2′,6′-Bis(4-carb­oxy­phen­yl)-4,4′-bipyridin-1-ium nitrate 0.25-hydrate

Li, Y.; Zang, H.; Su, G.

doi:10.1107/S1600536811051506

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o43

doi:10.1107/S1600536811051506

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2′,6′-Bis(4-carboxyphenyl)-4,4′-bipyridin-1-ium nitrate 0.25-hydrate

Yaping Li,^a Hu Zang ^b ^* and Guanfang Su ^a

^aDepartment of Ophthalmology, The Second Hospital of Jilin University, Changchun 130041, People's Republic of China, and ^bDepartment of Orthopedics, The China–Japan Union Hospital of Jilin University, Changchun 130033, People's Republic of China
^*Correspondence e-mail: doctorzang@163.com

(Received 22 November 2011; accepted 30 November 2011; online 7 December 2011)

In the title compound, C₂₄H₁₇N₂O₄⁺·NO₃⁻·0.25H₂O, the central pyridine ring of the 2′,6′-bis(4-carboxyphenyl)-4,4′-bipyridin-1-ium cation is almost coplanar with one benzene ring [dihedral angle = 1.03 (5)°], while it makes dihedral angles of 9.59 (5)° with the other benzene ring and 13.66 (6)° with the pyridinium ring. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link the cations and nitrate anions into a sheet in the (302) plane. The crystal structure also exhibits π–π interactions between the central pyridine ring and the benzene rings of neighboring molecules [centroid–centroid distance = 3.6756 (13) Å].

Related literature

For the properties and applications of molecular-ionic crystals, see: Katrusiak & Szafrański (2006 ); Liao et al. (2008 ); Wang (2010 ).

Experimental

Crystal data

C₂₄H₁₇N₂O₄⁺·NO₃⁻·0.25H₂O
M_r = 463.91
Monoclinic, P 2₁ /c
a = 13.6978 (11) Å
b = 16.0688 (12) Å
c = 9.6354 (8) Å
β = 92.696 (1)°
V = 2118.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.25 × 0.21 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.973, T_max = 0.978
11529 measured reflections
4158 independent reflections
2605 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.150
S = 1.04
4158 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5ⁱ	0.86	1.84	2.697 (2)	171
O2—H2A⋯O3ⁱⁱ	0.82	1.93	2.728 (2)	163
O4—H4⋯O5	0.82	1.78	2.598 (2)	173
O1W—H1A⋯O1Wⁱⁱⁱ	0.92	2.14	2.963 (18)	149
O1W—H1B⋯O1^iv	0.90	2.22	3.059 (8)	154
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y+2, -z; (iv) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811051506/bt5723sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811051506/bt5723Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811051506/bt5723Isup3.cml

checkCIF report

Comment top

Recently much attention has been devoted to simple molecular-ionic crystals containing organic cations and anions due to the tunability of their special structural features and their interesting physical properties (Katrusiak & Szafrański, 2006; Wang, 2010). Molecular building blocks associated with pyridine carboxylic acids are widely used in chiral catalysis, photoelectronic materials, hematopathology and medicine (Liao et al., 2008). In our laboratory, the compound containing a 2,6-bis(4-carboxyphenyl)-4,4'-bipyridinium cation, an NO₃^- anion and quarter water molecules has been synthesized and its crystal structure is reported here.

In the title compound (Fig. 1), the central pyridine ring of the cation is almost coplanar with one benzene ring, making a dihedral angle of 1.03 (5)°, while it makes dihedral angles of 9.59 (5)° with the other benzene ring and 13.66 (6)° with the protonated pyridinium ring. N—H···O and O—H···O hydrogen bonds link the organic cations and nitrate anions into a one-dimensional ribbon along [0 1 0] (Fig. 2). The crystal structure also exhibits π–π interactions between the central pyridine rings and the benzene rings of neighboring molecules [centroid–centroid distance = 3.6756 (13) Å].

Related literature top

For the properties and applications of molecular-ionic crystals, see: Katrusiak & Szafrański (2006); Liao et al. (2008); Wang (2010).

