1,4-Bis(4-pyridylmeth­yl)piperazin-1-ium perchlorate fumaric acid hemisolvate

Farnum, G.A.; LaDuca, R.L.

doi:10.1107/S1600536809026026

organic compounds

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Volume 65| Part 8| August 2009| Page o1817

doi:10.1107/S1600536809026026

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1,4-Bis(4-pyridylmethyl)piperazin-1-ium perchlorate fumaric acid hemisolvate

Gregory A. Farnum ^a and Robert L. LaDuca ^a ^*

^aLyman Briggs College, Department of Chemistry, Michigan State University, East Lansing, MI 48825, USA
^*Correspondence e-mail: laduca@msu.edu

(Received 29 June 2009; accepted 4 July 2009; online 11 July 2009)

In the title salt, C₁₆H₂₁N₄⁺·ClO₄⁻·0.5C₄H₄O₄, fumaric acid molecules, situated across crystallographic inversion centres, are O—H⋯N hydrogen bonded to two protonated 1,4-bis(4-pyridylmethyl)piperazine cations, forming trimolecular units. These construct one-dimensional supramolecular ribbons by N—H⋯N hydrogen bonding, and further aggregate via π–π interactions [shortest C⋯C contact = 3.640 (1) Å] and perchlorate-mediated C—H⋯O interactions.

Related literature

For the preparation of bis(4-pyridylmethyl)piperazine, see: Pocic et al. (2005 ). For a cadmium fumarate coordination polymer containing bis(4-pyridylmethyl)piperazine, see: Martin et al. (2009 ).

Experimental

Crystal data

C₁₆H₂₁N₄⁺·ClO₄⁻·0.5C₄H₄O₄
M_r = 426.85
Triclinic, $[P \overline 1]$
a = 7.7287 (9) Å
b = 9.6415 (11) Å
c = 14.3440 (17) Å
α = 88.691 (2)°
β = 83.785 (2)°
γ = 66.749 (2)°
V = 976.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 173 K
0.41 × 0.21 × 0.13 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.908, T_max = 0.969
14571 measured reflections
3593 independent reflections
3178 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.092
S = 1.05
3593 reflections
268 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯N4ⁱ	0.925 (19)	1.884 (19)	2.8067 (19)	175.0 (17)
O1—H1A⋯N1ⁱⁱ	0.93 (2)	1.68 (2)	2.6081 (19)	178 (2)
C10—H10A⋯O3ⁱⁱⁱ	0.99	2.37	3.281 (2)	153 (2)
C12—H12⋯O6^iv	0.95	2.49	3.138 (3)	126 (2)
Symmetry codes: (i) x-1, y, z; (ii) x, y+1, z; (iii) x-1, y+1, z; (iv) -x+2, -y+1, -z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2005 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026026/tk2492sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026026/tk2492Isup2.hkl

checkCIF report

Comment top

The title compound (I) was prepared during an attempt to prepare a divalent Cd coordination polymer containing both fumarate and N,N'-di(4-pyridyl- methyl)piperazine (bpmp) ligands. The coordination polymer [Cd(fumarate)(bpmp)(H₂O)₂]_n could only be prepared by using maleic acid, which underwent in situ cis-trans isomerization (Martin et al., 2009).

The asymmetric unit of the title compound (Fig. 1) consists of one bpmp molecule protonated at one of its piperazinyl-N atoms, one perchlorate anion, and one-half of a fumaric acid molecule situated across a crystallographic inversion centre. Hydrogen-bonding between the carboxylic acid functional groups of the fumaric acid molecules and pyridyl-N atoms within the Hbpmp⁺ moieties produces dicationic [(Hbpmp)₂(H₂fumarate)]²⁺ trimolecular aggregations (Fig. 2 & Table 1).

The [(Hbpmp)₂(H₂fumarate)]²⁺ units construct one-dimensional ribbon motifs (Fig. 3) by means of N—H···N hydrogen-bonding between the protonated piperazinyl-N atoms and pyridyl-N atoms. Individual ribbons aggregate into a 2-D supramolecular layer through C—H···O interactions mediated by the perchlorate anions (Table 1). Neighbouring layers stack into the 3-D crystal structure (Fig. 4) by π-π interactions between pyridyl rings. (Cg—Cg(-x + 1,-y + 2,-z) with distance = 3.640 (1) Å).

