N,N,N',N'-Tetrakis(2-pyridinio­methyl)­ethyl­enedi­amine tetraperchlorate

The title compound, (HpyCH₂)₂NCH₂CH₂N(CH₂PyH)₂(ClO₄)₄ or C₂₆H₃₂N₆⁴⁺·4ClO₄^-, is a salt of a centrosymmetric tetraprotonated tetra­pyridine. As in many related compounds, the pyridyl N atoms are protonated while the tertiary amine N atoms are not.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.061
• wR factor = 0.111
• Data-to-parameter ratio = 11.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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Computing details

Data collection: COLLECT (Nonius 2000); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al. 1993); program(s) used to refine structure: TEXSAN (Molecular Structure Corporation, 1997-1999); software used to prepare material for publication: TEXSAN.

(I)

Crystal data

C26H32N6^4+·4ClO4^−	Z = 1
Mr = 826.38	F(000) = 426.00
Triclinic, P1	Dx = 1.64 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.7107 Å
a = 8.4278 (2) Å	Cell parameters from 3927 reflections
b = 9.2848 (2) Å	θ = 2.5–30.0°
c = 11.3490 (3) Å	µ = 0.44 mm^−1
α = 100.2225 (9)°	T = 100 K
β = 105.5358 (10)°	Fragment, gold
γ = 94.4063 (13)°	0.25 × 0.25 × 0.10 mm
V = 834.76 (4) Å^3

Data collection

Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer	4500 independent reflections
Radiation source: fine-focus sealed tube	2656 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.030
ω scans with κ offsets	θmax = 29.5°, θmin = 2.7°
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997)	h = −11→11
Tmin = 0.891, Tmax = 0.957	k = −12→12
16863 measured reflections	l = −15→15

Refinement

Refinement on F^2	0 constraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.061	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo) + 0.0014|Fo|^2]
wR(F^2) = 0.111	(Δ/σ)max = 0.0004
S = 0.97	Δρmax = 0.47 e Å^−3
2656 reflections	Δρmin = −0.40 e Å^−3
236 parameters	Extinction correction: Zachariasen
0 restraints	Extinction coefficient: 0.204493

Special details

Geometry. The hydrogen atoms bound to C1 (H1 and H2) were found in difference maps, refined for several cycles, then fixed.

