2-{[N-(Pyridinium-2-ylmeth­yl)-N-(pyridin-2-ylmeth­yl)amino]meth­yl}-1-(pyridin-2-ylmeth­yl)pyridinium diperchlorate

The cation of the title salt, C₂₄H₂₅N₅²⁺·2ClO₄^-, contains a tris­(2-pyridylmeth­yl)amine core in which one of the pyridine N atoms is protonated and a second pyridine N atom forms an additional C-N bond to another 2-pyridylmeth­yl group, resulting in a second pyridinium center. The protonated pyridinium hydrogen bonds to a pyridine ring of a neighboring dication. The hydrogen-bonded H atom is disordered between the two N atoms.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.073
• wR factor = 0.161
• Data-to-parameter ratio = 13.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.64 Ratio

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.02
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.62 Ratio
PLAT221_ALERT_4_C Large Solvent/Anion  O     Ueq(max)/Ueq(min) ...       3.52 Ratio
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl2
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5
PLAT432_ALERT_2_C Short Inter X...Y Contact  O8     ..  C7      ..       2.94 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              Cl O4

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

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

(I)

Crystal data

C24H25N5^2+·2ClO4^−	F(000) = 1208
Mr = 582.40	Dx = 1.466 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8603 reflections
a = 13.9313 (2) Å	θ = 2.5–32.0°
b = 10.9888 (2) Å	µ = 0.30 mm^−1
c = 18.1280 (4) Å	T = 100 K
β = 108.0650 (8)°	Prism, colorless
V = 2638.38 (8) Å^3	0.20 × 0.12 × 0.10 mm
Z = 4

Data collection

Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer	9091 independent reflections
Radiation source: fine-focus sealed tube	4740 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω scans with κ offsets	θmax = 32.1°, θmin = 3.0°
Absorption correction: multi-scan (SCALEPACK: Otwinowski & Minor 1997)	h = 0→20
Tmin = 0.869, Tmax = 0.955	k = 0→16
48722 measured reflections	l = −26→25

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	0 constraints
R[F^2 > 2σ(F^2)] = 0.073	H-atom parameters constrained
wR(F^2) = 0.161	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo) + 0.003025|Fo|^2]
S = 0.94	(Δ/σ)max = 0.0003
4740 reflections	Δρmax = 0.77 e Å^−3
352 parameters	Δρmin = −0.57 e Å^−3