Related literature top

For the preparation of bis(4-pyridylmethyl)piperazine, see: Pocic et al. (2005). For a cadmium fumarate coordination polymer containing bis(4-pyridylmethyl)piperazine, see: Martin et al. (2009).

Experimental top

Cadmium perchlorate hexahydrate and fumaric acid were obtained commercially. N,N'-Di(4-pyridylmethyl)piperazine (bpmp) was prepared via a published procedure (Pocic et al., 2005). Cadmium perchlorate hexahydrate (0.0175 g, 0.0562 mmol) and fumaric acid (0.0065 g, 0.056 mmol) were placed in water (1.5 ml) in a glass vial along with 1.0 M NaOH (0.2 ml). This solution was heated to 373 K to dissolve the fumaric acid. An aliquot (0.75 ml) of a 1:1 water:ethanol solution was carefully layered on top. Then 0.075 M ethanolic solution (1.5 ml) of bpmp (0.11 mmol) was carefully layered on top. Colourless blocks of (I) were deposited after standing for one week at 293 K.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Asymmetric unit of (I), showing 50% probability ellipsoids and atom numbering scheme. Hydrogen atoms positions are marked as gray sticks. A complete fumaric acid moiety is shown. Symmetry code: i -x + 1, -y + 1, -z + 1.
	Fig. 2. A [(Hbpmp)₂(H₂fumarate)]²⁺ trimolecular aggregration in (I). Hydrogen bonding is shown as dashed lines.
	Fig. 3. A hydrogen-bonded ribbon motif consisting of [(Hbpmp)₂(H₂fumarate)]²⁺ trimolecular aggregration. Hydrogen bonding is shown as dashed lines.
	Fig. 4. Packing diagram for (I).

Bis[1,4-bis(4-pyridylmethyl)piperazin-1-ium] bis(perchlorate) fumaric acid solvate top

Crystal data top

C₁₆H₂₁N₄⁺·ClO₄⁻·0.5C₄H₄O₄	Z = 2
M_r = 426.85	F(000) = 448
Triclinic, P1	D_x = 1.452 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7287 (9) Å	Cell parameters from 14571 reflections
b = 9.6415 (11) Å	θ = 2.3–25.4°
c = 14.3440 (17) Å	µ = 0.24 mm⁻¹
α = 88.691 (2)°	T = 173 K
β = 83.785 (2)°	Block, colourless
γ = 66.749 (2)°	0.41 × 0.21 × 0.13 mm
V = 976.0 (2) Å³

Data collection top

Bruker APEXII diffractometer	3593 independent reflections
Radiation source: fine-focus sealed tube	3178 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω–ψ scans	θ_max = 25.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.908, T_max = 0.969	k = −11→11
14571 measured reflections	l = −17→17

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0395P)² + 0.5777P] where P = (F_o² + 2F_c²)/3
3593 reflections	(Δ/σ)_max < 0.001
268 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₆H₂₁N₄⁺·ClO₄⁻·0.5C₄H₄O₄	γ = 66.749 (2)°
M_r = 426.85	V = 976.0 (2) Å³
Triclinic, P1	Z = 2
a = 7.7287 (9) Å	Mo Kα radiation
b = 9.6415 (11) Å	µ = 0.24 mm⁻¹
c = 14.3440 (17) Å	T = 173 K
α = 88.691 (2)°	0.41 × 0.21 × 0.13 mm
β = 83.785 (2)°

Data collection top

Bruker APEXII diffractometer	3593 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3178 reflections with I > 2σ(I)
T_min = 0.908, T_max = 0.969	R_int = 0.031
14571 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.36 e Å⁻³
3593 reflections	Δρ_min = −0.38 e Å⁻³
268 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.

Supramolecular interactions were calculated using PLATON (Spek, 2009).