Refinement. Refinement of F². The weighted R-factor wR and goodness of fit are based on F², conventional R-factors R are based on F. R-factors based on F² are statistically about twice as large as those based on F.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.84351 (7)	0.63815 (7)	0.17548 (6)	0.0230 (2)
Cl2	0.73827 (7)	0.74387 (6)	0.67727 (6)	0.0216 (2)
O1	0.9857 (3)	0.7327 (2)	0.1791 (2)	0.0387 (7)
O2	0.7002 (3)	0.6622 (2)	0.0834 (2)	0.0367 (6)
O3	0.8708 (3)	0.4842 (2)	0.1450 (2)	0.0366 (6)
O4	0.8162 (3)	0.6646 (2)	0.2977 (2)	0.0358 (6)
O5	0.7968 (2)	0.8769 (2)	0.6446 (2)	0.0332 (6)
O6	0.7417 (3)	0.6186 (2)	0.5859 (2)	0.0485 (7)
O7	0.5726 (2)	0.7496 (2)	0.6860 (2)	0.0394 (7)
O8	0.8436 (3)	0.7323 (2)	0.7976 (2)	0.0449 (7)
N1	0.7134 (3)	0.1240 (2)	0.0577 (2)	0.0187 (6)
N2	0.8153 (3)	0.2779 (2)	0.3004 (2)	0.0210 (6)
N3	0.7004 (3)	0.3405 (2)	−0.1057 (2)	0.0225 (6)
C1	0.5326 (3)	0.0808 (3)	0.0335 (2)	0.0172 (6)
C2	0.8222 (3)	0.3616 (3)	0.4112 (3)	0.0230 (7)
C3	0.8304 (3)	0.2993 (3)	0.5117 (3)	0.0247 (7)
C4	0.8311 (3)	0.1470 (3)	0.4975 (3)	0.0271 (8)
C5	0.8220 (3)	0.0629 (3)	0.3812 (3)	0.0257 (7)
C6	0.8137 (3)	0.1298 (3)	0.2816 (3)	0.0218 (7)
C7	0.8130 (3)	0.0538 (3)	0.1530 (3)	0.0241 (7)
C8	0.6368 (3)	0.4327 (3)	−0.1791 (3)	0.0254 (7)
C9	0.5456 (3)	0.3778 (3)	−0.3002 (3)	0.0258 (8)
C10	0.5186 (3)	0.2266 (3)	−0.3449 (3)	0.0261 (7)
C11	0.5874 (3)	0.1338 (3)	−0.2670 (3)	0.0245 (7)
C12	0.6812 (3)	0.1923 (3)	−0.1460 (3)	0.0198 (7)
C13	0.7681 (3)	0.1034 (3)	−0.0556 (3)	0.0211 (7)
H1	0.5056	0.1070	0.1235	0.022*
H2	0.4668	0.1445	−0.0211	0.022*
H3	0.8115	0.3247	0.2320	0.025*
H4	0.8213	0.4651	0.4193	0.028*
H5	0.8356	0.3583	0.5904	0.030*
H6	0.8377	0.1012	0.5669	0.032*
H7	0.8216	−0.0409	0.3707	0.031*
H8	0.7674	−0.0467	0.1384	0.029*
H9	0.9238	0.0593	0.1477	0.029*
H10	0.7618	0.3812	−0.0214	0.027*
H11	0.6552	0.5362	−0.1469	0.030*
H12	0.5013	0.4424	−0.3531	0.031*
H13	0.4535	0.1865	−0.4284	0.031*
H14	0.5696	0.0300	−0.2973	0.029*
H15	0.7447	0.0018	−0.0950	0.025*