Special details

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	Occ. (<1)
Cl1	−0.04650 (6)	−0.13051 (7)	0.27292 (4)	0.0341 (2)
Cl2	0.36495 (6)	0.49562 (7)	0.62091 (4)	0.0348 (2)
O1	−0.0774 (2)	−0.2542 (3)	0.2573 (2)	0.0725 (9)
O2	−0.1317 (2)	−0.0509 (3)	0.2500 (2)	0.0795 (11)
O3	0.0072 (2)	−0.1158 (2)	0.35351 (12)	0.0430 (7)
O4	0.0189 (2)	−0.1000 (2)	0.22868 (12)	0.0400 (6)
O5	0.3658 (3)	0.3683 (2)	0.6332 (2)	0.0742 (10)
O6	0.4090 (3)	0.5282 (3)	0.5646 (2)	0.110 (1)
O7	0.4136 (2)	0.5569 (2)	0.69111 (12)	0.0329 (6)
O8	0.2608 (2)	0.5344 (4)	0.5979 (3)	0.1162 (13)
N1	0.1388 (2)	0.1485 (2)	0.47253 (13)	0.0208 (6)
N2	0.2301 (2)	−0.1106 (2)	0.5972 (1)	0.0245 (6)
N3	−0.0915 (2)	0.2702 (2)	0.48744 (13)	0.0235 (6)
N4	0.3828 (2)	−0.0465 (3)	0.3983 (2)	0.0391 (8)
N5	0.2789 (2)	0.1525 (2)	0.32925 (13)	0.0223 (6)
C1	0.3145 (2)	−0.1546 (3)	0.6479 (2)	0.0332 (8)
C2	0.3978 (2)	−0.0822 (3)	0.6811 (2)	0.0377 (9)
C3	0.3947 (2)	0.0393 (3)	0.6608 (2)	0.0322 (8)
C4	0.3069 (2)	0.0852 (3)	0.6091 (2)	0.0272 (7)
C5	0.2255 (2)	0.0086 (2)	0.5784 (2)	0.0206 (6)
C6	0.1266 (2)	0.0532 (2)	0.5253 (2)	0.0203 (6)
C7	−0.1304 (2)	0.3317 (3)	0.5360 (2)	0.0290 (8)
C8	−0.0715 (2)	0.4091 (3)	0.5916 (2)	0.0293 (8)
C9	0.0295 (2)	0.4210 (3)	0.5961 (2)	0.0275 (7)
C10	0.0685 (2)	0.3580 (2)	0.5466 (2)	0.0249 (7)
C11	0.0066 (2)	0.2812 (2)	0.4915 (2)	0.0214 (6)
C12	0.0421 (2)	0.2095 (2)	0.4343 (2)	0.0231 (7)
C13	0.4319 (2)	−0.1436 (4)	0.4395 (2)	0.0493 (11)
C14	0.4052 (3)	−0.2620 (4)	0.4205 (3)	0.0536 (12)
C15	0.3228 (3)	−0.2851 (3)	0.3571 (3)	0.0538 (12)
C16	0.2687 (3)	−0.1889 (3)	0.3141 (2)	0.0452 (10)
C17	0.3028 (2)	−0.0716 (3)	0.3367 (2)	0.0310 (8)
C18	0.2483 (2)	0.0349 (3)	0.2889 (2)	0.0273 (7)
C19	0.3424 (2)	0.2254 (3)	0.3053 (2)	0.0301 (8)
C20	0.3784 (2)	0.3312 (3)	0.3427 (2)	0.0347 (8)
C21	0.3502 (2)	0.3636 (3)	0.4063 (2)	0.0306 (8)
C22	0.2835 (2)	0.2913 (3)	0.4295 (2)	0.0255 (7)
C23	0.2487 (2)	0.1842 (2)	0.3906 (2)	0.0206 (6)
C24	0.1799 (2)	0.0971 (3)	0.4143 (2)	0.0261 (7)
H1	0.1741	−0.1625	0.5746	0.015*	0.5
H2	0.3172	−0.2383	0.6616	0.040*
H3	0.4565	−0.1155	0.7174	0.045*
H4	0.4517	0.0903	0.6820	0.039*
H5	0.3026	0.1687	0.5948	0.033*
H6	0.0879	0.0848	0.5557	0.024*
H7	0.0918	−0.0134	0.4953	0.024*
H8	−0.1996	0.3213	0.5318	0.035*
H9	−0.0990	0.4527	0.6256	0.035*
H10	0.0720	0.4735	0.6339	0.033*
H11	0.1376	0.3669	0.5501	0.030*
H12	−0.0073	0.1498	0.4107	0.028*
H13	0.0504	0.2631	0.3956	0.028*
H14	0.4882	−0.1284	0.4841	0.059*
H15	0.4429	−0.3268	0.4505	0.064*
H16	0.3027	−0.3666	0.3428	0.065*
H17	0.2106	−0.2028	0.2707	0.054*
H18	0.2633	0.0365	0.2412	0.033*
H19	0.1777	0.0245	0.2789	0.033*
H20	0.3619	0.2020	0.2615	0.036*
H21	0.4223	0.3817	0.3253	0.042*
H22	0.3764	0.4357	0.4343	0.037*
H23	0.2617	0.3153	0.4721	0.031*
H24	0.1255	0.0763	0.3697	0.031*
H25	0.2171	0.0258	0.4351	0.031*