Experimental top

A mixture of 2,6-di-4-carboxyphenyl-4,4'-bipyridine (0.2 mmol, 0.080 g), nitric acid (0.5 ml, 6 mol/L), ethanol (10 ml) and H₂O (5 ml) was stirred for 10 min. A small amount of white precipitate was filtered off and the filtrate was kept for several days at ambient conditions. Colorless block crystals of the title compound were isolated.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); 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 the 50% probability level.
	Fig. 2. View of the one-dimensional ribbon structure of the title compound built by hydrogen bonds (dashed lines).

2',6'-Bis(4-carboxyphenyl)-4,4'-bipyridin-1-ium nitrate hydrate top

Crystal data top

C₂₄H₁₇N₂O₄⁺·NO₃⁻·0.25H₂O	F(000) = 962
M_r = 463.91	D_x = 1.454 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4158 reflections
a = 13.6978 (11) Å	θ = 1.0–26.0°
b = 16.0688 (12) Å	µ = 0.11 mm⁻¹
c = 9.6354 (8) Å	T = 293 K
β = 92.696 (1)°	Block, colorless
V = 2118.5 (3) Å³	0.25 × 0.21 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	4158 independent reflections
Radiation source: fine-focus sealed tube	2605 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −16→16
T_min = 0.973, T_max = 0.978	k = −19→17
11529 measured reflections	l = −9→11

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0724P)² + 0.0957P] where P = (F_o² + 2F_c²)/3
4158 reflections	(Δ/σ)_max < 0.001
316 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₄H₁₇N₂O₄⁺·NO₃⁻·0.25H₂O	V = 2118.5 (3) Å³
M_r = 463.91	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.6978 (11) Å	µ = 0.11 mm⁻¹
b = 16.0688 (12) Å	T = 293 K
c = 9.6354 (8) Å	0.25 × 0.21 × 0.20 mm
β = 92.696 (1)°