H16	0.8844	0.1334	−0.0330	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0222 (3)	0.0168 (3)	0.0292 (4)	0.0026 (2)	0.0051 (3)	0.0056 (3)
Cl2	0.0230 (3)	0.0178 (3)	0.0247 (4)	0.0022 (2)	0.0082 (3)	0.0044 (3)
O1	0.0336 (12)	0.0335 (11)	0.054 (2)	−0.0031 (9)	0.0195 (11)	0.0157 (11)
O2	0.0349 (12)	0.0331 (11)	0.0366 (13)	0.0120 (9)	−0.0021 (10)	0.0090 (10)
O3	0.0499 (13)	0.0191 (10)	0.0370 (13)	0.0105 (9)	0.0045 (10)	0.0058 (9)
O4	0.0365 (12)	0.0426 (12)	0.0323 (13)	0.0062 (9)	0.0154 (10)	0.0093 (10)
O5	0.0323 (11)	0.0254 (10)	0.047 (1)	0.0015 (8)	0.0132 (10)	0.0182 (10)
O6	0.078 (2)	0.0253 (11)	0.048 (2)	0.0047 (11)	0.037 (1)	−0.0051 (10)
O7	0.0249 (11)	0.0324 (11)	0.064 (2)	0.0026 (9)	0.0199 (11)	0.0077 (11)
O8	0.0406 (13)	0.0465 (13)	0.041 (2)	−0.0084 (10)	−0.0041 (11)	0.0230 (11)
N1	0.0168 (10)	0.0191 (11)	0.0199 (12)	0.0017 (8)	0.0054 (9)	0.0033 (9)
N2	0.0227 (11)	0.0209 (11)	0.0199 (12)	0.0036 (9)	0.0051 (10)	0.0064 (9)
N3	0.0255 (11)	0.0209 (11)	0.0214 (13)	−0.0000 (9)	0.0090 (10)	0.0028 (9)
C1	0.0163 (11)	0.0162 (12)	0.019 (1)	0.0021 (9)	0.0051 (10)	0.0031 (10)
C2	0.0216 (13)	0.0205 (13)	0.026 (2)	0.0011 (10)	0.0067 (12)	0.0032 (11)
C3	0.0207 (13)	0.031 (2)	0.023 (2)	0.0022 (11)	0.0071 (12)	0.0065 (12)
C4	0.023 (1)	0.031 (2)	0.031 (2)	0.0025 (11)	0.0094 (12)	0.0138 (13)
C5	0.0199 (13)	0.0182 (13)	0.038 (2)	0.0010 (10)	0.0067 (12)	0.0073 (12)
C6	0.0137 (12)	0.0222 (13)	0.025 (2)	−0.0010 (10)	0.0014 (11)	0.0016 (11)
C7	0.0200 (13)	0.0189 (13)	0.030 (2)	0.0031 (10)	0.0023 (12)	0.0022 (11)
C8	0.030 (2)	0.0181 (13)	0.032 (2)	0.0022 (11)	0.0139 (13)	0.0086 (12)
C9	0.028 (1)	0.025 (1)	0.030 (2)	0.0038 (11)	0.0143 (13)	0.0130 (12)
C10	0.026 (1)	0.030 (2)	0.023 (2)	−0.0006 (11)	0.0088 (12)	0.0068 (12)
C11	0.025 (1)	0.0199 (13)	0.029 (2)	−0.0005 (11)	0.0119 (13)	0.0020 (11)
C12	0.0201 (12)	0.0182 (12)	0.025 (2)	−0.0003 (10)	0.0140 (12)	0.0045 (11)
C13	0.0176 (12)	0.0200 (12)	0.026 (2)	0.0014 (10)	0.0086 (11)	0.0035 (11)

