4-[2-(4-Pyridyl)­ethyl]­pyridinium nitrate trihydrate

Almeida Paz, F.A.; Khimyak, Y.Z.; Klinowski, J.

doi:10.1107/S1600536803000783

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4-[2-(4-Pyridyl)ethyl]pyridinium nitrate trihydrate

F. A. Almeida Paz, Y. Z. Khimyak and J. Klinowski

The title compound, C₁₂H₁₃N₂⁺·NO₃^-·3H₂O [where C₁₂H₁₃N₂⁺ is the monoprotonated form of 1,2-bis(4-pyridyl)ethane (BPEH⁺)] is monoclinic, space group P2₁/c, and contains two empirical formulae in the asymmetric unit. The compound has cationic [BPEH]_nⁿ⁺ organic layers, alternating in the b direction with anionic [(NO₃)·3H₂O]_n^n- inorganic layers. Hydrogen bonds between 4-pyridyl and 4-pyridinium groups, and between nitrate ions and water molecules, give rise to chains and two-dimensional hydrogen-bonding networks, respectively.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803000783/cf6229sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803000783/cf6229Isup2.hkl Contains datablock I

CCDC reference: 204679

checkCIF report

Key indicators

Single-crystal X-ray study
T = 180 K
Mean (C-C) = 0.003 Å
R factor = 0.076
wR factor = 0.222
Data-to-parameter ratio = 12.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



DIFMX_01  Alert C The maximum difference density is > 0.1*ZMAX*0.75
          _refine_diff_density_max given =      0.707
          Test value =      0.600

DIFMX_02  Alert C The minimum difference density is > 0.1*ZMAX*0.75
          The relevant atom site should be identified.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

Comment top

1,2-Bis(4-pyridyl)ethane (BPE) has been successfully employed in the synthesis of novel metal–organic frameworks (see, for example, Fujita et al., 1994; Wang et al., 1999; Bourne et al., 2001). We have focused our attention on this organic ligand to obtain novel crystal structures with Cd²⁺ and Co²⁺ ions, produced under hydrothermal conditions and in the presence of carboxylic acids and triethylamine (TEA) (Almeida Paz et al., 2002, 2002a). We have also found that, under the same experimental conditions, the absence of TEA can lead to the formation of a double-layered salt of BPE with trimesic acid residues (Almeida Paz et al., 2002b). The title compound, (I), was obtained in the presence of Cd²⁺ ions and, to our knowledge, is the first crystal structure of a BPE salt with a typical inorganic ion (NO₃⁻).

The structure determination of (I) reveals the presence of two BPE molecules in the asymmetric unit, both present in the typical anti conformation (Hennigar et al., 1997) and with one protonated 4-pyridyl group, BPEH⁺ (Fig. 1). Adjacent BPEH⁺ cations are linked via strong N⁺—H···N hydrogen bonds (Table 2), forming an infinite one-dimensional chain, which runs along the a direction (Fig. 2). These chains are close-packed in the ab plane, generating a positively charged [BPEH]_nⁿ⁺ organic layer, which alternates with an inorganic layer composed of nitrate ions and water molecules (Figs. 3 and 4). This negatively charged inorganic layer, [(NO₃)·3H₂O]_n^n-, is formed by an extensive and strong hydrogen-bonding network (Table 2), and can be described as the alternation of two graph sets, R₆⁸(14) and R₆⁶(14) (Fig. 3). In this layer, each water O atom acts as a single acceptor (with an adjacent water molecule) and as a double donor, donating the attached H atoms to a neighbouring water molecule and a nitrate ion (Fig. 3). An interesting feature in the crystal structure arises from the bifurcated donor nature of atoms O6W and O9W, with H6A and H9A, respectively, being almost equidistant from the O atoms in the neighbouring nitrate ions (Table 2). This suggests that the hydrogen-bonding interactions are very likely to be between the water molecules and the conjugated π system in the nitrate ions (Fig. 3, top).

