1,10-Phenanthrolin-1-ium hydrogen (S,S)-tartrate trihydrate and a correction

Derikvand, Z.; Olmstead, M.M.

doi:10.1107/S160053680905332X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o185

doi:10.1107/S160053680905332X

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1,10-Phenanthrolin-1-ium hydrogen (S,S)-tartrate trihydrate and a correction

Zohreh Derikvand ^a and Marilyn M. Olmstead ^b ^*

^aFaculty of Science, Department of Chemistry, Islamic Azad University, Khorramabad Branch, Khorramabad, Iran, and ^bDepartment of Chemistry, University of California, Davis, CA 95616-5292, USA
^*Correspondence e-mail: mmolmstead@ucdavis.edu

(Received 2 December 2009; accepted 10 December 2009; online 19 December 2009)

The title structure, C₁₂H₉N₂⁺·C₄H₅O₆⁻·3H₂O, shows that one of the protons of D-tartaric acid has been transferred to 1,10-phenanthroline. The D-hydrogen tartrate anions are joined together in a head-to-tail fashion via a short hydrogen bond with donor–acceptor distance of 2.4554 (12) Å, unsymmetrical O—H distances of 1.01 (4) Å and 1.45 (4) Å, and a 174 (4)° O—H—O bond angle. The phenanthrolinium rings are π-stacked with an average separation of 3.58 (11) Å. The structural report corrects a previous report in the literature [Wang et al. (2006 ). Acta Cryst. E62, o2508–o2509] of the isostructural L-hydrogen tartrate enantiomer in which the proton transfer and short hydrogen bond were missed.

Related literature

For related proton-transfer hydrogen tartrate structures, see: Bai et al. (2005 ); Paixão et al. (1999 ); Smith et al. (2006 ); Su et al. (2009 ); Suresh et al. (2006 ); Wang et al. (2006, 2008 ); Zhang et al. (2006 ).

Experimental

Crystal data

C₁₂H₉N₂⁺·C₄H₅O₆⁻·3H₂O
M_r = 384.34
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.1163 (14) Å
b = 12.482 (3) Å
c = 19.466 (4) Å
V = 1729.2 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 90 K
0.42 × 0.21 × 0.13 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.880, T_max = 0.984
39094 measured reflections
3251 independent reflections
3149 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.06
3251 reflections
324 parameters
All H-atom parameters refined
Δρ_max = 0.41 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
O2—H2A⋯O6ⁱ	1.01 (4)	1.45 (4)	2.4554 (12)	174 (4)
O3—H3A⋯O8ⁱⁱ	0.86 (2)	1.86 (2)	2.6817 (13)	159 (2)
O4—H4A⋯O9ⁱ	0.81 (3)	1.90 (3)	2.7102 (13)	173 (3)
N2—H2B⋯O7	0.912 (19)	1.763 (19)	2.6426 (14)	161.3 (18)
O7—H7A⋯O6ⁱⁱⁱ	0.91 (2)	1.87 (2)	2.7727 (13)	170 (2)
O7—H7B⋯O5	0.81 (3)	2.02 (3)	2.7141 (14)	144 (3)
O7—H7B⋯O4	0.81 (3)	2.36 (3)	3.0442 (14)	143 (3)
O8—H8A⋯O3ⁱ	0.85 (3)	1.90 (3)	2.7497 (13)	171 (2)
O8—H8B⋯O1	0.92 (3)	1.77 (3)	2.6730 (14)	165 (3)
O9—H9A⋯O2ⁱⁱⁱ	0.87 (3)	2.15 (3)	2.9472 (14)	152 (3)
O9—H9B⋯O5	0.79 (3)	1.96 (3)	2.7452 (14)	179 (3)
Symmetry codes: (i) x-1, y, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680905332X/nk2019sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680905332X/nk2019Isup2.hkl