Geometric parameters (Å, º)

Cl1—O1	1.417 (2)	C8—C9	1.366 (4)
Cl1—O2	1.432 (2)	C9—C10	1.384 (4)
Cl1—O3	1.460 (2)	C10—C11	1.390 (4)
Cl1—O4	1.447 (2)	C11—C12	1.376 (4)
Cl2—O5	1.440 (2)	C12—C13	1.504 (4)
Cl2—O6	1.422 (2)	N2—H3	0.950
Cl2—O7	1.431 (2)	N3—H10	0.950
Cl2—O8	1.443 (2)	C1—H1	1.096
N1—C1	1.483 (3)	C1—H2	1.019
N1—C7	1.465 (3)	C2—H4	0.950
N1—C13	1.466 (3)	C3—H5	0.950
N2—C2	1.340 (3)	C4—H6	0.950
N2—C6	1.352 (3)	C5—H7	0.950
N3—C8	1.341 (3)	C7—H8	0.950
N3—C12	1.354 (3)	C7—H9	0.950
C1—C1^i	1.542 (5)	C8—H11	0.950
C2—C3	1.356 (4)	C9—H12	0.950
C3—C4	1.395 (4)	C10—H13	0.950
C4—C5	1.389 (4)	C11—H14	0.950
C5—C6	1.372 (4)	C13—H15	0.950
C6—C7	1.502 (4)	C13—H16	0.950
O1···C12^ii	2.977 (3)	O4···O6	3.582 (3)
O1···N3^ii	3.068 (3)	O4···N2	3.596 (3)
O1···C13^ii	3.227 (3)	O5···C6^iv	3.172 (3)
O1···C7^iii	3.442 (3)	O5···C11^vi	3.250 (3)
O1···C3^iv	3.511 (4)	O5···C4^iii	3.285 (3)
O1···C4^iv	3.513 (4)	O5···C5^iv	3.317 (3)
O1···C11^ii	3.526 (3)	O5···C7^iv	3.407 (3)
O2···C8	3.228 (4)	O6···C2	3.062 (3)
O2···N3	3.355 (3)	O6···C3	3.139 (3)
O2···C8^v	3.411 (3)	O6···C9^vii	3.318 (3)
O2···C1^v	3.428 (3)	O6···C9^v	3.496 (4)
O2···N3^v	3.451 (3)	O6···N2^iv	3.599 (3)
O2···C7^iii	3.577 (3)	O7···C2^viii	3.233 (3)
O3···N3	2.847 (3)	O7···N2^viii	3.306 (3)
O3···N2	2.917 (3)	O7···C9^vii	3.477 (3)
O3···O8^iv	3.261 (3)	O7···C3^viii	3.478 (3)
O3···N1	3.371 (3)	O7···C11^vi	3.500 (3)
O3···C2	3.522 (3)	O7···C8^vii	3.562 (3)
O4···C9^v	3.053 (3)	O8···C7^iv	3.238 (4)
O4···C3^iv	3.131 (3)	O8···C8^vii	3.257 (3)
O4···C10^v	3.214 (3)	O8···N2^iv	3.351 (3)
O4···C2	3.294 (3)	O8···C6^iv	3.467 (3)
O4···C4^iv	3.369 (4)	C3···C10^vii	3.524 (4)
O1—Cl1—O2	110.9 (1)	C6—N2—H3	118.48
O1—Cl1—O3	109.9 (1)	C8—N3—H10	118.43
O1—Cl1—O4	109.1 (1)	C12—N3—H10	118.43
O2—Cl1—O3	108.7 (1)	N1—C1—H1	107.03
O2—Cl1—O4	110.2 (1)	N1—C1—H2	110.19
O3—Cl1—O4	108.0 (1)	C1^i—C1—H1	111.66
O5—Cl2—O6	110.1 (1)	C1^i—C1—H2	106.23
O5—Cl2—O7	109.9 (1)	H1—C1—H2	106.03
O5—Cl2—O8	109.1 (1)	N2—C2—H4	119.83
O6—Cl2—O7	109.8 (1)	C3—C2—H4	119.83
O6—Cl2—O8	109.6 (1)	C2—C3—H5	120.55
O7—Cl2—O8	108.3 (1)	C4—C3—H5	120.55
C1—N1—C7	112.1 (2)	C3—C4—H6	120.28
C1—N1—C13	113.7 (2)	C5—C4—H6	120.28
C7—N1—C13	111.8 (2)	C4—C5—H7	119.98
C2—N2—C6	123.0 (2)	C6—C5—H7	119.98
C8—N3—C12	123.1 (2)	N1—C7—H8	109.14
N1—C1—C1^i	115.3 (2)	N1—C7—H9	109.14
N2—C2—C3	120.3 (2)	C6—C7—H8	109.14
C2—C3—C4	118.9 (3)	C6—C7—H9	109.14
C3—C4—C5	119.4 (3)	H8—C7—H9	109.46
C4—C5—C6	120.0 (2)	N3—C8—H11	120.03
N2—C6—C5	118.2 (3)	C9—C8—H11	120.03
N2—C6—C7	116.1 (2)	C8—C9—H12	120.44
C5—C6—C7	125.6 (2)	C10—C9—H12	120.44
N1—C7—C6	110.8 (2)	C9—C10—H13	120.17
N3—C8—C9	119.9 (2)	C11—C10—H13	120.18
C8—C9—C10	119.1 (2)	C10—C11—H14	119.98
C9—C10—C11	119.7 (3)	C12—C11—H14	119.98
C10—C11—C12	120.0 (2)	N1—C13—H15	108.94
N3—C12—C11	118.1 (2)	N1—C13—H16	108.94
N3—C12—C13	117.3 (2)	C12—C13—H15	108.95
C11—C12—C13	124.6 (2)	C12—C13—H16	108.94
N1—C13—C12	111.6 (2)	H15—C13—H16	109.46
C2—N2—H3	118.48
N1—C1—C1^i—N1^i	180	C2—N2—C6—C7	−177.5 (2)
N1—C7—C6—N2	−36.3 (3)	C2—C3—C4—C5	−0.5 (4)
N1—C7—C6—C5	147.6 (3)	C3—C2—N2—C6	1.0 (4)
N1—C13—C12—N3	59.6 (3)	C3—C4—C5—C6	0.5 (4)
N1—C13—C12—C11	−122.0 (3)	C4—C5—C6—C7	176.4 (2)
N2—C2—C3—C4	−0.2 (4)	C6—C7—N1—C13	153.6 (2)
N2—C6—C5—C4	0.3 (4)	C7—N1—C13—C12	−172.3 (2)
N3—C8—C9—C10	0.7 (4)	C8—N3—C12—C11	−2.2 (4)
N3—C12—C11—C10	1.5 (4)	C8—N3—C12—C13	176.4 (2)
C1—N1—C7—C6	−77.4 (3)	C8—C9—C10—C11	−1.3 (4)
C1—N1—C13—C12	59.5 (3)	C9—C8—N3—C12	1.1 (4)
C1^i—C1—N1—C7	−69.7 (3)	C9—C10—C11—C12	0.2 (4)
C1^i—C1—N1—C13	58.3 (3)	C10—C11—C12—C13	−176.9 (2)
C2—N2—C6—C5	−1.1 (4)

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