Experimental top

All chemicals were obtained from commercial sources and were used as received. To a solution of Cd(NO₃)₂·4H₂O (0.629 g, Aldrich) in distilled water (11.60 g), 1,2-bis(4-pyridyl)ethane (BPE, 0.382 g, Aldrich) was added, and the resulting mixture was stirred thoroughly for 1 h at ambient temperature. The suspension, with a Cd²⁺:BPE:H₂O molar ratio of 1.00:1.02:315, was placed in a Parr stainless steel teflon-lined reaction vessel (21 ml, 70% full). The reaction was performed under autogeneous pressure and static conditions in a preheated oven at 418 K, using a previously reported temperature profile (Almeida Paz et al., 2002). The microcrystalline product was placed inside a refrigerator for 24 h, after which crystals of the title compound were separated manually.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at the 30% probability level, and showing the labelling scheme for non-H atoms.
	Fig. 2. View, along the b axis, of the [BPEH]_nⁿ⁺ organic cationic layer, showing the packing of the one-dimensional BPEH⁺ chains.
	Fig. 3. View, along the b axis, of the [(NO₃)·3H₂O]_n^n- anionic inorganic layer, showing the two-dimensional hydrogen-bonding network (dashed lines) between the nitrate ions and the water molecules. For hydrogen-bonding geometry and symmetry codes, see Table 2.
	Fig. 4. Perspective view of (I), showing the hydrogen-bonding network (dashed lines).

4-[2-(4-Pyridyl)ethyl]pyridinium nitrate trihydrate top

Crystal data top

C₁₂H₁₃N₂⁺·NO₃⁻·3H₂O	F(000) = 1280
M_r = 301.30	D_x = 1.322 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.7751 (4) Å	Cell parameters from 15908 reflections
b = 16.1980 (7) Å	θ = 1.0–25.0°
c = 15.8787 (4) Å	µ = 0.11 mm⁻¹
β = 90.175 (2)°	T = 180 K
V = 3028.58 (18) Å³	Block, colourless
Z = 8	0.46 × 0.39 × 0.12 mm

Data collection top

Nonius KappaCCD diffractometer	5304 independent reflections
Radiation source: fine-focus sealed tube	3982 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Thin–slice ω and ϕ scans	θ_max = 25.1°, θ_min = 3.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −14→14
T_min = 0.953, T_max = 0.987	k = −18→19
21624 measured reflections	l = −18→18

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.222	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.1132P)² + 1.9726P] where P = (F_o² + 2F_c²)/3
5304 reflections	(Δ/σ)_max = 0.026
423 parameters	Δρ_max = 0.71 e Å⁻³
20 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₂H₁₃N₂⁺·NO₃⁻·3H₂O	V = 3028.58 (18) Å³
M_r = 301.30	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.7751 (4) Å	µ = 0.11 mm⁻¹
b = 16.1980 (7) Å	T = 180 K
c = 15.8787 (4) Å	0.46 × 0.39 × 0.12 mm
β = 90.175 (2)°