checkCIF report

Comment top

Tartaric acid is a colorless, diprotic organic acid that occurs naturally in many plants, particularly grapes, bananas, and tamarinds, and is one of the main acids found in wine. It is added to other foods to give a sour taste, and is used as an antioxidant. Many proton transfer compounds of tartaric acid and various bases have been reported, for example, (Paixão et al., 1999; Bai et al., 2005; Zhang et al., 2006; Suresh et al., 2006; Wang et al., 2008; Su et al., 2009). The title structure contains a cation of protonated 1,10-phenanthroline, an anion of mono-deprotonated D-tartaric acid, and three water molecules (Fig. 1). Thus, the crystal structure shows that one of the protons of the tartaric acid carboxylic groups has been transferred to one of the nitrogen atoms of the 1,10-phenanthroline molecule. A portion of the hydrogen bonding motif involving the anions, cations and water molecules is presented in Fig. 2; details of the O—H···O and N—H···O hydrogen bonds are given in Table 1. Fig. 2 also shows how the 1,10-phenanthrolinium rings are π-stacked such that they are perpendicular to the chain of tartrate anions that run along the a axis. The average perpendicular distance between the plane of N1/N2/C1/C2/C3/C4/C5/C6/C7/C8/C9/C10/C11/C12 and the 14 atoms at ii = 1/2 + x, 3/2 - y, 1 - z of the stacked phenanthroline ring is 3.58 (11) Å. The tartrate anions are connected head-to-tail by a short hydrogen bond between H2A, bonded to O2, and O6ⁱ of the anion at i = x - 1, y, z. The O2—H2A distance is 1.01 (4) Å, H2A—O6ⁱ is 1.45 (4) Å and O2···O6ⁱ is 2.4554 (12) Å. The O2—H2A—O6ⁱ angle is 174 (4)°. Electrostatic considerations, together with the use of resonance structures, could be used to explain the short hydrogen bond. Additionally, the existence of a number of supporting hydrogen bonds could be a factor, and these are depicted in Fig. 3. A similar head-to-tail arrangement with a short donor- acceptor distance is seen in some other hydrogen tartrate structures (Paixão et al., 1999; Zhang et al., 2006). The geometry of the hydrogen atom, H2A, that is involved in the short hydrogen bond has larger standard uncertainties than other hydrogen atoms in the structure. The larger uncertainty can be accounted for by examination of a plot of difference electron density (Fig. 4) (EDEN, Sheldrick (2008)), which shows that H2A resides in a shallow potential well that has a single minimum close to O2 but tails off towards O6ⁱ.

A previous structural determination of the isostructural L-tartrate enantiomer (II) (Wang et al., 2006) missed the proton transfer and identified the compound as 1,10-phenanthroline (2R,3R)-tartaric acid. We have examined their data and confirmed that the proton transfer did occur, and refinement of the structure using the model of the title compound results in lower R values. Interestingly, a subsequent paper on the quinoline analog by Smith et al., 2006, expressed surprise that the proton in (II) was not transferred: "···the absence of transfer in the L-tartaric acid-1,10-phenanthroline compound reported by Wang et al. (2006) when compared with the structurally similar [quinolinium] is not understood, considering that the pK_a value for 1,10-phenanthroline (4.86) is very close to that of quinoline (4.81)." We note that, in the structure of (II), the details of the short hydrogen bond are not revealed because tartaric acid O—H distance restraints of 0.82 (1) Å were applied, and also because the acceptor O atom has the misplaced H atom. In the refinement of the title compound, hydrogen atoms were freely refined. In (II), data were collected at 293 (2) K, and the data/parameter ratio is 7.34. In the title compound, data were collected at 90 (2) K, and the data/parameter ratio is 10.03.

Related literature top

For related proton-transfer hydrogen tartrate structures, see: Bai et al. (2005); Paixão et al. (1999); Smith et al. (2006); Su et al. (2009); Suresh et al. (2006); Wang et al. (2006, 2008); Zhang et al. (2006).