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
N2	0.14315 (19)	0.60021 (15)	0.29972 (9)	0.0221 (3)
N3	0.12885 (19)	0.80520 (15)	0.14915 (9)	0.0195 (3)
H3N	0.005 (3)	0.828 (2)	0.1385 (13)	0.023*
C7	0.1416 (2)	0.55727 (19)	0.20264 (12)	0.0251 (4)
H7A	0.0094	0.5841	0.1892	0.030*
H7B	0.2108	0.4467	0.1936	0.030*
N1	0.3877 (2)	0.04563 (16)	0.39116 (10)	0.0283 (3)
C2	0.0899 (3)	0.2558 (2)	0.39796 (12)	0.0284 (4)
H2	−0.0442	0.2929	0.4102	0.034*
C10	0.1253 (2)	0.84885 (18)	0.24896 (11)	0.0226 (3)
H10A	0.0515	0.9588	0.2586	0.027*
H10B	0.2561	0.8254	0.2637	0.027*
C8	0.2342 (2)	0.63786 (18)	0.13586 (12)	0.0241 (4)
H8A	0.3676	0.6088	0.1480	0.029*
H8B	0.2333	0.6081	0.0704	0.029*
C3	0.1772 (2)	0.35304 (18)	0.36903 (11)	0.0234 (4)
N4	0.76043 (19)	0.86552 (17)	0.10634 (10)	0.0261 (3)
C11	0.1980 (2)	0.89600 (18)	0.07906 (12)	0.0224 (3)
H11A	0.1951	0.8615	0.0150	0.027*
H11B	0.1099	1.0034	0.0862	0.027*
C9	0.0361 (2)	0.76287 (18)	0.31339 (12)	0.0238 (4)
H9A	0.0339	0.7917	0.3794	0.029*
H9B	−0.0962	0.7896	0.3002	0.029*
C4	0.3730 (2)	0.29139 (19)	0.34948 (11)	0.0244 (4)
H4	0.4382	0.3534	0.3280	0.029*
C15	0.4238 (2)	0.99776 (19)	0.13418 (12)	0.0249 (4)
H15	0.3188	1.0839	0.1600	0.030*
C16	0.6071 (2)	0.9846 (2)	0.14065 (12)	0.0268 (4)
H16	0.6248	1.0639	0.1709	0.032*
C5	0.4719 (3)	0.13881 (19)	0.36167 (12)	0.0273 (4)
H5	0.6060	0.0981	0.3485	0.033*
C14	0.3955 (2)	0.88367 (18)	0.08945 (11)	0.0202 (3)
C6	0.0591 (2)	0.51999 (19)	0.36533 (13)	0.0282 (4)
H6A	−0.0668	0.5346	0.3472	0.034*
H6B	0.0398	0.5652	0.4289	0.034*
C1	0.1992 (3)	0.1050 (2)	0.40882 (12)	0.0300 (4)
H1	0.1375	0.0403	0.4298	0.036*
C12	0.7322 (2)	0.7561 (2)	0.06285 (12)	0.0261 (4)
H12	0.8397	0.6706	0.0383	0.031*
O1	0.55138 (19)	0.75287 (15)	0.40307 (10)	0.0365 (3)
H1A	0.496 (3)	0.857 (3)	0.3980 (15)	0.044*
C17	0.4406 (2)	0.70070 (19)	0.45469 (12)	0.0261 (4)
Cl1	0.78159 (6)	0.33434 (5)	0.16421 (3)	0.02773 (13)
O5	0.7247 (2)	0.45702 (18)	0.22864 (11)	0.0539 (4)
O6	0.9359 (3)	0.3305 (3)	0.10017 (15)	0.0877 (7)
C18	0.5308 (2)	0.53460 (19)	0.46587 (13)	0.0281 (4)
H18	0.6356	0.4764	0.4228	0.034*
O2	0.28278 (17)	0.77780 (14)	0.49090 (10)	0.0342 (3)
O3	0.8334 (3)	0.19613 (18)	0.21367 (14)	0.0673 (5)
O4	0.6259 (2)	0.34683 (18)	0.11388 (11)	0.0555 (4)