Data collection top

Nonius KappaCCD diffractometer	5304 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	3982 reflections with I > 2σ(I)
T_min = 0.953, T_max = 0.987	R_int = 0.041
21624 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	20 restraints
wR(F²) = 0.222	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.71 e Å⁻³
5304 reflections	Δρ_min = −0.30 e Å⁻³
423 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
N11	−0.25795 (16)	1.01182 (13)	0.86038 (13)	0.0354 (5)
N12	0.51924 (16)	1.01354 (14)	0.88350 (13)	0.0351 (5)
H12N	0.5925 (11)	1.015 (3)	0.871 (2)	0.089 (4)*
C11	−0.1976 (2)	1.08140 (16)	0.85559 (17)	0.0394 (6)
H11A	−0.2356	1.1330	0.8595	0.047*
C12	−0.0815 (2)	1.08024 (16)	0.84503 (16)	0.0391 (6)
H12A	−0.0403	1.1306	0.8419	0.047*
C13	−0.0250 (2)	1.00569 (16)	0.83906 (15)	0.0336 (6)
C14	−0.0889 (2)	0.93446 (17)	0.84450 (18)	0.0422 (6)
H14A	−0.0532	0.8820	0.8410	0.051*
C15	−0.2042 (2)	0.93975 (17)	0.85495 (18)	0.0439 (7)
H15A	−0.2473	0.8903	0.8584	0.053*
C16	0.1025 (2)	1.00308 (18)	0.83076 (16)	0.0389 (6)
H16A	0.1282	1.0502	0.7960	0.047*
H16B	0.1251	0.9515	0.8019	0.047*
C17	0.1595 (2)	1.00711 (19)	0.91745 (16)	0.0411 (6)
H17A	0.1335	1.0571	0.9477	0.049*
H17B	0.1374	0.9582	0.9510	0.049*
C18	0.2861 (2)	1.00948 (16)	0.90836 (14)	0.0334 (6)
C19	0.3429 (2)	1.08334 (16)	0.89421 (16)	0.0387 (6)
H19A	0.3018	1.1338	0.8928	0.046*
C110	0.4587 (2)	1.08349 (16)	0.88228 (16)	0.0388 (6)
H11B	0.4965	1.1345	0.8730	0.047*
C111	0.4666 (2)	0.94185 (16)	0.89694 (16)	0.0388 (6)
H11C	0.5100	0.8924	0.8975	0.047*
C112	0.3508 (2)	0.93746 (17)	0.91000 (16)	0.0401 (6)
H11D	0.3155	0.8857	0.9200	0.048*
N21	−0.00299 (17)	1.00612 (13)	0.60946 (13)	0.0358 (5)
H21N	−0.0770 (10)	1.001 (2)	0.617 (2)	0.089 (4)*
N22	0.77418 (16)	1.00920 (13)	0.63403 (13)	0.0349 (5)
C21	0.0523 (2)	1.07773 (17)	0.60263 (18)	0.0439 (7)
H21A	0.0107	1.1279	0.6051	0.053*
C22	0.1683 (2)	1.08034 (17)	0.59213 (18)	0.0434 (7)
H22A	0.2059	1.1320	0.5871	0.052*
C23	0.2299 (2)	1.00780 (16)	0.58892 (14)	0.0327 (6)
C24	0.1705 (2)	0.93431 (16)	0.59563 (16)	0.0398 (6)
H24A	0.2098	0.8831	0.5930	0.048*
C25	0.0537 (2)	0.93559 (16)	0.60615 (17)	0.0398 (6)
H25A	0.0136	0.8849	0.6111	0.048*
C26	0.3575 (2)	1.00845 (17)	0.58087 (16)	0.0378 (6)
H26A	0.3809	1.0544	0.5437	0.045*
H26B	0.3832	0.9561	0.5549	0.045*
C27	0.4136 (2)	1.01861 (18)	0.66735 (15)	0.0388 (6)
H27A	0.3903	1.0719	0.6925	0.047*
H27B	0.3884	0.9737	0.7052	0.047*
C28	0.54147 (19)	1.01622 (15)	0.65877 (14)	0.0322 (6)
