⁱ	0.97 (3)	1.70 (3)	2.663 (3)	174 (3)
O4W—H41···O11E	0.87 (4)	1.88 (4)	2.756 (3)	176 (3)
O4W—H42···O10F	1.02 (4)	1.65 (4)	2.674 (3)	177 (3)

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

Experimental details

Crystal data
Chemical formula	C₂H₁₀N₂²⁺·2C₇H₄NO₄⁻·2H₂O
M_r	430.38
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	12.213 (2), 22.317 (2), 7.091 (5)
α, β, γ (°)	89.47 (2), 89.17 (2), 84.72 (8)
V (Å³)	1924.2 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.40 × 0.20 × 0.10

Data collection
Diffractometer	Rigaku AFC7-R diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6810, 6810, 3360
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.150, 1.00
No. of reflections	6810
No. of parameters	577
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.30

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1985), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997), SHELXL97.