Experimental top

The reaction between solutions of D-tartaric acid (7 mg, 1 mmol) in water (10 ml) and 1,10-phenanthroline (9 mg, 1 mmol) in methanol (5 ml) in a 1:1 molar ratio gave colorless rod crystals after slow evaporation of the solvent at room temperature.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A drawing of the asymmetric unit of the title compound. Thermal ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view showing how the phenanthrolinium ions pack together in a parallel fashion while the tartrate anions string together via a strong hydrogen bond along the a direction of the crystal. Symmetry code: (i) x - 1, y, z.
	Fig. 3. The hydrogen bonding interactions that support the strong hydrogen bonding interaction between tartrate anions. Symmetry codes: (i) x - 1, y, z; (ii) 1 - x, y - 1/2, 1.5 - z; (iii) -x, y - 1/2, 1.5 - z.
	Fig. 4. A plot of electron density contours showing the difference Fourier map for H2A, the hydrogen atom involved in the short hydrogen bond. The maximum density contour is 0.45 e/Å³.

(I) top

Crystal data top

C₁₂H₉N₂⁺·C₄H₅O₆⁻·3H₂O	F(000) = 808
M_r = 384.34	D_x = 1.476 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9999 reflections
a = 7.1163 (14) Å	θ = 2.8–31.5°
b = 12.482 (3) Å	µ = 0.12 mm⁻¹
c = 19.466 (4) Å	T = 90 K
V = 1729.2 (6) Å³	Rod, colourless
Z = 4	0.42 × 0.21 × 0.13 mm

Data collection top

Bruker SMART APEXII diffractometer	3251 independent reflections
Radiation source: fine-focus sealed tube	3149 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 8.3 pixels mm^-1	θ_max = 31.6°, θ_min = 1.9°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −18→18
T_min = 0.880, T_max = 0.984	l = −28→28
39094 measured reflections

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)] = 0.032	Hydrogen site location: difference Fourier map
wR(F²) = 0.089	All H-atom parameters refined
S = 1.06	w = 1/[σ²(F_o²) + (0.0669P)² + 0.1713P] where P = (F_o² + 2F_c²)/3
3251 reflections	(Δ/σ)_max = 0.003
324 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₂H₉N₂⁺·C₄H₅O₆⁻·3H₂O	V = 1729.2 (6) Å³
M_r = 384.34	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.1163 (14) Å	µ = 0.12 mm⁻¹
b = 12.482 (3) Å	T = 90 K
c = 19.466 (4) Å	0.42 × 0.21 × 0.13 mm

