4-(Dimethyl­amino)pyridinium 2-(4-hydroxy­phenyl­diazen­yl)benzoate

Arman, H.D.; Miller, T.; Tiekink, E.R.T.

doi:10.1107/S1600536809050132

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3226

doi:10.1107/S1600536809050132

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4-(Dimethylamino)pyridinium 2-(4-hydroxyphenyldiazenyl)benzoate

Hadi D. Arman,^a Tyler Miller ^a and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 20 November 2009; accepted 21 November 2009; online 28 November 2009)

In the title molecular salt, C₇H₁₁N₂⁺·C₁₃H₉N₂O₃⁻, the dihedral angle between the benzene rings in the anion is 35.14 (8)°. In the crystal, centrosymmetrically related anions associate via hydroxyl–carboxylate O—H⋯O hydrogen bonds, resulting in a 24-membered {⋯OC₃N₂C₄OH}₂ synthon. The cations are associated with this dimeric unit via pyridinium–carboxylate N—H⋯O hydrogen bonds. Weak C—H⋯O links further consolidate the packing, generating layers.

Related literature

For a discussion of co-crystal terminology, see: Zukerman-Schpector & Tiekink (2008 ). For related co-crystallization studies, see: Broker & Tiekink (2007 ); Broker et al. (2008 ); Ellis et al. (2009 ). For related investigations with 2-(4-hydroxyphenylazo)benzoic acid, see: Corlette & Tiekink (2009 ); Arman et al. (2009 ). For hydrogen-bond motifs, see: Etter (1990 ).

Experimental

Crystal data

C₇H₁₁N₂⁺·C₁₃H₉N₂O₃⁻
M_r = 364.40
Monoclinic, P 2₁ /n
a = 9.240 (4) Å
b = 10.924 (4) Å
c = 17.598 (7) Å
β = 92.002 (8)°
V = 1775.2 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 98 K
0.35 × 0.25 × 0.15 mm

Data collection

Rigaku AFC12K/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.769, T_max = 1
12887 measured reflections
4060 independent reflections
3553 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.135
S = 1.12
4060 reflections
252 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3o⋯O2ⁱ	0.84	1.77	2.602 (2)	174
N3—H3n⋯O1	0.88	1.78	2.641 (2)	166
C15—H15⋯O2ⁱⁱ	0.95	2.41	3.300 (3)	157
C19—H19a⋯O3ⁱⁱⁱ	0.98	2.58	2.968 (3)	103
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y, z-1.

Data collection: CrystalClear (Rigaku/MSC, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809050132/hb5243sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050132/hb5243Isup2.hkl

checkCIF report

Comment top

The motivation of our studies into co-crystal formation (Broker & Tiekink, 2007; Broker et al., 2008; Ellis et al., 2009) revolves around a desire to establish a hierarchy of hydrogen bonding interactions (Etter, 1990). Studies with 2-(4-hydroxyphenylazo)benzoic acid reveal the formation of a co-crystal when co-crystallized with N,N'-bis(4-pyridylmethyl)oxamide (Arman et al., 2009) but a salt was formed with 1,2-(4-pyridyl)ethane (Corlette & Tiekink, 2009); see Zukerman-Schpector & Tiekink (2008) for a discussion on terminology.

In (I), proton transfer from the carboxylic acid group in 2-(4-hydroxyphenylazo)benzoic acid to the pyridine-N1 atom has occurred during co-crystallization from a methanol solution containing stoichiometric amounts of the reagents, Figs 1 and 2. The NMe₂ group in the cation is co-planar with the (N3, C14—C18) ring as seen in the C15–C14–N4–C19 torsion angle of -179.04 (17) °. By contrast, the 2-(4-hydroxyphenylazo)benzoate anion is non-planar with the dihedral angle formed between the (C1—C6) and (C8—C13) rings being 35.14 (8) °. There is a twist about the C2–N1 bond as seen in the C1–C2–N1–N2 torsion angle of -148.88 (15) °. Further, the carboxylate group is twisted out of the benzene ring to which it is connected: the C2–C1–C7–O1 torsion angle is -134.83 (17) °. The C7–O1 and C7–O2 bond distances of 1.259 (2) Å and 1.260 (2) Å are indistinguishable, consistent with deprotonation.