H26	−0.1341	0.2180	0.4495	0.014*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0342 (4)	0.0435 (4)	0.0235 (4)	−0.0145 (3)	0.0074 (3)	−0.0005 (3)
Cl2	0.0467 (4)	0.0314 (4)	0.0222 (4)	−0.0204 (3)	0.0047 (3)	0.0015 (3)
O1	0.105 (2)	0.060 (2)	0.035 (2)	−0.058 (2)	−0.002 (2)	0.0024 (13)
O2	0.039 (2)	0.117 (3)	0.083 (2)	0.018 (2)	0.019 (2)	0.007 (2)
O3	0.056 (1)	0.052 (1)	0.0224 (12)	−0.0267 (11)	0.0134 (10)	−0.0092 (10)
O4	0.053 (1)	0.0446 (13)	0.0252 (12)	−0.0057 (11)	0.0159 (10)	0.0066 (10)
O5	0.143 (3)	0.0265 (13)	0.066 (2)	−0.021 (2)	0.052 (2)	−0.0044 (12)
O6	0.201 (4)	0.108 (3)	0.044 (2)	−0.108 (3)	0.072 (2)	−0.032 (2)
O7	0.0310 (10)	0.0398 (12)	0.0267 (12)	−0.0074 (9)	0.0073 (9)	−0.0084 (9)
O8	0.047 (2)	0.107 (3)	0.139 (3)	−0.028 (2)	−0.051 (2)	0.049 (3)
N1	0.0247 (11)	0.0220 (11)	0.0188 (12)	−0.0047 (9)	0.0113 (9)	−0.0005 (9)
N2	0.0230 (11)	0.0238 (11)	0.0268 (13)	−0.0011 (9)	0.0079 (10)	−0.0031 (10)
N3	0.0296 (11)	0.0208 (11)	0.0192 (12)	−0.0005 (9)	0.0063 (9)	0.0011 (9)
N4	0.0287 (13)	0.044 (2)	0.043 (2)	0.0067 (12)	0.0087 (12)	0.0130 (13)
N5	0.0181 (10)	0.0292 (12)	0.0196 (12)	0.0020 (9)	0.0059 (9)	0.0022 (9)
C1	0.033 (2)	0.029 (2)	0.034 (2)	0.0063 (13)	0.0055 (13)	−0.0002 (13)
C2	0.027 (2)	0.045 (2)	0.037 (2)	0.009 (1)	0.0040 (13)	−0.003 (2)
C3	0.0226 (13)	0.041 (2)	0.031 (2)	−0.0054 (12)	0.0062 (12)	−0.006 (1)
C4	0.0276 (13)	0.028 (1)	0.027 (2)	−0.0041 (12)	0.0089 (12)	−0.0020 (12)
C5	0.0208 (12)	0.0244 (13)	0.0190 (13)	−0.0013 (10)	0.0100 (10)	−0.0039 (10)
C6	0.0219 (12)	0.0211 (12)	0.021 (1)	−0.0026 (10)	0.0104 (10)	−0.0002 (10)
C7	0.032 (1)	0.027 (1)	0.029 (2)	0.0020 (12)	0.0108 (12)	0.0002 (12)
C8	0.035 (2)	0.028 (1)	0.025 (2)	0.0057 (12)	0.0104 (12)	−0.0040 (12)
C9	0.034 (2)	0.0256 (13)	0.019 (1)	0.0001 (12)	0.0024 (12)	−0.0017 (11)
C10	0.0265 (13)	0.0226 (13)	0.023 (2)	−0.0014 (11)	0.0034 (11)	0.0014 (11)
C11	0.0277 (13)	0.0186 (12)	0.018 (1)	−0.0001 (10)	0.0071 (10)	0.0033 (10)
C12	0.0279 (13)	0.0232 (13)	0.018 (1)	−0.0037 (11)	0.0064 (11)	0.0017 (11)
C13	0.034 (2)	0.056 (2)	0.055 (2)	0.009 (2)	0.009 (2)	0.020 (2)
C14	0.051 (2)	0.044 (2)	0.070 (3)	0.019 (2)	0.026 (2)	0.024 (2)
C15	0.071 (3)	0.034 (2)	0.063 (3)	0.008 (2)	0.031 (2)	0.007 (2)
C16	0.057 (2)	0.036 (2)	0.044 (2)	0.005 (2)	0.018 (2)	−0.005 (2)
C17	0.031 (2)	0.035 (2)	0.033 (2)	0.0073 (13)	0.0198 (13)	0.0026 (13)
C18	0.029 (1)	0.032 (1)	0.022 (2)	0.0012 (12)	0.0106 (12)	−0.0039 (12)
C19	0.0243 (13)	0.043 (2)	0.026 (2)	0.0010 (12)	0.0131 (12)	0.0060 (13)
C20	0.027 (1)	0.043 (2)	0.035 (2)	−0.0096 (13)	0.0119 (13)	0.008 (1)
C21	0.030 (1)	0.031 (2)	0.029 (2)	−0.0099 (12)	0.0066 (12)	0.0024 (13)
C22	0.0294 (13)	0.028 (1)	0.021 (1)	−0.0054 (11)	0.0098 (11)	0.0014 (11)
C23	0.0190 (11)	0.0245 (13)	0.0178 (13)	−0.0013 (10)	0.0052 (10)	0.0026 (10)
C24	0.031 (1)	0.0261 (13)	0.026 (2)	−0.0065 (11)	0.0163 (12)	−0.0062 (12)