Data collection top

Bruker SMART APEXII diffractometer	3251 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3149 reflections with I > 2σ(I)
T_min = 0.880, T_max = 0.984	R_int = 0.027
39094 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.089	All H-atom parameters refined
S = 1.06	Δρ_max = 0.41 e Å⁻³
3251 reflections	Δρ_min = −0.18 e Å⁻³
324 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
O1	−0.02434 (15)	0.28085 (14)	0.60625 (5)	0.0387 (3)
O2	−0.01282 (11)	0.22520 (7)	0.71533 (4)	0.01530 (16)
H2A	−0.155 (5)	0.227 (3)	0.7139 (19)	0.082 (11)*
O3	0.34399 (12)	0.27724 (8)	0.59021 (4)	0.01825 (18)
H3A	0.266 (3)	0.2529 (17)	0.5600 (11)	0.025 (5)*
O4	0.29691 (13)	0.43589 (7)	0.69506 (5)	0.01723 (17)
H4A	0.202 (4)	0.450 (2)	0.7164 (15)	0.052 (7)*
O5	0.65945 (13)	0.40940 (7)	0.69497 (5)	0.02051 (18)
O6	0.64269 (11)	0.23538 (7)	0.71823 (4)	0.01439 (15)
N1	0.56039 (18)	0.85195 (8)	0.60703 (5)	0.01821 (19)
N2	0.55402 (17)	0.64831 (8)	0.55452 (5)	0.01820 (19)
H2B	0.558 (3)	0.6546 (15)	0.6011 (10)	0.020 (4)*
C1	0.5526 (2)	0.54779 (10)	0.53258 (7)	0.0244 (3)
H1	0.545 (4)	0.494 (2)	0.5654 (13)	0.038 (6)*
C2	0.5479 (2)	0.52505 (11)	0.46232 (7)	0.0267 (3)
H2	0.545 (4)	0.4546 (18)	0.4486 (12)	0.033 (5)*
C3	0.5443 (2)	0.60764 (12)	0.41615 (7)	0.0238 (2)
H3	0.533 (4)	0.590 (2)	0.3720 (13)	0.042 (6)*
C4	0.54614 (19)	0.71407 (10)	0.43933 (6)	0.0194 (2)
C5	0.5432 (2)	0.80340 (13)	0.39336 (6)	0.0263 (3)
H5	0.533 (5)	0.792 (3)	0.3465 (16)	0.071 (9)*
C6	0.5492 (2)	0.90440 (12)	0.41791 (6)	0.0266 (3)
H6	0.549 (4)	0.966 (2)	0.3898 (14)	0.053 (8)*
C7	0.55687 (19)	0.92492 (10)	0.49056 (6)	0.0190 (2)
C8	0.5681 (2)	1.02891 (10)	0.51766 (7)	0.0217 (2)
H8	0.568 (3)	1.0922 (17)	0.4873 (10)	0.026 (5)*
C9	0.5760 (2)	1.04196 (10)	0.58747 (7)	0.0206 (2)
H9	0.584 (3)	1.1120 (18)	0.6092 (10)	0.029 (5)*
C10	0.5697 (2)	0.95135 (10)	0.63030 (6)	0.0201 (2)
H10	0.577 (3)	0.9670 (17)	0.6820 (11)	0.027 (5)*
C11	0.55581 (17)	0.83917 (9)	0.53766 (5)	0.01526 (19)
C12	0.55133 (17)	0.73284 (9)	0.51062 (6)	0.0157 (2)
C13	0.06195 (15)	0.25433 (10)	0.65712 (5)	0.01487 (19)
C14	0.27564 (14)	0.25118 (9)	0.65602 (5)	0.01263 (18)
H14	0.308 (3)	0.1803 (15)	0.6702 (9)	0.018 (4)*
C15	0.35517 (14)	0.33050 (8)	0.70860 (5)	0.01159 (17)
H15	0.316 (3)	0.3068 (14)	0.7552 (9)	0.017 (4)*
C16	0.57000 (15)	0.32740 (8)	0.70659 (5)	0.01187 (18)
O7	0.57458 (15)	0.62117 (7)	0.68894 (5)	0.01850 (17)
H7A	0.491 (3)	0.6571 (19)	0.7160 (11)	0.034 (6)*
H7B	0.549 (4)	0.558 (2)	0.6918 (12)	0.040 (6)*
O8	−0.31974 (13)	0.30315 (9)	0.52265 (4)	0.02028 (18)
H8A	−0.422 (4)	0.2882 (19)	0.5431 (12)	0.035 (6)*
H8B	−0.231 (4)	0.301 (2)	0.5572 (12)	0.041 (6)*
O9	0.97193 (13)	0.49415 (8)	0.75731 (5)	0.01928 (18)
H9A	0.952 (4)	0.563 (2)	0.7552 (14)	0.047 (7)*
H9B	0.883 (4)	0.4694 (19)	0.7395 (13)	0.038 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0136 (4)	0.0860 (11)	0.0166 (4)	0.0040 (5)	−0.0014 (3)	0.0110 (5)
O2	0.0102 (3)	0.0187 (4)	0.0171 (3)	0.0010 (3)	0.0016 (3)	0.0048 (3)
O3	0.0133 (3)	0.0298 (4)	0.0117 (3)	−0.0028 (3)	0.0021 (3)	−0.0019 (3)
O4	0.0153 (3)	0.0125 (3)	0.0240 (4)	0.0043 (3)	0.0014 (3)	0.0015 (3)
O5	0.0138 (3)	0.0135 (3)	0.0343 (5)	−0.0021 (3)	−0.0009 (3)	0.0033 (3)
O6	0.0097 (3)	0.0125 (3)	0.0209 (4)	0.0009 (3)	0.0011 (3)	0.0031 (3)
N1	0.0262 (5)	0.0151 (4)	0.0134 (4)	0.0032 (4)	0.0004 (4)	−0.0002 (3)
N2	0.0240 (5)	0.0154 (4)	0.0152 (4)	0.0024 (4)	−0.0009 (4)	−0.0013 (3)
C1	0.0332 (7)	0.0167 (5)	0.0234 (6)	0.0027 (5)	−0.0030 (5)	−0.0039 (4)
C2	0.0333 (7)	0.0210 (5)	0.0259 (6)	0.0034 (6)	−0.0050 (5)	−0.0095 (5)
C3	0.0255 (6)	0.0276 (6)	0.0182 (5)	0.0008 (5)	−0.0021 (5)	−0.0092 (4)
C4	0.0208 (5)	0.0238 (5)	0.0138 (4)	−0.0007 (5)	−0.0007 (4)	−0.0037 (4)
C5	0.0347 (7)	0.0318 (6)	0.0124 (4)	−0.0030 (6)	−0.0003 (5)	0.0008 (4)
C6	0.0376 (7)	0.0282 (6)	0.0140 (5)	−0.0036 (6)	−0.0008 (5)	0.0061 (4)
C7	0.0223 (5)	0.0198 (5)	0.0148 (4)	−0.0010 (5)	−0.0004 (4)	0.0041 (4)
C8	0.0266 (6)	0.0173 (5)	0.0214 (5)	0.0009 (5)	0.0001 (5)	0.0052 (4)
C9	0.0262 (5)	0.0139 (4)	0.0217 (5)	0.0034 (5)	0.0011 (5)	0.0016 (4)
C10	0.0292 (6)	0.0153 (4)	0.0158 (4)	0.0038 (5)	0.0011 (4)	−0.0006 (4)
C11	0.0173 (5)	0.0148 (4)	0.0137 (4)	0.0013 (4)	0.0003 (4)	0.0006 (3)
C12	0.0168 (5)	0.0168 (5)	0.0135 (4)	0.0006 (4)	−0.0005 (4)	−0.0012 (4)
C13	0.0097 (4)	0.0206 (5)	0.0143 (4)	−0.0004 (4)	0.0003 (3)	−0.0016 (4)
C14	0.0093 (4)	0.0161 (4)	0.0124 (4)	0.0003 (4)	0.0004 (3)	−0.0015 (3)
C15	0.0098 (4)	0.0116 (4)	0.0134 (4)	0.0011 (3)	−0.0002 (3)	−0.0001 (3)
C16	0.0105 (4)	0.0133 (4)	0.0118 (4)	0.0001 (4)	−0.0001 (3)	−0.0001 (3)
O7	0.0251 (4)	0.0114 (3)	0.0190 (4)	0.0008 (3)	0.0038 (3)	−0.0004 (3)
O8	0.0146 (4)	0.0316 (5)	0.0146 (3)	0.0005 (4)	0.0001 (3)	−0.0010 (3)
O9	0.0173 (4)	0.0166 (4)	0.0240 (4)	0.0006 (3)	−0.0010 (3)	−0.0015 (3)