The crystal packing in (I) is dominated by O–H···O and N–H···O hydrogen bonding. Centrosymmetrically related anions associate by hydrogen bonds formed between the hydroxyl and O2-carboxylate groups. The association leads to the formation of a 24-membered {···OC₃N₂C₄OH}₂ synthon, Fig. 3. Two cations associate with the dimeric aggregate via pyridinium-N···O1-carboxylate hydrogen bonds, Fig. 3. The resulting four component tectons are linked into effectively flat 2-D arrays in the (100) plane via C–H···O contacts, Table 1 and Fig. 4. Links between layers comprise weaker C–H···O contacts, Table 1, and C–H···π interactions: C20–H20a···Cg(N3,C14—C18)ⁱ = 2.61 Å, C20···Cg(N2, C14—C18)ⁱ = 3.527 (3) Å, with an angle subtended at H20a = 155 °; i: 2 - x, 1 - y, -z.

Related literature top

For discussion on co-crystal terminology, see: Zukerman-Schpector & Tiekink (2008). For related co-crystallization studies, see: Broker & Tiekink (2007); Broker et al. (2008); Ellis et al. (2009). For related investigations with 2-(4-hydroxyphenylazo)benzoic acid, see: Corlette & Tiekink (2009); Arman et al. (2009). For hydrogen-bond motifs, see: Etter (1990).

Experimental top

Orange blocks of (I) were isolated from the co-crystallization of 1:1 molar equivalents of 2-(4-hydroxyphenylazo)benzoic acid and p-dimethylpyridine in a methanol solution.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. Molecular structure of the p-dimethylaminopyridinium cation in (I), showing displacement ellipsoids at the 50% probability level.
	Fig. 2. Molecular structure of the 2-(4-hydroxyphenylazo)benzoate anion in (I), showing displacement ellipsoids at the 50% probability level.
	Fig. 3. A view of a supramolecular dimer mediated by O—H···O hydrogen bonds (orange dashed lines) highlighting the centrosymmetric 24-membered {···OC₃N₂C₄OH}₂ synthon formed between anions, and the attachment of two cations via N—H···O hydrogen bonding (orange dashed lines). Hydrogen atoms not participating in hydrogen bonding are omitted for clarity. Colour code: O, red; N, blue; C, grey; and H, green.
	Fig. 4. A view of the layer in (I) in which the aggregates shown in Fig. 3 are linked via C–H···O contacts (green dashed lines). Hydrogen atoms not participating in intermolecular interactions are omitted for clarity. Colour code: O, red; N, blue; C, grey; and H, green.

4-(Dimethylamino)pyridinium 2-(4-hydroxyphenyldiazenyl)benzoate top

Crystal data top

C₇H₁₁N₂⁺·C₁₃H₉N₂O₃⁻	F(000) = 768
M_r = 364.40	D_x = 1.363 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 7530 reflections
a = 9.240 (4) Å	θ = 2.2–40.7°
b = 10.924 (4) Å	µ = 0.09 mm⁻¹
c = 17.598 (7) Å	T = 98 K
β = 92.002 (8)°	Block, orange
V = 1775.2 (12) Å³	0.35 × 0.25 × 0.15 mm
Z = 4

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	4060 independent reflections
Radiation source: fine-focus sealed tube	3553 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→12
T_min = 0.769, T_max = 1	k = −14→14
12887 measured reflections	l = −20→22

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0531P)² + 0.902P] where P = (F_o² + 2F_c²)/3
4060 reflections	(Δ/σ)_max < 0.001
252 parameters	Δρ_max = 0.33 e Å⁻³
2 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₇H₁₁N₂⁺·C₁₃H₉N₂O₃⁻	V = 1775.2 (12) Å³
M_r = 364.40	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.240 (4) Å	µ = 0.09 mm⁻¹
b = 10.924 (4) Å	T = 98 K
c = 17.598 (7) Å	0.35 × 0.25 × 0.15 mm
β = 92.002 (8)°