C29	0.6045 (2)	1.08762 (17)	0.64825 (16)	0.0405 (6)
H29A	0.5685	1.1401	0.6496	0.049*
C210	0.7195 (2)	1.08194 (17)	0.63581 (17)	0.0405 (6)
H21B	0.7619	1.1312	0.6282	0.049*
C211	0.7141 (2)	0.94015 (17)	0.64531 (16)	0.0395 (6)
H21C	0.7524	0.8885	0.6448	0.047*
C212	0.5986 (2)	0.94157 (16)	0.65767 (16)	0.0373 (6)
H21D	0.5581	0.8914	0.6654	0.045*
N31	−0.3773 (2)	0.74636 (14)	0.98086 (15)	0.0462 (6)
O31	−0.4662 (2)	0.74849 (15)	0.94000 (13)	0.0649 (6)
O32	−0.28801 (19)	0.76856 (15)	0.94417 (14)	0.0645 (6)
O33	−0.3752 (2)	0.72427 (14)	1.05453 (14)	0.0673 (7)
N41	0.1340 (2)	0.76654 (13)	0.77466 (14)	0.0433 (6)
O41	0.1325 (2)	0.76995 (14)	0.69782 (13)	0.0599 (6)
O42	0.2236 (2)	0.77828 (16)	0.81497 (14)	0.0691 (7)
O43	0.04672 (18)	0.74937 (14)	0.81572 (13)	0.0565 (6)
O5W	0.4197 (2)	0.7775 (2)	0.70942 (17)	0.0826 (9)
H5A	0.365 (2)	0.782 (3)	0.7367 (19)	0.089 (4)*
H5B	0.402 (3)	0.770 (3)	0.6629 (12)	0.089 (4)*
O6W	0.1359 (2)	0.7730 (2)	0.98979 (15)	0.0910 (10)
H6A	0.128 (3)	0.773 (3)	0.9411 (11)	0.089 (4)*
H6B	0.078 (2)	0.762 (3)	1.010 (2)	0.089 (4)*
O7W	−0.0855 (2)	0.7533 (3)	1.0474 (2)	0.1004 (11)
H7A	−0.142 (2)	0.754 (3)	1.021 (2)	0.089 (4)*
H7B	−0.104 (3)	0.752 (3)	1.0941 (12)	0.089 (4)*
O8W	−0.6535 (2)	0.7428 (3)	1.05106 (18)	0.1065 (12)
H8A	−0.610 (3)	0.732 (3)	1.0166 (19)	0.089 (4)*
H8B	−0.7138 (18)	0.747 (3)	1.032 (2)	0.089 (4)*
O9W	−0.3625 (2)	0.7473 (2)	0.76751 (14)	0.0777 (8)
H9A	−0.374 (3)	0.753 (3)	0.8156 (12)	0.089 (4)*
H9B	−0.4227 (19)	0.748 (3)	0.747 (2)	0.089 (4)*
O10W	−0.1474 (3)	0.7373 (3)	0.7077 (2)	0.1367 (18)
H10A	−0.2084 (17)	0.735 (3)	0.726 (2)	0.089 (4)*
H10B	−0.104 (2)	0.724 (3)	0.7416 (19)	0.089 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N11	0.0241 (11)	0.0431 (12)	0.0389 (12)	0.0009 (9)	−0.0022 (8)	−0.0013 (9)
N12	0.0199 (10)	0.0468 (13)	0.0386 (11)	0.0013 (9)	−0.0015 (8)	−0.0017 (9)
C11	0.0281 (13)	0.0392 (14)	0.0510 (15)	0.0033 (11)	0.0002 (11)	−0.0033 (11)
C12	0.0272 (13)	0.0400 (14)	0.0502 (15)	−0.0050 (11)	−0.0015 (11)	0.0001 (11)
C13	0.0227 (12)	0.0462 (15)	0.0318 (13)	0.0013 (10)	−0.0029 (9)	−0.0011 (10)
C14	0.0288 (14)	0.0367 (14)	0.0611 (17)	0.0026 (11)	−0.0009 (12)	−0.0015 (12)
C15	0.0286 (14)	0.0401 (15)	0.0630 (17)	−0.0052 (11)	−0.0032 (12)	0.0027 (12)
C16	0.0220 (13)	0.0575 (17)	0.0373 (14)	0.0010 (11)	−0.0002 (10)	−0.0037 (11)
C17	0.0213 (12)	0.0656 (18)	0.0363 (14)	−0.0013 (11)	0.0008 (10)	0.0017 (12)
C18	0.0226 (12)	0.0498 (15)	0.0279 (12)	−0.0018 (11)	−0.0015 (9)	0.0000 (10)