Geometric parameters (Å, º) top

O1—C13	1.2113 (15)	C5—H5	0.92 (3)
O2—C13	1.3036 (13)	C6—C7	1.4384 (17)
O2—H2A	1.01 (4)	C6—H6	0.95 (3)
O3—C14	1.4082 (13)	C7—C8	1.4034 (18)
O3—H3A	0.86 (2)	C7—C11	1.4094 (16)
O4—C15	1.4043 (13)	C8—C9	1.3696 (18)
O4—H4A	0.81 (3)	C8—H8	0.99 (2)
O5—C16	1.2264 (14)	C9—C10	1.4059 (17)
O6—C16	1.2800 (13)	C9—H9	0.97 (2)
N1—C10	1.3226 (15)	C10—H10	1.03 (2)
N1—C11	1.3602 (14)	C11—C12	1.4282 (16)
N2—C1	1.3254 (16)	C13—C14	1.5214 (15)
N2—C12	1.3579 (15)	C14—C15	1.5324 (15)
N2—H2B	0.912 (19)	C14—H14	0.955 (19)
C1—C2	1.3973 (19)	C15—C16	1.5298 (15)
C1—H1	0.93 (3)	C15—H15	0.994 (17)
C2—C3	1.368 (2)	O7—H7A	0.91 (2)
C2—H2	0.92 (2)	O7—H7B	0.81 (3)
C3—C4	1.4030 (18)	O8—H8A	0.85 (3)
C3—H3	0.89 (3)	O8—H8B	0.92 (3)
C4—C12	1.4079 (15)	O9—H9A	0.87 (3)
C4—C5	1.4299 (19)	O9—H9B	0.79 (3)
C5—C6	1.349 (2)