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	4060 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3553 reflections with I > 2σ(I)
T_min = 0.769, T_max = 1	R_int = 0.046
12887 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	2 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.12	Δρ_max = 0.33 e Å⁻³
4060 reflections	Δρ_min = −0.32 e Å⁻³
252 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	0.52078 (13)	0.70075 (11)	0.20136 (6)	0.0231 (3)
O2	0.51014 (13)	0.74136 (12)	0.32532 (6)	0.0248 (3)
O3	0.72197 (13)	0.39214 (12)	0.69176 (7)	0.0252 (3)
H3O	0.6507	0.3446	0.6871	0.038*
N1	0.79272 (15)	0.65156 (12)	0.37743 (8)	0.0198 (3)
N2	0.86170 (15)	0.66758 (13)	0.43984 (8)	0.0213 (3)
N3	0.65513 (17)	0.60354 (14)	0.08591 (8)	0.0244 (3)
H3N	0.6072	0.6460	0.1193	0.029*
N4	0.86335 (17)	0.38316 (14)	−0.06666 (8)	0.0253 (3)
C1	0.73363 (18)	0.77410 (15)	0.26482 (9)	0.0186 (3)
C2	0.83605 (18)	0.73634 (14)	0.32047 (9)	0.0187 (3)
C3	0.97934 (18)	0.77841 (15)	0.31800 (9)	0.0210 (3)
H3	1.0502	0.7485	0.3537	0.025*
C4	1.01826 (19)	0.86322 (16)	0.26387 (9)	0.0229 (4)
H4	1.1151	0.8924	0.2631	0.028*
C5	0.91532 (19)	0.90559 (16)	0.21068 (9)	0.0228 (4)
H5	0.9406	0.9662	0.1748	0.027*
C6	0.77532 (18)	0.85902 (15)	0.21011 (9)	0.0206 (3)
H6	0.7068	0.8852	0.1720	0.025*
C7	0.57669 (18)	0.73456 (14)	0.26416 (9)	0.0183 (3)
C8	0.82313 (18)	0.58820 (15)	0.49950 (9)	0.0200 (3)
C9	0.8914 (2)	0.61107 (19)	0.56988 (10)	0.0318 (4)
H9	0.9628	0.6736	0.5741	0.038*
C10	0.8577 (2)	0.5449 (2)	0.63363 (10)	0.0331 (5)
H10	0.9058	0.5618	0.6811	0.040*
C11	0.75306 (18)	0.45340 (15)	0.62834 (9)	0.0204 (3)
C12	0.6840 (2)	0.42969 (16)	0.55792 (10)	0.0248 (4)
H12	0.6124	0.3674	0.5538	0.030*
C13	0.7188 (2)	0.49608 (16)	0.49430 (9)	0.0244 (4)
H13	0.6715	0.4789	0.4467	0.029*
C14	0.79702 (18)	0.45414 (15)	−0.01652 (9)	0.0213 (3)
C15	0.82162 (19)	0.44292 (16)	0.06333 (9)	0.0230 (3)
H15	0.8879	0.3836	0.0832	0.028*
C16	0.7501 (2)	0.51729 (16)	0.11111 (10)	0.0249 (4)
H16	0.7675	0.5084	0.1644	0.030*
C17	0.6284 (2)	0.61699 (17)	0.01041 (10)	0.0261 (4)
H17	0.5608	0.6771	−0.0071	0.031*
C18	0.6963 (2)	0.54610 (17)	−0.04107 (10)	0.0255 (4)
H18	0.6764	0.5580	−0.0939	0.031*
C19	0.8367 (2)	0.39889 (19)	−0.14862 (10)	0.0307 (4)