Geometric parameters (Å, º)

Cl1—O1	1.427 (3)	C16—C17	1.391 (5)
Cl1—O2	1.429 (3)	C17—C18	1.513 (4)
Cl1—O3	1.429 (2)	C19—C20	1.362 (4)
Cl1—O4	1.428 (2)	C20—C21	1.375 (4)
Cl2—O5	1.417 (3)	C21—C22	1.383 (4)
Cl2—O6	1.391 (3)	C22—C23	1.381 (4)
Cl2—O7	1.413 (2)	C23—C24	1.508 (4)
Cl2—O8	1.444 (4)	N2—H1	0.950
N1—C6	1.462 (3)	C1—H2	0.950
N1—C12	1.472 (3)	C2—H3	0.950
N1—C24	1.462 (3)	C3—H4	0.950
N2—C1	1.339 (4)	C4—H5	0.950
N2—C5	1.349 (4)	C6—H6	0.950
N3—C7	1.350 (4)	C6—H7	0.950
N3—C11	1.351 (3)	C7—H8	0.950
N4—C13	1.360 (4)	C8—H9	0.950
N4—C17	1.338 (4)	C9—H10	0.950
N5—C18	1.480 (4)	C10—H11	0.950
N5—C19	1.360 (3)	C12—H12	0.950
N5—C23	1.351 (3)	C12—H13	0.950
C1—C2	1.382 (5)	C13—H14	0.950
C2—C3	1.381 (5)	C14—H15	0.950
C3—C4	1.385 (4)	C15—H16	0.950
C4—C5	1.383 (4)	C16—H17	0.950
C5—C6	1.498 (4)	C18—H18	0.950
C7—C8	1.378 (4)	C18—H19	0.950
C8—C9	1.390 (4)	C19—H20	0.950
C9—C10	1.372 (4)	C20—H21	0.950
C10—C11	1.385 (4)	C21—H22	0.950
C11—C12	1.503 (4)	C22—H23	0.950
C13—C14	1.367 (6)	C24—H24	0.950
C14—C15	1.373 (6)	C24—H25	0.950
C15—C16	1.388 (5)	N3—H26	0.950
O1···N5^i	2.943 (3)	O8···C7^ii	2.938 (5)
O1—Cl1—O2	110.7 (2)	C7—N3—H26	119.2
O1—Cl1—O3	110.0 (2)	C11—N3—H26	119.2
O1—Cl1—O4	108.5 (2)	N2—C1—H2	119.0
O2—Cl1—O3	110.6 (2)	C2—C1—H2	119.0
O2—Cl1—O4	108.0 (2)	C1—C2—H3	120.4
O3—Cl1—O4	108.9 (1)	C3—C2—H3	120.4
O5—Cl2—O6	112.7 (2)	C2—C3—H4	120.6
O5—Cl2—O7	110.5 (2)	C4—C3—H4	120.6
O5—Cl2—O8	107.2 (2)	C3—C4—H5	120.3
O6—Cl2—O7	109.9 (2)	C5—C4—H5	120.3
O6—Cl2—O8	110.2 (3)	N1—C6—H6	108.7
O7—Cl2—O8	106.1 (2)	N1—C6—H7	108.7
C6—N1—C12	111.1 (2)	C5—C6—H6	108.7
C6—N1—C24	110.2 (2)	C5—C6—H7	108.7
C12—N1—C24	110.0 (2)	H6—C6—H7	109.5
C1—N2—C5	119.1 (2)	N3—C7—H8	119.4
C7—N3—C11	121.6 (2)	C8—C7—H8	119.4
C13—N4—C17	116.3 (3)	C7—C8—H9	121.2
C18—N5—C19	118.2 (2)	C9—C8—H9	121.2
C18—N5—C23	121.1 (2)	C8—C9—H10	119.6
C19—N5—C23	120.7 (2)	C10—C9—H10	119.6
N2—C1—C2	122.0 (3)	C9—C10—H11	120.2
C1—C2—C3	119.2 (3)	C11—C10—H11	120.2
C2—C3—C4	118.7 (3)	N1—C12—H12	109.0
C3—C4—C5	119.5 (3)	N1—C12—H13	109.0
N2—C5—C4	121.4 (2)	C11—C12—H12	109.0
N2—C5—C6	116.2 (2)	C11—C12—H13	109.0
C4—C5—C6	122.4 (2)	H12—C12—H13	109.5
N1—C6—C5	112.7 (2)	N4—C13—H14	118.1
N3—C7—C8	121.1 (3)	C14—C13—H14	118.1
C7—C8—C9	117.6 (3)	C13—C14—H15	120.7