C13—O2—H2A	112 (2)	C8—C9—H9	122.7 (12)
C14—O3—H3A	108.6 (14)	C10—C9—H9	117.8 (12)
C15—O4—H4A	111 (2)	N1—C10—C9	123.59 (11)
C10—N1—C11	116.83 (10)	N1—C10—H10	121.1 (12)
C1—N2—C12	122.19 (11)	C9—C10—H10	115.2 (12)
C1—N2—H2B	113.7 (12)	N1—C11—C7	123.82 (11)
C12—N2—H2B	124.1 (12)	N1—C11—C12	118.39 (10)
N2—C1—C2	120.52 (12)	C7—C11—C12	117.79 (10)
N2—C1—H1	117.8 (15)	N2—C12—C4	119.43 (11)
C2—C1—H1	121.5 (15)	N2—C12—C11	119.33 (10)
C3—C2—C1	119.37 (12)	C4—C12—C11	121.23 (10)
C3—C2—H2	121.9 (14)	O1—C13—O2	125.45 (11)
C1—C2—H2	118.7 (14)	O1—C13—C14	120.15 (10)
C2—C3—C4	120.14 (11)	O2—C13—C14	114.40 (9)
C2—C3—H3	116.8 (17)	O3—C14—C13	110.62 (9)
C4—C3—H3	122.9 (17)	O3—C14—C15	109.32 (9)
C3—C4—C12	118.35 (11)	C13—C14—C15	110.06 (9)
C3—C4—C5	122.48 (11)	O3—C14—H14	113.3 (11)
C12—C4—C5	119.17 (12)	C13—C14—H14	105.1 (13)
C6—C5—C4	120.45 (11)	C15—C14—H14	108.4 (12)
C6—C5—H5	119 (2)	O4—C15—C16	108.30 (9)
C4—C5—H5	120 (2)	O4—C15—C14	111.77 (9)
C5—C6—C7	121.07 (12)	C16—C15—C14	109.61 (9)
C5—C6—H6	123.9 (16)	O4—C15—H15	111.5 (11)
C7—C6—H6	115.1 (16)	C16—C15—H15	107.4 (11)
C8—C7—C11	117.27 (11)	C14—C15—H15	108.2 (11)
C8—C7—C6	122.45 (11)	O5—C16—O6	124.88 (10)
C11—C7—C6	120.27 (12)	O5—C16—C15	120.16 (10)
C9—C8—C7	119.03 (11)	O6—C16—C15	114.96 (9)
C9—C8—H8	120.0 (12)	H7A—O7—H7B	107 (2)
C7—C8—H8	121.0 (12)	H8A—O8—H8B	104 (2)
C8—C9—C10	119.43 (11)	H9A—O9—H9B	104 (3)