C19	0.0286 (13)	0.0412 (14)	0.0463 (15)	0.0077 (11)	−0.0019 (11)	−0.0032 (11)
C110	0.0297 (13)	0.0399 (14)	0.0469 (14)	−0.0024 (11)	−0.0015 (11)	−0.0006 (11)
C111	0.0296 (13)	0.0384 (14)	0.0483 (15)	0.0039 (11)	−0.0047 (11)	0.0021 (11)
C112	0.0290 (14)	0.0427 (15)	0.0485 (15)	−0.0040 (11)	−0.0039 (11)	0.0074 (12)
N21	0.0204 (10)	0.0458 (13)	0.0412 (12)	0.0000 (9)	−0.0011 (9)	−0.0021 (9)
N22	0.0229 (10)	0.0438 (12)	0.0381 (11)	0.0011 (9)	−0.0013 (8)	−0.0010 (9)
C21	0.0305 (14)	0.0393 (15)	0.0618 (17)	0.0060 (11)	−0.0002 (12)	−0.0049 (12)
C22	0.0298 (14)	0.0389 (15)	0.0614 (17)	−0.0066 (11)	0.0005 (12)	−0.0002 (12)
C23	0.0225 (12)	0.0469 (15)	0.0288 (12)	0.0002 (10)	0.0003 (9)	−0.0019 (10)
C24	0.0293 (13)	0.0384 (14)	0.0517 (15)	0.0064 (11)	0.0003 (11)	−0.0012 (11)
C25	0.0261 (13)	0.0395 (14)	0.0537 (16)	−0.0018 (11)	−0.0034 (11)	0.0032 (11)
C26	0.0217 (12)	0.0542 (16)	0.0375 (14)	−0.0024 (11)	0.0024 (10)	−0.0019 (11)
C27	0.0221 (12)	0.0584 (17)	0.0359 (13)	0.0018 (11)	0.0014 (10)	−0.0039 (12)
C28	0.0226 (12)	0.0446 (14)	0.0296 (12)	0.0019 (10)	−0.0027 (9)	−0.0032 (10)
C29	0.0319 (14)	0.0396 (15)	0.0499 (15)	0.0068 (11)	−0.0003 (11)	−0.0013 (11)
C210	0.0299 (14)	0.0391 (15)	0.0525 (15)	−0.0044 (11)	−0.0016 (11)	0.0004 (12)
C211	0.0303 (14)	0.0406 (15)	0.0476 (15)	0.0044 (11)	−0.0018 (11)	−0.0007 (11)
C212	0.0272 (13)	0.0385 (14)	0.0460 (14)	−0.0013 (10)	0.0003 (10)	−0.0003 (11)
N31	0.0551 (16)	0.0381 (13)	0.0453 (14)	0.0027 (11)	0.0042 (12)	0.0014 (10)
O31	0.0562 (14)	0.0898 (17)	0.0486 (12)	−0.0092 (12)	−0.0078 (10)	−0.0011 (11)
O32	0.0551 (14)	0.0757 (16)	0.0627 (14)	−0.0037 (11)	0.0099 (11)	0.0073 (11)
O33	0.0774 (16)	0.0737 (16)	0.0507 (13)	−0.0016 (12)	−0.0021 (11)	0.0221 (11)
N41	0.0513 (15)	0.0327 (12)	0.0458 (14)	0.0004 (10)	0.0016 (11)	0.0005 (9)
O41	0.0702 (15)	0.0680 (14)	0.0415 (12)	−0.0095 (11)	0.0003 (10)	0.0122 (10)
O42	0.0578 (14)	0.0952 (18)	0.0542 (13)	−0.0188 (13)	−0.0026 (11)	−0.0084 (12)
O43	0.0457 (12)	0.0730 (14)	0.0509 (12)	−0.0023 (10)	0.0129 (9)	0.0037 (10)
O5W	0.0406 (13)	0.145 (3)	0.0626 (15)	−0.0073 (15)	0.0044 (11)	0.0126 (17)
O6W	0.0582 (15)	0.173 (3)	0.0419 (13)	−0.0002 (18)	−0.0016 (11)	−0.0014 (17)
O7W	0.0499 (15)	0.171 (3)	0.0801 (19)	0.0071 (18)	−0.0027 (13)	−0.040 (2)
O8W	0.0484 (15)	0.200 (4)	0.0705 (18)	−0.006 (2)	0.0022 (13)	0.030 (2)
O9W	0.0564 (15)	0.134 (2)	0.0428 (13)	0.0021 (15)	−0.0028 (11)	0.0067 (14)
O10W	0.0437 (16)	0.286 (6)	0.080 (2)	0.017 (2)	−0.0081 (14)	−0.041 (3)