C13	0.5544 (2)	0.76136 (19)	0.05197 (12)	0.0243 (4)
H13	0.5408	0.6823	0.0192	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0246 (7)	0.0196 (7)	0.0218 (7)	−0.0091 (6)	−0.0001 (6)	0.0040 (5)
N3	0.0152 (6)	0.0221 (7)	0.0233 (7)	−0.0091 (6)	−0.0048 (5)	0.0053 (5)
C7	0.0299 (9)	0.0217 (8)	0.0265 (9)	−0.0128 (7)	−0.0051 (7)	0.0032 (7)
N1	0.0347 (8)	0.0221 (7)	0.0273 (8)	−0.0110 (6)	−0.0015 (6)	0.0027 (6)
C2	0.0277 (9)	0.0285 (9)	0.0300 (9)	−0.0131 (7)	0.0002 (7)	0.0046 (7)
C10	0.0253 (8)	0.0197 (8)	0.0240 (8)	−0.0097 (7)	−0.0050 (7)	0.0023 (6)
C8	0.0258 (9)	0.0217 (8)	0.0236 (8)	−0.0083 (7)	−0.0022 (7)	0.0011 (6)
C3	0.0288 (9)	0.0235 (8)	0.0187 (8)	−0.0118 (7)	−0.0010 (7)	0.0033 (6)
N4	0.0213 (7)	0.0348 (8)	0.0265 (7)	−0.0152 (6)	−0.0046 (6)	0.0054 (6)
C11	0.0182 (8)	0.0253 (8)	0.0252 (8)	−0.0097 (7)	−0.0055 (6)	0.0093 (7)
C9	0.0233 (8)	0.0220 (8)	0.0242 (8)	−0.0077 (7)	0.0001 (7)	0.0022 (7)
C4	0.0286 (9)	0.0251 (9)	0.0229 (8)	−0.0147 (7)	−0.0011 (7)	0.0020 (7)
C15	0.0222 (8)	0.0239 (8)	0.0288 (9)	−0.0102 (7)	0.0002 (7)	0.0022 (7)
C16	0.0285 (9)	0.0305 (9)	0.0277 (9)	−0.0185 (8)	−0.0032 (7)	0.0021 (7)
C5	0.0270 (9)	0.0264 (9)	0.0277 (9)	−0.0101 (7)	−0.0019 (7)	0.0014 (7)
C14	0.0184 (8)	0.0242 (8)	0.0201 (8)	−0.0105 (7)	−0.0044 (6)	0.0084 (6)
C6	0.0271 (9)	0.0245 (9)	0.0298 (9)	−0.0091 (7)	0.0051 (7)	0.0054 (7)
C1	0.0371 (10)	0.0262 (9)	0.0317 (9)	−0.0183 (8)	−0.0017 (8)	0.0048 (7)
C12	0.0195 (8)	0.0299 (9)	0.0273 (9)	−0.0088 (7)	−0.0007 (7)	0.0019 (7)
O1	0.0351 (7)	0.0220 (7)	0.0471 (8)	−0.0093 (6)	0.0085 (6)	0.0065 (6)
C17	0.0285 (9)	0.0253 (9)	0.0269 (9)	−0.0127 (7)	−0.0054 (7)	0.0042 (7)
Cl1	0.0276 (2)	0.0264 (2)	0.0286 (2)	−0.01057 (17)	0.00035 (17)	−0.00359 (17)
O5	0.0618 (10)	0.0491 (9)	0.0518 (9)	−0.0238 (8)	0.0021 (8)	−0.0249 (7)
O6	0.0777 (14)	0.1239 (18)	0.0735 (13)	−0.0640 (14)	0.0431 (11)	−0.0279 (12)
C18	0.0270 (9)	0.0237 (9)	0.0335 (9)	−0.0101 (7)	−0.0030 (7)	0.0012 (7)
O2	0.0263 (7)	0.0255 (7)	0.0473 (8)	−0.0082 (5)	0.0007 (6)	0.0072 (6)
O3	0.0694 (12)	0.0396 (9)	0.0948 (14)	−0.0176 (8)	−0.0373 (10)	0.0257 (9)
O4	0.0474 (9)	0.0555 (10)	0.0560 (10)	−0.0064 (8)	−0.0259 (8)	−0.0122 (8)
C13	0.0228 (8)	0.0276 (9)	0.0252 (9)	−0.0127 (7)	−0.0032 (7)	0.0011 (7)