Data collection top

Bruker APEXII CCD diffractometer	4158 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2605 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.978	R_int = 0.040
11529 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.04	Δρ_max = 0.30 e Å⁻³
4158 reflections	Δρ_min = −0.27 e Å⁻³
316 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	Occ. (<1)
C1	0.42765 (16)	0.78749 (14)	0.5913 (2)	0.0286 (5)
C2	0.46419 (18)	0.71363 (14)	0.5406 (3)	0.0334 (6)
H2	0.4404	0.6631	0.5715	0.040*
C3	0.53576 (18)	0.71478 (14)	0.4445 (3)	0.0337 (6)
H3	0.5597	0.6647	0.4117	0.040*
C4	0.57286 (16)	0.78937 (13)	0.3957 (2)	0.0258 (5)
C5	0.53495 (17)	0.86287 (14)	0.4469 (3)	0.0330 (6)
H5	0.5579	0.9135	0.4152	0.040*
C6	0.46397 (17)	0.86229 (14)	0.5438 (2)	0.0322 (6)
H6	0.4404	0.9123	0.5774	0.039*
C7	0.35134 (17)	0.78863 (14)	0.6971 (3)	0.0321 (6)
C8	0.65044 (16)	0.78741 (13)	0.2920 (2)	0.0254 (5)
C9	0.69124 (16)	0.85873 (14)	0.2365 (2)	0.0279 (5)
H9	0.6711	0.9110	0.2651	0.033*
C10	0.76210 (16)	0.85180 (13)	0.1382 (2)	0.0260 (5)
C11	0.78848 (16)	0.77208 (14)	0.0987 (2)	0.0273 (5)
H11	0.8352	0.7648	0.0327	0.033*
C12	0.74523 (16)	0.70341 (13)	0.1575 (2)	0.0249 (5)
C13	0.80567 (16)	0.92684 (13)	0.0741 (2)	0.0261 (5)
C14	0.7948 (2)	1.00598 (14)	0.1296 (3)	0.0438 (7)
H14	0.7611	1.0128	0.2104	0.053*
C15	0.8333 (2)	1.07395 (15)	0.0661 (3)	0.0460 (7)
H15	0.8248	1.1267	0.1033	0.055*
C16	0.89662 (18)	0.99033 (13)	−0.1044 (3)	0.0328 (6)
H16	0.9319	0.9856	−0.1842	0.039*
C17	0.85909 (17)	0.92067 (14)	−0.0450 (2)	0.0306 (6)
H17	0.8693	0.8688	−0.0844	0.037*
C18	0.76886 (16)	0.61666 (13)	0.1168 (2)	0.0247 (5)
C19	0.71249 (16)	0.55022 (14)	0.1607 (2)	0.0295 (5)
H19	0.6597	0.5606	0.2154	0.035*
C20	0.73369 (16)	0.46961 (14)	0.1246 (2)	0.0303 (6)
H20	0.6958	0.4262	0.1563	0.036*
C21	0.81127 (16)	0.45261 (13)	0.0410 (2)	0.0272 (5)
C22	0.86680 (18)	0.51865 (14)	−0.0048 (3)	0.0323 (6)
H22	0.9182	0.5083	−0.0622	0.039*
C23	0.84681 (16)	0.59942 (14)	0.0335 (2)	0.0301 (6)
H23	0.8857	0.6427	0.0036	0.036*
C24	0.83576 (16)	0.36588 (14)	0.0027 (2)	0.0286 (5)
N1	0.88275 (14)	1.06493 (12)	−0.0482 (2)	0.0337 (5)
H1	0.9064	1.1082	−0.0869	0.040*
N2	0.67797 (13)	0.71123 (10)	0.25346 (19)	0.0260 (4)
N3	0.99617 (14)	0.19689 (12)	−0.2573 (2)	0.0312 (5)
O2	0.31962 (13)	0.71380 (10)	0.72797 (19)	0.0456 (5)
H2A	0.2781	0.7176	0.7863	0.068*
O1	0.32181 (13)	0.85207 (11)	0.74803 (19)	0.0469 (5)
O4	0.89796 (12)	0.36227 (9)	−0.09689 (18)	0.0387 (5)
H4	0.9094	0.3135	−0.1148	0.058*
O3	0.80256 (12)	0.30430 (9)	0.05852 (18)	0.0350 (4)
O5	0.94948 (15)	0.21008 (10)	−0.14753 (19)	0.0496 (5)
O6	1.02518 (13)	0.25580 (11)	−0.32456 (19)	0.0451 (5)
O7	1.01033 (13)	0.12364 (10)	−0.28914 (18)	0.0428 (5)
O1W	0.5358 (6)	1.0131 (4)	0.1459 (10)	0.062 (2)	0.25