Geometric parameters (Å, º) top

N11—C15	1.331 (3)	C23—C24	1.385 (4)
N11—C11	1.335 (3)	C23—C26	1.509 (3)
N12—C111	1.334 (3)	C24—C25	1.387 (4)
N12—C110	1.339 (3)	C24—H24A	0.950
N12—H12N	0.887 (10)	C25—H25A	0.950
C11—C12	1.379 (4)	C26—C27	1.531 (4)
C11—H11A	0.950	C26—H26A	0.990
C12—C13	1.382 (4)	C26—H26B	0.990
C12—H12A	0.950	C27—C28	1.512 (3)
C13—C14	1.381 (4)	C27—H27A	0.990
C13—C16	1.507 (3)	C27—H27B	0.990
C14—C15	1.371 (4)	C28—C212	1.384 (3)
C14—H14A	0.950	C28—C29	1.385 (4)
C15—H15A	0.950	C29—C210	1.371 (4)
C16—C17	1.531 (4)	C29—H29A	0.950
C16—H16A	0.990	C210—H21B	0.950
C16—H16B	0.990	C211—C212	1.376 (3)
C17—C18	1.499 (3)	C211—H21C	0.950
C17—H17A	0.990	C212—H21D	0.950
C17—H17B	0.990	N31—O33	1.224 (3)
C18—C19	1.389 (4)	N31—O31	1.230 (3)
C18—C112	1.393 (4)	N31—O32	1.257 (3)
C19—C110	1.377 (4)	N41—O41	1.221 (3)
C19—H19A	0.950	N41—O42	1.246 (3)
C110—H11B	0.950	N41—O43	1.250 (3)
C111—C112	1.382 (4)	O5W—H5A	0.785 (17)
C111—H11C	0.950	O5W—H5B	0.778 (17)
C112—H11D	0.950	O6W—H6A	0.779 (17)
N21—C25	1.324 (3)	O6W—H6B	0.776 (17)
N21—C21	1.335 (3)	O7W—H7A	0.793 (17)
N21—H21N	0.883 (10)	O7W—H7B	0.774 (17)
N22—C211	1.336 (3)	O8W—H8A	0.772 (17)
N22—C210	1.343 (3)	O8W—H8B	0.775 (17)
C21—C22	1.378 (4)	O9W—H9A	0.782 (17)
C21—H21A	0.950	O9W—H9B	0.783 (17)
C22—C23	1.382 (4)	O10W—H10A	0.778 (17)
C22—H22A	0.950	O10W—H10B	0.771 (17)

C15—N11—C11	118.9 (2)	C22—C21—H21A	119.3
C111—N12—C110	119.4 (2)	C21—C22—C23	120.0 (2)
C111—N12—H12N	121 (3)	C21—C22—H22A	120.0
C110—N12—H12N	119 (3)	C23—C22—H22A	120.0
N11—C11—C12	121.6 (2)	C22—C23—C24	117.6 (2)
N11—C11—H11A	119.2	C22—C23—C26	121.4 (2)
C12—C11—H11A	119.2	C24—C23—C26	121.0 (2)
C11—C12—C13	119.9 (2)	C23—C24—C25	119.8 (2)
C11—C12—H12A	120.1	C23—C24—H24A	120.1
C13—C12—H12A	120.1	C25—C24—H24A	120.1
C14—C13—C12	117.6 (2)	N21—C25—C24	121.2 (2)
C14—C13—C16	121.7 (2)	N21—C25—H25A	119.4
C12—C13—C16	120.7 (2)	C24—C25—H25A	119.4
C15—C14—C13	119.7 (2)	C23—C26—C27	110.6 (2)
C15—C14—H14A	120.1	C23—C26—H26A	109.5
C13—C14—H14A	120.1	C27—C26—H26A	109.5
N11—C15—C14	122.3 (2)	C23—C26—H26B	109.5
N11—C15—H15A	118.9	C27—C26—H26B	109.5
C14—C15—H15A	118.9	H26A—C26—H26B	108.1
C13—C16—C17	110.7 (2)	C28—C27—C26	110.1 (2)
C13—C16—H16A	109.5	C28—C27—H27A	109.6
C17—C16—H16A	109.5	C26—C27—H27A	109.6
C13—C16—H16B	109.5	C28—C27—H27B	109.6
C17—C16—H16B	109.5	C26—C27—H27B	109.6
H16A—C16—H16B	108.1	H27A—C27—H27B	108.2
C18—C17—C16	110.4 (2)	C212—C28—C29	117.9 (2)
C18—C17—H17A	109.6	C212—C28—C27	120.5 (2)
C16—C17—H17A	109.6	C29—C28—C27	121.6 (2)
C18—C17—H17B	109.6	C210—C29—C28	119.4 (2)
C16—C17—H17B	109.6	C210—C29—H29A	120.3
H17A—C17—H17B	108.1	C28—C29—H29A	120.3
C19—C18—C112	117.4 (2)	N22—C210—C29	122.4 (2)
C19—C18—C17	121.1 (2)	N22—C210—H21B	118.8
C112—C18—C17	121.4 (2)	C29—C210—H21B	118.8
C110—C19—C18	120.1 (2)	N22—C211—C212	122.0 (2)
C110—C19—H19A	120.0	N22—C211—H21C	119.0
C18—C19—H19A	120.0	C212—C211—H21C	119.0
N12—C110—C19	121.6 (2)	C211—C212—C28	119.8 (2)
N12—C110—H11B	119.2	C211—C212—H21D	120.1
C19—C110—H11B	119.2	C28—C212—H21D	120.1
N12—C111—C112	121.9 (2)	O33—N31—O31	121.9 (3)
N12—C111—H11C	119.1	O33—N31—O32	120.8 (3)
C112—C111—H11C	119.1	O31—N31—O32	117.3 (2)
C111—C112—C18	119.6 (2)	O41—N41—O42	121.0 (2)
C111—C112—H11D	120.2	O41—N41—O43	121.4 (3)
C18—C112—H11D	120.2	O42—N41—O43	117.5 (2)
C25—N21—C21	120.1 (2)	H5A—O5W—H5B	108 (3)
C25—N21—H21N	115 (3)	H6A—O6W—H6B	108 (3)
C21—N21—H21N	125 (3)	H7A—O7W—H7B	106 (2)
C211—N22—C210	118.5 (2)	H8A—O8W—H8B	111 (3)
N21—C21—C22	121.4 (2)	H9A—O9W—H9B	105 (2)
N21—C21—H21A	119.3	H10A—O10W—H10B	109 (3)