Geometric parameters (Å, º) top

N2—C6	1.462 (2)	C9—H9A	0.9900
N2—C9	1.462 (2)	C9—H9B	0.9900
N2—C7	1.464 (2)	C4—C5	1.382 (2)
N3—C10	1.496 (2)	C4—H4	0.9500
N3—C8	1.499 (2)	C15—C16	1.385 (2)
N3—C11	1.5082 (19)	C15—C14	1.386 (2)
N3—H3N	0.925 (19)	C15—H15	0.9500
C7—C8	1.513 (2)	C16—H16	0.9500
C7—H7A	0.9900	C5—H5	0.9500
C7—H7B	0.9900	C14—C13	1.389 (2)
N1—C1	1.336 (2)	C6—H6A	0.9900
N1—C5	1.340 (2)	C6—H6B	0.9900
C2—C1	1.379 (2)	C1—H1	0.9500
C2—C3	1.388 (2)	C12—C13	1.381 (2)
C2—H2	0.9500	C12—H12	0.9500
C10—C9	1.515 (2)	O1—C17	1.312 (2)
C10—H10A	0.9900	O1—H1A	0.93 (2)
C10—H10B	0.9900	C17—O2	1.214 (2)
C8—H8A	0.9900	C17—C18	1.486 (2)
C8—H8B	0.9900	Cl1—O6	1.4129 (17)
C3—C4	1.388 (2)	Cl1—O5	1.4135 (14)
C3—C6	1.508 (2)	Cl1—O3	1.4271 (16)
N4—C16	1.338 (2)	Cl1—O4	1.4329 (15)
N4—C12	1.339 (2)	C18—C18ⁱ	1.323 (4)
C11—C14	1.507 (2)	C18—H18	0.9500
C11—H11A	0.9900	C13—H13	0.9500
C11—H11B	0.9900

C6—N2—C9	109.37 (13)	C10—C9—H9B	109.6
C6—N2—C7	110.81 (13)	H9A—C9—H9B	108.1
C9—N2—C7	109.43 (13)	C5—C4—C3	119.24 (15)
C10—N3—C8	109.52 (12)	C5—C4—H4	120.4
C10—N3—C11	113.55 (12)	C3—C4—H4	120.4
C8—N3—C11	113.77 (13)	C16—C15—C14	119.15 (16)
C10—N3—H3N	107.0 (11)	C16—C15—H15	120.4
C8—N3—H3N	107.2 (11)	C14—C15—H15	120.4
C11—N3—H3N	105.2 (11)	N4—C16—C15	123.15 (16)
N2—C7—C8	110.08 (13)	N4—C16—H16	118.4
N2—C7—H7A	109.6	C15—C16—H16	118.4
C8—C7—H7A	109.6	N1—C5—C4	123.06 (16)
N2—C7—H7B	109.6	N1—C5—H5	118.5
C8—C7—H7B	109.6	C4—C5—H5	118.5
H7A—C7—H7B	108.2	C15—C14—C13	117.85 (15)
C1—N1—C5	117.52 (15)	C15—C14—C11	120.58 (15)
C1—C2—C3	119.45 (17)	C13—C14—C11	121.53 (15)
C1—C2—H2	120.3	N2—C6—C3	113.82 (14)
C3—C2—H2	120.3	N2—C6—H6A	108.8
N3—C10—C9	109.59 (13)	C3—C6—H6A	108.8
N3—C10—H10A	109.8	N2—C6—H6B	108.8
C9—C10—H10A	109.8	C3—C6—H6B	108.8
N3—C10—H10B	109.8	H6A—C6—H6B	107.7
C9—C10—H10B	109.8	N1—C1—C2	123.08 (16)
H10A—C10—H10B	108.2	N1—C1—H1	118.5
N3—C8—C7	109.62 (13)	C2—C1—H1	118.5
N3—C8—H8A	109.7	N4—C12—C13	123.18 (16)
C7—C8—H8A	109.7	N4—C12—H12	118.4
N3—C8—H8B	109.7	C13—C12—H12	118.4
C7—C8—H8B	109.7	C17—O1—H1A	112.1 (14)
H8A—C8—H8B	108.2	O2—C17—O1	124.70 (16)
C4—C3—C2	117.62 (16)	O2—C17—C18	122.91 (16)
C4—C3—C6	122.93 (15)	O1—C17—C18	112.39 (15)
C2—C3—C6	119.36 (15)	O6—Cl1—O5	111.03 (11)
C16—N4—C12	117.42 (14)	O6—Cl1—O3	109.67 (14)
C14—C11—N3	113.66 (12)	O5—Cl1—O3	109.73 (11)
C14—C11—H11A	108.8	O6—Cl1—O4	109.55 (12)
N3—C11—H11A	108.8	O5—Cl1—O4	109.66 (10)
C14—C11—H11B	108.8	O3—Cl1—O4	107.13 (10)
N3—C11—H11B	108.8	C18ⁱ—C18—C17	121.9 (2)
H11A—C11—H11B	107.7	C18ⁱ—C18—H18	119.1
N2—C9—C10	110.42 (13)	C17—C18—H18	119.1
N2—C9—H9A	109.6	C12—C13—C14	119.23 (15)
C10—C9—H9A	109.6	C12—C13—H13	120.4
N2—C9—H9B	109.6	C14—C13—H13	120.4