H19A	0.7346	0.3821	−0.1615	0.046*
H19B	0.8978	0.3419	−0.1762	0.046*
H19C	0.8599	0.4831	−0.1630	0.046*
C20	0.9618 (2)	0.28541 (17)	−0.04192 (11)	0.0289 (4)
H20A	1.0554	0.3207	−0.0258	0.043*
H20B	0.9755	0.2285	−0.0841	0.043*
H20C	0.9207	0.2414	0.0008	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0229 (6)	0.0285 (6)	0.0177 (5)	−0.0021 (5)	−0.0007 (4)	−0.0009 (5)
O2	0.0268 (6)	0.0295 (7)	0.0182 (6)	−0.0064 (5)	0.0033 (5)	−0.0022 (5)
O3	0.0237 (6)	0.0323 (7)	0.0196 (6)	−0.0071 (5)	−0.0010 (5)	0.0071 (5)
N1	0.0228 (7)	0.0189 (7)	0.0177 (6)	0.0007 (5)	0.0005 (5)	0.0003 (5)
N2	0.0226 (7)	0.0223 (7)	0.0189 (7)	−0.0005 (5)	−0.0002 (5)	0.0014 (6)
N3	0.0289 (8)	0.0249 (7)	0.0194 (7)	−0.0001 (6)	0.0029 (6)	−0.0015 (6)
N4	0.0280 (8)	0.0263 (8)	0.0214 (7)	0.0064 (6)	−0.0031 (6)	−0.0024 (6)
C1	0.0226 (8)	0.0186 (7)	0.0145 (7)	−0.0009 (6)	0.0008 (6)	−0.0018 (6)
C2	0.0233 (8)	0.0170 (7)	0.0157 (7)	−0.0012 (6)	0.0013 (6)	−0.0017 (6)
C3	0.0224 (8)	0.0226 (8)	0.0181 (7)	−0.0001 (6)	0.0002 (6)	−0.0014 (6)
C4	0.0222 (8)	0.0256 (8)	0.0210 (8)	−0.0043 (7)	0.0017 (6)	−0.0031 (7)
C5	0.0288 (9)	0.0234 (8)	0.0163 (7)	−0.0045 (7)	0.0030 (6)	0.0005 (6)
C6	0.0251 (8)	0.0219 (8)	0.0146 (7)	−0.0021 (6)	−0.0009 (6)	0.0003 (6)
C7	0.0213 (8)	0.0167 (7)	0.0167 (7)	−0.0001 (6)	0.0006 (6)	0.0014 (6)
C8	0.0216 (8)	0.0202 (8)	0.0183 (8)	0.0001 (6)	0.0007 (6)	0.0013 (6)
C9	0.0311 (10)	0.0398 (11)	0.0241 (9)	−0.0168 (8)	−0.0049 (7)	0.0059 (8)
C10	0.0337 (10)	0.0447 (11)	0.0204 (8)	−0.0158 (9)	−0.0081 (7)	0.0069 (8)
C11	0.0204 (8)	0.0226 (8)	0.0182 (7)	0.0010 (6)	0.0013 (6)	0.0037 (6)
C12	0.0306 (9)	0.0229 (8)	0.0208 (8)	−0.0084 (7)	−0.0021 (7)	0.0005 (7)
C13	0.0314 (9)	0.0244 (8)	0.0171 (8)	−0.0051 (7)	−0.0037 (7)	0.0001 (7)
C14	0.0232 (8)	0.0193 (8)	0.0211 (8)	−0.0010 (6)	−0.0005 (6)	0.0011 (6)
C15	0.0262 (9)	0.0216 (8)	0.0211 (8)	−0.0017 (6)	−0.0015 (6)	0.0049 (7)
C16	0.0299 (9)	0.0256 (8)	0.0192 (8)	−0.0036 (7)	−0.0008 (7)	0.0035 (7)
C17	0.0285 (9)	0.0263 (9)	0.0234 (8)	0.0040 (7)	−0.0013 (7)	0.0019 (7)
C18	0.0297 (9)	0.0294 (9)	0.0172 (8)	0.0063 (7)	−0.0020 (7)	0.0008 (7)
C19	0.0348 (10)	0.0374 (10)	0.0200 (8)	0.0098 (8)	0.0000 (7)	−0.0036 (8)
C20	0.0311 (10)	0.0230 (8)	0.0325 (9)	0.0077 (7)	−0.0005 (7)	−0.0013 (8)