C15—N11—C11—C12	0.1 (4)	C25—N21—C21—C22	0.0 (4)
N11—C11—C12—C13	0.1 (4)	N21—C21—C22—C23	−0.3 (4)
C11—C12—C13—C14	−0.3 (4)	C21—C22—C23—C24	0.7 (4)
C11—C12—C13—C16	−177.7 (2)	C21—C22—C23—C26	−177.6 (2)
C12—C13—C14—C15	0.4 (4)	C22—C23—C24—C25	−0.7 (4)
C16—C13—C14—C15	177.7 (2)	C26—C23—C24—C25	177.6 (2)
C11—N11—C15—C14	−0.1 (4)	C21—N21—C25—C24	0.0 (4)
C13—C14—C15—N11	−0.2 (4)	C23—C24—C25—N21	0.4 (4)
C14—C13—C16—C17	−92.2 (3)	C22—C23—C26—C27	84.1 (3)
C12—C13—C16—C17	85.0 (3)	C24—C23—C26—C27	−94.2 (3)
C13—C16—C17—C18	−176.7 (2)	C23—C26—C27—C28	178.1 (2)
C16—C17—C18—C19	84.4 (3)	C26—C27—C28—C212	−85.0 (3)
C16—C17—C18—C112	−92.7 (3)	C26—C27—C28—C29	92.3 (3)
C112—C18—C19—C110	0.1 (4)	C212—C28—C29—C210	1.1 (4)
C17—C18—C19—C110	−177.1 (2)	C27—C28—C29—C210	−176.2 (2)
C111—N12—C110—C19	−0.3 (4)	C211—N22—C210—C29	−0.4 (4)
C18—C19—C110—N12	0.3 (4)	C28—C29—C210—N22	−0.5 (4)
C110—N12—C111—C112	−0.2 (4)	C210—N22—C211—C212	0.7 (4)
N12—C111—C112—C18	0.7 (4)	N22—C211—C212—C28	−0.1 (4)
C19—C18—C112—C111	−0.6 (4)	C29—C28—C212—C211	−0.8 (4)
C17—C18—C112—C111	176.6 (2)	C27—C28—C212—C211	176.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12N···N11ⁱ	0.88 (1)	1.77 (1)	2.650 (3)	171 (4)
N21—H21N···N22ⁱⁱ	0.88 (1)	1.78 (1)	2.654 (3)	171 (4)
O5W—H5A···O42	0.78 (2)	2.08 (2)	2.858 (3)	172 (4)
O5W—H5B···O8Wⁱⁱⁱ	0.78 (2)	1.90 (2)	2.676 (4)	176 (4)
O6W—H6A···O43	0.78 (2)	2.24 (2)	2.979 (3)	158 (4)
O6W—H6A···O42	0.78 (2)	2.30 (2)	2.966 (3)	144 (3)
O6W—H6B···O7W	0.78 (2)	2.02 (2)	2.785 (4)	169 (4)
O7W—H7A···O32	0.78 (2)	2.11 (2)	2.900 (4)	173 (4)
O7W—H7B···O10W^iv	0.77 (2)	1.88 (2)	2.654 (5)	174 (5)
O8W—H8A···O31	0.77 (2)	2.10 (2)	2.829 (4)	157 (4)
O8W—H8B···O6Wⁱⁱ	0.78 (2)	1.94 (2)	2.705 (4)	172 (4)
O9W—H9A···O31	0.78 (2)	2.26 (2)	3.003 (3)	160 (4)
O9W—H9A···O32	0.78 (2)	2.29 (2)	2.957 (3)	144 (3)
O9W—H9B···O5Wⁱⁱ	0.78 (2)	2.00 (2)	2.767 (3)	165 (4)
O10W—H10A···O9W	0.78 (2)	1.94 (2)	2.713 (4)	172 (4)
O10W—H10B···O43	0.77 (2)	2.17 (3)	2.860 (4)	150 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃N₂⁺·NO₃⁻·3H₂O
M_r	301.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	180
a, b, c (Å)	11.7751 (4), 16.1980 (7), 15.8787 (4)
β (°)	90.175 (2)
V (Å³)	3028.58 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.46 × 0.39 × 0.12