C6—N2—C7—C8	−178.35 (13)	C1—N1—C5—C4	0.3 (3)
C9—N2—C7—C8	60.97 (17)	C3—C4—C5—N1	0.5 (3)
C8—N3—C10—C9	−57.20 (16)	C16—C15—C14—C13	−0.8 (2)
C11—N3—C10—C9	174.41 (12)	C16—C15—C14—C11	−178.52 (15)
C10—N3—C8—C7	57.58 (16)	N3—C11—C14—C15	−101.07 (17)
C11—N3—C8—C7	−174.15 (12)	N3—C11—C14—C13	81.28 (19)
N2—C7—C8—N3	−59.62 (17)	C9—N2—C6—C3	−170.06 (14)
C1—C2—C3—C4	1.9 (3)	C7—N2—C6—C3	69.22 (18)
C1—C2—C3—C6	−174.69 (16)	C4—C3—C6—N2	28.0 (2)
C10—N3—C11—C14	59.12 (18)	C2—C3—C6—N2	−155.56 (16)
C8—N3—C11—C14	−67.06 (18)	C5—N1—C1—C2	0.1 (3)
C6—N2—C9—C10	177.63 (14)	C3—C2—C1—N1	−1.2 (3)
C7—N2—C9—C10	−60.81 (17)	C16—N4—C12—C13	0.2 (2)
N3—C10—C9—N2	59.18 (17)	O2—C17—C18—C18ⁱ	−18.1 (3)
C2—C3—C4—C5	−1.6 (2)	O1—C17—C18—C18ⁱ	160.9 (2)
C6—C3—C4—C5	174.91 (16)	N4—C12—C13—C14	−1.6 (3)
C12—N4—C16—C15	0.9 (2)	C15—C14—C13—C12	1.8 (2)
C14—C15—C16—N4	−0.6 (3)	C11—C14—C13—C12	179.51 (15)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N4ⁱⁱ	0.925 (19)	1.884 (19)	2.8067 (19)	175.0 (17)
O1—H1A···N1ⁱⁱⁱ	0.93 (2)	1.68 (2)	2.6081 (19)	178 (2)
C10—H10A···O3^iv	0.99	2.37	3.281 (2)	153 (2)
C12—H12···O6^v	0.95	2.49	3.138 (3)	126 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₆H₂₁N₄⁺·ClO₄⁻·0.5C₄H₄O₄
M_r	426.85
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	7.7287 (9), 9.6415 (11), 14.3440 (17)
α, β, γ (°)	88.691 (2), 83.785 (2), 66.749 (2)
V (Å³)	976.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.41 × 0.21 × 0.13

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.908, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	14571, 3593, 3178
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.092, 1.05
No. of reflections	3593
No. of parameters	268
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.38

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), Crystal Maker (Palmer, 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N4ⁱ	0.925 (19)	1.884 (19)	2.8067 (19)	175.0 (17)
O1—H1A···N1ⁱⁱ	0.93 (2)	1.68 (2)	2.6081 (19)	178 (2)
C10—H10A···O3ⁱⁱⁱ	0.99	2.37	3.281 (2)	153 (2)
C12—H12···O6^iv	0.95	2.49	3.138 (3)	126 (2)

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

Acknowledgements

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work.

References

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