Geometric parameters (Å, º) top

O1—C7	1.259 (2)	C8—C9	1.393 (2)
O2—C7	1.260 (2)	C8—C13	1.394 (2)
O3—C11	1.341 (2)	C9—C10	1.379 (3)
O3—H3O	0.8401	C9—H9	0.9500
N1—N2	1.263 (2)	C10—C11	1.392 (2)
N1—C2	1.432 (2)	C10—H10	0.9500
N2—C8	1.417 (2)	C11—C12	1.398 (2)
N3—C17	1.351 (2)	C12—C13	1.381 (2)
N3—C16	1.352 (2)	C12—H12	0.9500
N3—H3N	0.8801	C13—H13	0.9500
N4—C14	1.339 (2)	C14—C15	1.421 (2)
N4—C20	1.459 (2)	C14—C18	1.426 (2)
N4—C19	1.465 (2)	C15—C16	1.358 (3)
C1—C2	1.400 (2)	C15—H15	0.9500
C1—C6	1.401 (2)	C16—H16	0.9500
C1—C7	1.513 (2)	C17—C18	1.362 (2)
C2—C3	1.404 (2)	C17—H17	0.9500
C3—C4	1.385 (2)	C18—H18	0.9500
C3—H3	0.9500	C19—H19A	0.9800
C4—C5	1.390 (2)	C19—H19B	0.9800
C4—H4	0.9500	C19—H19C	0.9800
C5—C6	1.390 (2)	C20—H20A	0.9800
C5—H5	0.9500	C20—H20B	0.9800
C6—H6	0.9500	C20—H20C	0.9800

C11—O3—H3O	114.6	C11—C10—H10	120.1
N2—N1—C2	111.98 (14)	O3—C11—C10	118.12 (15)
N1—N2—C8	115.30 (14)	O3—C11—C12	122.74 (16)
C17—N3—C16	119.54 (15)	C10—C11—C12	119.15 (15)
C17—N3—H3N	121.3	C13—C12—C11	120.58 (16)
C16—N3—H3N	119.0	C13—C12—H12	119.7
C14—N4—C20	121.47 (15)	C11—C12—H12	119.7
C14—N4—C19	121.06 (15)	C12—C13—C8	120.40 (16)
C20—N4—C19	117.45 (15)	C12—C13—H13	119.8
C2—C1—C6	118.72 (15)	C8—C13—H13	119.8
C2—C1—C7	123.06 (14)	N4—C14—C15	122.72 (16)
C6—C1—C7	118.07 (14)	N4—C14—C18	121.14 (15)
C1—C2—C3	119.81 (15)	C15—C14—C18	116.14 (15)
C1—C2—N1	118.78 (15)	C16—C15—C14	119.77 (16)
C3—C2—N1	121.37 (15)	C16—C15—H15	120.1
C4—C3—C2	120.54 (16)	C14—C15—H15	120.1
C4—C3—H3	119.7	N3—C16—C15	122.57 (16)
C2—C3—H3	119.7	N3—C16—H16	118.7
C3—C4—C5	119.84 (16)	C15—C16—H16	118.7
C3—C4—H4	120.1	N3—C17—C18	121.32 (16)
C5—C4—H4	120.1	N3—C17—H17	119.3
C6—C5—C4	119.85 (16)	C18—C17—H17	119.3
C6—C5—H5	120.1	C17—C18—C14	120.67 (16)
C4—C5—H5	120.1	C17—C18—H18	119.7
C5—C6—C1	121.05 (15)	C14—C18—H18	119.7
C5—C6—H6	119.5	N4—C19—H19A	109.5
C1—C6—H6	119.5	N4—C19—H19B	109.5
O1—C7—O2	124.71 (16)	H19A—C19—H19B	109.5
O1—C7—C1	117.02 (14)	N4—C19—H19C	109.5
O2—C7—C1	118.22 (14)	H19A—C19—H19C	109.5
C9—C8—C13	118.59 (16)	H19B—C19—H19C	109.5
C9—C8—N2	115.54 (15)	N4—C20—H20A	109.5
C13—C8—N2	125.76 (15)	N4—C20—H20B	109.5
C10—C9—C8	121.40 (17)	H20A—C20—H20B	109.5
C10—C9—H9	119.3	N4—C20—H20C	109.5
C8—C9—H9	119.3	H20A—C20—H20C	109.5
C9—C10—C11	119.87 (17)	H20B—C20—H20C	109.5
C9—C10—H10	120.1