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.953, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	21624, 5304, 3982
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.222, 1.06
No. of reflections	5304
No. of parameters	423
No. of restraints	20
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.30

Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SIR92 (Altomare et al., 1994), SHELXTL (Bruker, 2001), SHELXTL.

Selected geometric parameters (Å, º) top

N31—O33	1.224 (3)	N41—O41	1.221 (3)
N31—O31	1.230 (3)	N41—O42	1.246 (3)
N31—O32	1.257 (3)	N41—O43	1.250 (3)

O33—N31—O31	121.9 (3)	O41—N41—O42	121.0 (2)
O33—N31—O32	120.8 (3)	O41—N41—O43	121.4 (3)
O31—N31—O32	117.3 (2)	O42—N41—O43	117.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12N···N11ⁱ	0.88 (1)	1.77 (1)	2.650 (3)	171 (4)
N21—H21N···N22ⁱⁱ	0.88 (1)	1.78 (1)	2.654 (3)	171 (4)
O5W—H5A···O42	0.78 (2)	2.08 (2)	2.858 (3)	172 (4)
O5W—H5B···O8Wⁱⁱⁱ	0.78 (2)	1.90 (2)	2.676 (4)	176 (4)
O6W—H6A···O43	0.78 (2)	2.24 (2)	2.979 (3)	158 (4)
O6W—H6A···O42	0.78 (2)	2.30 (2)	2.966 (3)	144 (3)
O6W—H6B···O7W	0.78 (2)	2.02 (2)	2.785 (4)	169 (4)
O7W—H7A···O32	0.78 (2)	2.11 (2)	2.900 (4)	173 (4)
O7W—H7B···O10W^iv	0.77 (2)	1.88 (2)	2.654 (5)	174 (5)
O8W—H8A···O31	0.77 (2)	2.10 (2)	2.829 (4)	157 (4)
O8W—H8B···O6Wⁱⁱ	0.78 (2)	1.94 (2)	2.705 (4)	172 (4)
O9W—H9A···O31	0.78 (2)	2.26 (2)	3.003 (3)	160 (4)
O9W—H9A···O32	0.78 (2)	2.29 (2)	2.957 (3)	144 (3)
O9W—H9B···O5Wⁱⁱ	0.78 (2)	2.00 (2)	2.767 (3)	165 (4)
O10W—H10A···O9W	0.78 (2)	1.94 (2)	2.713 (4)	172 (4)
O10W—H10B···O43	0.77 (2)	2.17 (3)	2.860 (4)	150 (4)

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

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