H1A	0.5359	0.9943	0.0556	0.092*	0.25
H1B	0.5683	1.0618	0.1548	0.092*	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0288 (13)	0.0303 (13)	0.0272 (13)	0.0037 (10)	0.0056 (10)	0.0019 (10)
C2	0.0407 (14)	0.0244 (13)	0.0365 (15)	−0.0024 (10)	0.0156 (12)	0.0025 (10)
C3	0.0403 (14)	0.0224 (12)	0.0398 (15)	0.0029 (10)	0.0149 (12)	−0.0015 (10)
C4	0.0257 (12)	0.0270 (12)	0.0248 (13)	0.0015 (9)	0.0037 (10)	−0.0004 (9)
C5	0.0345 (14)	0.0245 (13)	0.0407 (15)	0.0012 (10)	0.0095 (12)	0.0001 (11)
C6	0.0363 (14)	0.0243 (13)	0.0367 (15)	0.0064 (10)	0.0100 (11)	−0.0032 (10)
C7	0.0315 (13)	0.0303 (14)	0.0351 (15)	0.0043 (11)	0.0084 (11)	0.0037 (11)
C8	0.0256 (12)	0.0234 (12)	0.0274 (13)	0.0015 (9)	0.0030 (10)	−0.0001 (9)
C9	0.0318 (13)	0.0221 (12)	0.0305 (13)	0.0007 (10)	0.0091 (10)	−0.0036 (10)
C10	0.0278 (12)	0.0246 (12)	0.0259 (13)	0.0004 (10)	0.0038 (10)	−0.0009 (9)
C11	0.0257 (12)	0.0264 (12)	0.0304 (13)	0.0010 (10)	0.0072 (10)	−0.0011 (10)
C12	0.0256 (12)	0.0243 (12)	0.0249 (13)	0.0010 (9)	0.0024 (10)	0.0010 (9)
C13	0.0268 (12)	0.0213 (12)	0.0305 (13)	0.0003 (9)	0.0051 (10)	0.0005 (9)
C14	0.0612 (18)	0.0250 (14)	0.0480 (17)	−0.0023 (12)	0.0325 (14)	−0.0033 (11)
C15	0.0628 (18)	0.0240 (14)	0.0538 (18)	−0.0013 (12)	0.0293 (15)	−0.0022 (12)
C16	0.0391 (14)	0.0277 (13)	0.0327 (14)	−0.0011 (11)	0.0119 (12)	−0.0005 (11)
C17	0.0363 (13)	0.0225 (12)	0.0333 (14)	0.0019 (10)	0.0063 (11)	−0.0026 (10)
C18	0.0258 (12)	0.0208 (12)	0.0276 (13)	−0.0004 (9)	0.0033 (10)	0.0023 (9)
C19	0.0273 (12)	0.0264 (13)	0.0361 (14)	0.0012 (10)	0.0134 (10)	0.0006 (10)
C20	0.0305 (13)	0.0223 (12)	0.0389 (15)	−0.0031 (10)	0.0098 (11)	0.0020 (10)
C21	0.0290 (12)	0.0229 (12)	0.0300 (13)	−0.0015 (10)	0.0047 (10)	−0.0012 (10)
C22	0.0329 (13)	0.0294 (13)	0.0357 (14)	0.0005 (11)	0.0147 (11)	−0.0011 (11)
C23	0.0327 (13)	0.0200 (12)	0.0384 (14)	−0.0020 (10)	0.0121 (11)	0.0021 (10)
C24	0.0282 (13)	0.0260 (13)	0.0321 (14)	−0.0001 (10)	0.0057 (11)	0.0004 (10)
N1	0.0399 (12)	0.0244 (11)	0.0380 (12)	−0.0038 (9)	0.0146 (10)	0.0045 (9)
N2	0.0272 (10)	0.0231 (10)	0.0278 (11)	0.0014 (8)	0.0043 (8)	−0.0005 (8)
N3	0.0333 (11)	0.0273 (11)	0.0338 (12)	−0.0033 (9)	0.0089 (9)	0.0009 (9)
O2	0.0508 (11)	0.0341 (10)	0.0541 (13)	0.0027 (8)	0.0271 (10)	0.0052 (9)
O1	0.0550 (12)	0.0346 (10)	0.0534 (13)	0.0088 (9)	0.0277 (10)	−0.0016 (9)
O4	0.0485 (10)	0.0250 (9)	0.0446 (11)	0.0010 (8)	0.0218 (9)	−0.0032 (8)
O3	0.0389 (10)	0.0240 (9)	0.0431 (11)	−0.0011 (7)	0.0141 (8)	0.0018 (7)
O5	0.0812 (14)	0.0267 (10)	0.0441 (12)	−0.0023 (9)	0.0370 (11)	−0.0029 (8)
O6	0.0528 (12)	0.0370 (10)	0.0466 (12)	−0.0102 (9)	0.0156 (9)	0.0122 (9)
O7	0.0522 (12)	0.0295 (10)	0.0482 (12)	0.0052 (8)	0.0181 (9)	−0.0051 (8)
O1W	0.069 (5)	0.023 (4)	0.093 (7)	0.006 (4)	−0.002 (5)	0.010 (4)