C8—C9—C10	120.9 (3)	C15—C14—H15	120.7
C9—C10—C11	119.7 (2)	C14—C15—H16	120.1
N3—C11—C10	119.1 (2)	C16—C15—H16	120.1
N3—C11—C12	117.3 (2)	C15—C16—H17	121.2
C10—C11—C12	123.6 (2)	C17—C16—H17	121.2
N1—C12—C11	111.2 (2)	N5—C18—H18	108.8
N4—C13—C14	123.8 (4)	N5—C18—H19	108.8
C13—C14—C15	118.6 (3)	C17—C18—H18	108.8
C14—C15—C16	119.8 (4)	C17—C18—H19	108.8
C15—C16—C17	117.6 (4)	H18—C18—H19	109.5
N4—C17—C16	123.8 (3)	N5—C19—H20	119.4
N4—C17—C18	117.3 (3)	C20—C19—H20	119.4
C16—C17—C18	118.9 (3)	C19—C20—H21	120.6
N5—C18—C17	112.1 (2)	C21—C20—H21	120.6
N5—C19—C20	121.3 (3)	C20—C21—H22	120.0
C19—C20—C21	118.8 (3)	C22—C21—H22	120.0
C20—C21—C22	120.0 (3)	C21—C22—H23	120.1
C21—C22—C23	119.8 (3)	C23—C22—H23	120.1
N5—C23—C22	119.4 (2)	N1—C24—H24	108.6
N5—C23—C24	117.3 (2)	N1—C24—H25	108.6
C22—C23—C24	123.2 (2)	C23—C24—H24	108.6
N1—C24—C23	112.8 (2)	C23—C24—H25	108.6
C1—N2—H1	120.4	H24—C24—H25	109.5
C5—N2—H1	120.4
N1—C6—C5—N2	−145.6 (2)	C7—N3—C11—C10	−0.4 (4)
N1—C6—C5—C4	36.6 (3)	C7—N3—C11—C12	−179.5 (2)
N1—C12—C11—N3	−134.6 (2)	C7—C8—C9—C10	0.2 (4)
N1—C12—C11—C10	46.3 (3)	C8—C7—N3—C11	0.5 (4)
N1—C24—C23—N5	−170.6 (2)	C8—C9—C10—C11	−0.1 (4)
N1—C24—C23—C22	11.1 (4)	C9—C10—C11—C12	179.3 (3)
N2—C1—C2—C3	−0.7 (5)	C11—C12—N1—C24	−170.3 (2)
N2—C5—C4—C3	−0.7 (4)	C12—N1—C24—C23	90.9 (3)
N3—C7—C8—C9	−0.4 (4)	C13—N4—C17—C16	0.4 (4)
N3—C11—C10—C9	0.2 (4)	C13—N4—C17—C18	−178.7 (3)
N4—C13—C14—C15	−1.4 (6)	C13—C14—C15—C16	0.0 (6)
N4—C17—C16—C15	−1.6 (5)	C14—C13—N4—C17	1.2 (5)
N4—C17—C18—N5	−13.3 (3)	C14—C15—C16—C17	1.4 (5)
N5—C18—C17—C16	167.6 (3)	C15—C16—C17—C18	177.4 (3)
N5—C19—C20—C21	0.4 (5)	C17—C18—N5—C19	104.2 (3)
N5—C23—C22—C21	−1.2 (4)	C17—C18—N5—C23	−72.7 (3)
C1—N2—C5—C4	1.6 (4)	C18—N5—C19—C20	−176.0 (3)
C1—N2—C5—C6	−176.3 (2)	C18—N5—C23—C22	176.3 (2)
C1—C2—C3—C4	1.5 (5)	C18—N5—C23—C24	−2.0 (4)
C2—C1—N2—C5	−0.9 (4)	C19—N5—C23—C22	−0.6 (4)
C2—C3—C4—C5	−0.8 (4)	C19—N5—C23—C24	−178.9 (2)
C3—C4—C5—C6	177.0 (3)	C19—C20—C21—C22	−2.2 (5)
C5—C6—N1—C12	−166.9 (2)	C20—C19—N5—C23	0.9 (4)
C5—C6—N1—C24	70.9 (3)	C20—C21—C22—C23	2.6 (4)
C6—N1—C12—C11	67.3 (3)	C21—C22—C23—C24	177.0 (3)
C6—N1—C24—C23	−146.2 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···N3^iii	0.95	1.79	2.706 (3)	162

Symmetry code: (iii) −x, −y, −z+1.