C2—N1—N2—C8	179.04 (13)	N2—C8—C9—C10	176.36 (19)
C6—C1—C2—C3	−3.6 (2)	C8—C9—C10—C11	−0.2 (3)
C7—C1—C2—C3	−179.01 (15)	C9—C10—C11—O3	−179.18 (18)
C6—C1—C2—N1	178.65 (14)	C9—C10—C11—C12	0.2 (3)
C7—C1—C2—N1	3.2 (2)	O3—C11—C12—C13	179.40 (17)
N2—N1—C2—C1	−148.88 (15)	C10—C11—C12—C13	0.0 (3)
N2—N1—C2—C3	33.4 (2)	C11—C12—C13—C8	−0.3 (3)
C1—C2—C3—C4	4.2 (2)	C9—C8—C13—C12	0.3 (3)
N1—C2—C3—C4	−178.05 (15)	N2—C8—C13—C12	−175.72 (17)
C2—C3—C4—C5	−1.1 (2)	C20—N4—C14—C15	2.5 (3)
C3—C4—C5—C6	−2.6 (3)	C19—N4—C14—C15	−179.04 (17)
C4—C5—C6—C1	3.2 (3)	C20—N4—C14—C18	−177.34 (17)
C2—C1—C6—C5	−0.1 (2)	C19—N4—C14—C18	1.1 (3)
C7—C1—C6—C5	175.56 (15)	N4—C14—C15—C16	−179.58 (17)
C2—C1—C7—O1	−134.83 (17)	C18—C14—C15—C16	0.3 (2)
C6—C1—C7—O1	49.7 (2)	C17—N3—C16—C15	0.4 (3)
C2—C1—C7—O2	47.4 (2)	C14—C15—C16—N3	−0.3 (3)
C6—C1—C7—O2	−128.09 (17)	C16—N3—C17—C18	−0.6 (3)
N1—N2—C8—C9	−175.62 (16)	N3—C17—C18—C14	0.7 (3)
N1—N2—C8—C13	0.5 (2)	N4—C14—C18—C17	179.35 (17)
C13—C8—C9—C10	−0.1 (3)	C15—C14—C18—C17	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3o···O2ⁱ	0.84	1.77	2.602 (2)	174
N3—H3n···O1	0.88	1.78	2.641 (2)	166
C15—H15···O2ⁱⁱ	0.95	2.41	3.300 (3)	157
C19—H19a···O3ⁱⁱⁱ	0.98	2.58	2.968 (3)	103

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

Experimental details

Crystal data
Chemical formula	C₇H₁₁N₂⁺·C₁₃H₉N₂O₃⁻
M_r	364.40
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	98
a, b, c (Å)	9.240 (4), 10.924 (4), 17.598 (7)
β (°)	92.002 (8)
V (Å³)	1775.2 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.35 × 0.25 × 0.15

Data collection
Diffractometer	Rigaku AFC12K/SATURN724 diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.769, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	12887, 4060, 3553
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.135, 1.12
No. of reflections	4060
No. of parameters	252
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.32

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3o···O2ⁱ	0.84	1.77	2.602 (2)	174
N3—H3n···O1	0.88	1.78	2.641 (2)	166
C15—H15···O2ⁱⁱ	0.95	2.41	3.300 (3)	157
C19—H19a···O3ⁱⁱⁱ	0.98	2.58	2.968 (3)	103

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

References

Arman, H. D., Miller, T., Poplaukhin, P. & Tiekink, E. R. T. (2009). Acta Cryst. E65, o3178–o3179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Broker, G. A., Bettens, R. P. A. & Tiekink, E. R. T. (2008). CrystEngComm, 10, 879–887. Web of Science CSD CrossRef CAS Google Scholar
Broker, G. A. & Tiekink, E. R. T. (2007). CrystEngComm, 9, 1096–1109. Web of Science CSD CrossRef CAS Google Scholar
Corlette, E. M. & Tiekink, E. R. T. (2009). J. Chem. Crystallogr. 39, 603–606. Web of Science CSD CrossRef CAS Google Scholar
Ellis, C. A., Miller, M. A., Spencer, J., Zukerman-Schpector, J. & Tiekink, E. R. T. (2009). CrystEngComm, 11, 1352–1361. Web of Science CSD CrossRef CAS Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar
Zukerman-Schpector, J. & Tiekink, E. R. T. (2008). Z. Kristallogr. 223, 233–234. Web of Science CrossRef CAS Google Scholar

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Volume 65| Part 12| December 2009| Page o3226

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