Geometric parameters (Å, º) top

C1—C2	1.386 (3)	C15—N1	1.328 (3)
C1—C6	1.387 (3)	C15—H15	0.9300
C1—C7	1.495 (3)	C16—N1	1.333 (3)
C2—C3	1.380 (3)	C16—C17	1.369 (3)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.392 (3)	C17—H17	0.9300
C3—H3	0.9300	C18—C23	1.393 (3)
C4—C5	1.390 (3)	C18—C19	1.395 (3)
C4—C8	1.493 (3)	C19—C20	1.376 (3)
C5—C6	1.379 (3)	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.390 (3)
C6—H6	0.9300	C20—H20	0.9300
C7—O1	1.209 (3)	C21—C22	1.390 (3)
C7—O2	1.317 (3)	C21—C24	1.484 (3)
C8—N2	1.338 (3)	C22—C23	1.380 (3)
C8—C9	1.393 (3)	C22—H22	0.9300
C9—C10	1.392 (3)	C23—H23	0.9300
C9—H9	0.9300	C24—O3	1.224 (3)
C10—C11	1.389 (3)	C24—O4	1.314 (3)
C10—C13	1.492 (3)	N1—H1	0.8600
C11—C12	1.386 (3)	N3—O6	1.224 (2)
C11—H11	0.9300	N3—O7	1.234 (2)
C12—N2	1.341 (3)	N3—O5	1.279 (2)
C12—C18	1.488 (3)	O2—H2A	0.8200
C13—C14	1.390 (3)	O4—H4	0.8200
C13—C17	1.393 (3)	O1W—H1A	0.9210
C14—C15	1.370 (3)	O1W—H1B	0.9027
C14—H14	0.9300

C2—C1—C6	119.0 (2)	C13—C14—H14	119.8
C2—C1—C7	121.8 (2)	N1—C15—C14	120.4 (2)
C6—C1—C7	119.2 (2)	N1—C15—H15	119.8
C3—C2—C1	120.3 (2)	C14—C15—H15	119.8
C3—C2—H2	119.8	N1—C16—C17	120.1 (2)
C1—C2—H2	119.8	N1—C16—H16	119.9
C2—C3—C4	121.3 (2)	C17—C16—H16	119.9
C2—C3—H3	119.3	C16—C17—C13	120.6 (2)
C4—C3—H3	119.3	C16—C17—H17	119.7
C5—C4—C3	117.6 (2)	C13—C17—H17	119.7
C5—C4—C8	123.0 (2)	C23—C18—C19	118.2 (2)
C3—C4—C8	119.4 (2)	C23—C18—C12	121.34 (19)
C6—C5—C4	121.4 (2)	C19—C18—C12	120.5 (2)
C6—C5—H5	119.3	C20—C19—C18	121.2 (2)
C4—C5—H5	119.3	C20—C19—H19	119.4
C5—C6—C1	120.3 (2)	C18—C19—H19	119.4
C5—C6—H6	119.9	C19—C20—C21	120.5 (2)
C1—C6—H6	119.9	C19—C20—H20	119.7
O1—C7—O2	123.9 (2)	C21—C20—H20	119.7
O1—C7—C1	123.0 (2)	C22—C21—C20	118.6 (2)
O2—C7—C1	113.0 (2)	C22—C21—C24	120.3 (2)
N2—C8—C9	121.5 (2)	C20—C21—C24	121.1 (2)
N2—C8—C4	115.06 (19)	C23—C22—C21	120.9 (2)
C9—C8—C4	123.41 (19)	C23—C22—H22	119.5
C10—C9—C8	120.0 (2)	C21—C22—H22	119.5
C10—C9—H9	120.0	C22—C23—C18	120.5 (2)
C8—C9—H9	120.0	C22—C23—H23	119.7
C11—C10—C9	117.3 (2)	C18—C23—H23	119.7
C11—C10—C13	121.2 (2)	O3—C24—O4	123.5 (2)
C9—C10—C13	121.5 (2)	O3—C24—C21	123.8 (2)
C12—C11—C10	120.0 (2)	O4—C24—C21	112.65 (19)
C12—C11—H11	120.0	C15—N1—C16	121.6 (2)
C10—C11—H11	120.0	C15—N1—H1	119.2
N2—C12—C11	121.9 (2)	C16—N1—H1	119.2
N2—C12—C18	115.74 (19)	C8—N2—C12	119.23 (19)
C11—C12—C18	122.4 (2)	O6—N3—O7	123.2 (2)
C14—C13—C17	116.9 (2)	O6—N3—O5	119.81 (19)
C14—C13—C10	121.8 (2)	O7—N3—O5	117.02 (18)
C17—C13—C10	121.3 (2)	C7—O2—H2A	109.5
C15—C14—C13	120.5 (2)	C24—O4—H4	109.5
C15—C14—H14	119.8	H1A—O1W—H1B	110.5