C12—N2—C1—C2	−0.1 (2)	C1—N2—C12—C11	−179.10 (13)
N2—C1—C2—C3	−0.2 (3)	C3—C4—C12—N2	−0.10 (19)
C1—C2—C3—C4	0.3 (2)	C5—C4—C12—N2	179.96 (12)
C2—C3—C4—C12	−0.2 (2)	C3—C4—C12—C11	179.23 (12)
C2—C3—C4—C5	179.78 (15)	C5—C4—C12—C11	−0.71 (19)
C3—C4—C5—C6	−178.60 (15)	N1—C11—C12—N2	−0.78 (18)
C12—C4—C5—C6	1.3 (2)	C7—C11—C12—N2	178.68 (12)
C4—C5—C6—C7	−0.6 (3)	N1—C11—C12—C4	179.89 (12)
C5—C6—C7—C8	178.30 (15)	C7—C11—C12—C4	−0.65 (18)
C5—C6—C7—C11	−0.8 (2)	O1—C13—C14—O3	−2.66 (18)
C11—C7—C8—C9	−0.5 (2)	O2—C13—C14—O3	176.32 (9)
C6—C7—C8—C9	−179.65 (14)	O1—C13—C14—C15	118.25 (14)
C7—C8—C9—C10	−1.0 (2)	O2—C13—C14—C15	−62.78 (13)
C11—N1—C10—C9	−0.3 (2)	O3—C14—C15—O4	62.27 (11)
C8—C9—C10—N1	1.5 (2)	C13—C14—C15—O4	−59.41 (12)
C10—N1—C11—C7	−1.2 (2)	O3—C14—C15—C16	−57.81 (11)
C10—N1—C11—C12	178.18 (12)	C13—C14—C15—C16	−179.49 (9)
C8—C7—C11—N1	1.7 (2)	O4—C15—C16—O5	0.45 (14)
C6—C7—C11—N1	−179.15 (14)	C14—C15—C16—O5	122.63 (11)
C8—C7—C11—C12	−177.76 (12)	O4—C15—C16—O6	179.93 (9)
C6—C7—C11—C12	1.42 (19)	C14—C15—C16—O6	−57.89 (12)
C1—N2—C12—C4	0.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O6ⁱ	1.01 (4)	1.45 (4)	2.4554 (12)	174 (4)
O3—H3A···O8ⁱⁱ	0.86 (2)	1.86 (2)	2.6817 (13)	159 (2)
O4—H4A···O9ⁱ	0.81 (3)	1.90 (3)	2.7102 (13)	173 (3)
N2—H2B···O7	0.912 (19)	1.763 (19)	2.6426 (14)	161.3 (18)
O7—H7A···O6ⁱⁱⁱ	0.91 (2)	1.87 (2)	2.7727 (13)	170 (2)
O7—H7B···O5	0.81 (3)	2.02 (3)	2.7141 (14)	144 (3)
O7—H7B···O4	0.81 (3)	2.36 (3)	3.0442 (14)	143 (3)
O8—H8A···O3ⁱ	0.85 (3)	1.90 (3)	2.7497 (13)	171 (2)
O8—H8B···O1	0.92 (3)	1.77 (3)	2.6730 (14)	165 (3)
O9—H9A···O2ⁱⁱⁱ	0.87 (3)	2.15 (3)	2.9472 (14)	152 (3)
O9—H9B···O5	0.79 (3)	1.96 (3)	2.7452 (14)	179 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₉N₂⁺·C₄H₅O₆⁻·3H₂O
M_r	384.34
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	90
a, b, c (Å)	7.1163 (14), 12.482 (3), 19.466 (4)
V (Å³)	1729.2 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.42 × 0.21 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.880, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	39094, 3251, 3149
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.737

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.06
No. of reflections	3251
No. of parameters	324
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.18

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O6ⁱ	1.01 (4)	1.45 (4)	2.4554 (12)	174 (4)
O3—H3A···O8ⁱⁱ	0.86 (2)	1.86 (2)	2.6817 (13)	159 (2)
O4—H4A···O9ⁱ	0.81 (3)	1.90 (3)	2.7102 (13)	173 (3)
N2—H2B···O7	0.912 (19)	1.763 (19)	2.6426 (14)	161.3 (18)
O7—H7A···O6ⁱⁱⁱ	0.91 (2)	1.87 (2)	2.7727 (13)	170 (2)
O7—H7B···O5	0.81 (3)	2.02 (3)	2.7141 (14)	144 (3)
O7—H7B···O4	0.81 (3)	2.36 (3)	3.0442 (14)	143 (3)
O8—H8A···O3ⁱ	0.85 (3)	1.90 (3)	2.7497 (13)	171 (2)
O8—H8B···O1	0.92 (3)	1.77 (3)	2.6730 (14)	165 (3)
O9—H9A···O2ⁱⁱⁱ	0.87 (3)	2.15 (3)	2.9472 (14)	152 (3)
O9—H9B···O5	0.79 (3)	1.96 (3)	2.7452 (14)	179 (3)

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

Acknowledgements

MMO thanks the Department of Chemistry, University of California, Davis, for the purchase of the X-ray diffractometer.

References

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