C6—C1—C2—C3	0.1 (4)	C17—C13—C14—C15	1.6 (4)
C7—C1—C2—C3	−178.9 (2)	C10—C13—C14—C15	−178.2 (2)
C1—C2—C3—C4	−0.2 (4)	C13—C14—C15—N1	−0.9 (4)
C2—C3—C4—C5	−0.2 (4)	N1—C16—C17—C13	0.4 (4)
C2—C3—C4—C8	179.9 (2)	C14—C13—C17—C16	−1.4 (4)
C3—C4—C5—C6	0.7 (4)	C10—C13—C17—C16	178.4 (2)
C8—C4—C5—C6	−179.4 (2)	N2—C12—C18—C23	−170.8 (2)
C4—C5—C6—C1	−0.8 (4)	C11—C12—C18—C23	10.3 (3)
C2—C1—C6—C5	0.4 (4)	N2—C12—C18—C19	9.7 (3)
C7—C1—C6—C5	179.5 (2)	C11—C12—C18—C19	−169.2 (2)
C2—C1—C7—O1	176.2 (2)	C23—C18—C19—C20	0.8 (3)
C6—C1—C7—O1	−2.9 (4)	C12—C18—C19—C20	−179.7 (2)
C2—C1—C7—O2	−4.2 (4)	C18—C19—C20—C21	−1.1 (4)
C6—C1—C7—O2	176.7 (2)	C19—C20—C21—C22	0.1 (4)
C5—C4—C8—N2	−179.6 (2)	C19—C20—C21—C24	179.2 (2)
C3—C4—C8—N2	0.3 (3)	C20—C21—C22—C23	1.2 (4)
C5—C4—C8—C9	−0.5 (4)	C24—C21—C22—C23	−177.9 (2)
C3—C4—C8—C9	179.4 (2)	C21—C22—C23—C18	−1.5 (4)
N2—C8—C9—C10	0.3 (3)	C19—C18—C23—C22	0.4 (3)
C4—C8—C9—C10	−178.8 (2)	C12—C18—C23—C22	−179.1 (2)
C8—C9—C10—C11	0.6 (3)	C22—C21—C24—O3	166.1 (2)
C8—C9—C10—C13	178.5 (2)	C20—C21—C24—O3	−13.0 (4)
C9—C10—C11—C12	−0.5 (3)	C22—C21—C24—O4	−13.2 (3)
C13—C10—C11—C12	−178.5 (2)	C20—C21—C24—O4	167.7 (2)
C10—C11—C12—N2	−0.3 (3)	C14—C15—N1—C16	−0.1 (4)
C10—C11—C12—C18	178.5 (2)	C17—C16—N1—C15	0.4 (4)
C11—C10—C13—C14	−167.6 (2)	C9—C8—N2—C12	−1.1 (3)
C9—C10—C13—C14	14.5 (4)	C4—C8—N2—C12	178.05 (19)
C11—C10—C13—C17	12.6 (3)	C11—C12—N2—C8	1.2 (3)
C9—C10—C13—C17	−165.3 (2)	C18—C12—N2—C8	−177.77 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱ	0.86	1.84	2.697 (2)	171
O2—H2A···O3ⁱⁱ	0.82	1.93	2.728 (2)	163
O4—H4···O5	0.82	1.78	2.598 (2)	173
O1W—H1A···O1Wⁱⁱⁱ	0.92	2.14	2.963 (18)	149
O1W—H1B···O1^iv	0.90	2.22	3.059 (8)	154

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

Experimental details

Crystal data
Chemical formula	C₂₄H₁₇N₂O₄⁺·NO₃⁻·0.25H₂O
M_r	463.91
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.6978 (11), 16.0688 (12), 9.6354 (8)
β (°)	92.696 (1)
V (Å³)	2118.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.25 × 0.21 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.973, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	11529, 4158, 2605
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.150, 1.04
No. of reflections	4158
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.27

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱ	0.86	1.84	2.697 (2)	171
O2—H2A···O3ⁱⁱ	0.82	1.93	2.728 (2)	163
O4—H4···O5	0.82	1.78	2.598 (2)	173
O1W—H1A···O1Wⁱⁱⁱ	0.92	2.14	2.963 (18)	149
O1W—H1B···O1^iv	0.90	2.22	3.059 (8)	154

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

Acknowledgements

The authors thank Jilin University for supporting this work.

References

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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