4-[N,N-Bis(2-cyano­ethyl)­amino]­pyridinium perchlorate

In the title compound, C₁₁H₁₃N₄⁺·ClO₄⁻, the planar geometry around the amino N atom in the cation suggests conjugation with the π-system of the pyridine ring. N—H...O, C—H...O and C—H...N hydrogen-bonding interactions play a key role in the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.049
• wR factor = 0.118
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....        Cl1
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              Cl O4

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

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

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

4-[N,N-bis(2-cyanoethyl)amino]pyridine perchlorate

Crystal data

C11H13N4^+·ClO4^−	F(000) = 624
Mr = 300.70	Dx = 1.493 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2473 reflections
a = 5.403 (1) Å	θ = 2.6–25.9°
b = 30.252 (5) Å	µ = 0.31 mm^−1
c = 8.293 (2) Å	T = 293 K
β = 99.24 (1)°	Needle, colorless
V = 1337.9 (5) Å^3	0.40 × 0.20 × 0.15 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2345 independent reflections
Radiation source: fine-focus sealed tube	1848 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
φ and ω scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −6→6
Tmin = 0.925, Tmax = 0.957	k = −35→35
6812 measured reflections	l = −8→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 0.8P] where P = (Fo^2 + 2Fc^2)/3
2345 reflections	(Δ/σ)max = 0.001
185 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

Refinement. The structure was solved by direct methods(Bruker, 2000) and successive difference Fourier syntheses. 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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	−0.29800 (12)	0.67181 (2)	0.89840 (9)	0.0525 (2)
O1	−0.3531 (5)	0.63189 (6)	0.9712 (3)	0.0871 (8)
O2	−0.0382 (4)	0.67343 (6)	0.8831 (3)	0.0731 (6)
O3	−0.4441 (6)	0.67699 (11)	0.7432 (4)	0.1311 (12)
O4	−0.3501 (5)	0.70762 (7)	0.9995 (4)	0.1000 (9)
N1	0.1321 (5)	0.76466 (9)	0.8764 (3)	0.0655 (8)
N2	0.2172 (4)	0.89903 (6)	0.8803 (2)	0.0369 (5)
N3	−0.2007 (4)	0.97220 (8)	0.6239 (3)	0.0559 (6)
N4	0.6700 (5)	0.96439 (9)	1.1714 (3)	0.0719 (8)
C1	0.2853 (6)	0.78309 (9)	0.7850 (3)	0.0567 (7)
H1	0.3739	0.7652	0.7232	0.068*
C2	0.3144 (5)	0.82742 (7)	0.7806 (3)	0.0437 (6)
H2	0.4181	0.8398	0.7134	0.052*
C3	0.1880 (4)	0.85505 (7)	0.8777 (3)	0.0369 (5)
C4	0.0295 (5)	0.83360 (9)	0.9730 (3)	0.0495 (6)
H4	−0.0578	0.8501	1.0400	0.059*
C5	0.0048 (6)	0.78943 (10)	0.9670 (4)	0.0614 (8)
H5	−0.1042	0.7758	1.0278	0.074*
C6	0.3622 (4)	0.92171 (7)	0.7706 (3)	0.0380 (5)
H6A	0.5084	0.9041	0.7594	0.046*
H6B	0.4206	0.9498	0.8186	0.046*
C7	0.2105 (5)	0.92984 (8)	0.6018 (3)	0.0426 (6)
H7A	0.3108	0.9468	0.5368	0.051*
H7B	0.1709	0.9017	0.5477	0.051*
C8	−0.0223 (5)	0.95373 (8)	0.6110 (3)	0.0426 (6)
C9	0.0956 (5)	0.92687 (8)	0.9883 (3)	0.0431 (6)
H9A	−0.0738	0.9162	0.9881	0.052*
H9B	0.0843	0.9568	0.9459	0.052*
C10	0.2345 (5)	0.92756 (9)	1.1639 (3)	0.0475 (6)
H10A	0.1374	0.9441	1.2321	0.057*
H10B	0.2530	0.8976	1.2056	0.057*
C11	0.4820 (6)	0.94776 (9)	1.1721 (3)	0.0515 (7)
H11	0.113 (6)	0.7370 (11)	0.878 (4)	0.069 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0504 (4)	0.0422 (4)	0.0654 (5)	−0.0065 (3)	0.0106 (3)	0.0071 (3)
O1	0.0981 (18)	0.0494 (12)	0.122 (2)	−0.0068 (11)	0.0439 (16)	0.0176 (12)
O2	0.0588 (13)	0.0638 (13)	0.1018 (17)	−0.0070 (10)	0.0280 (12)	0.0032 (11)
O3	0.115 (2)	0.160 (3)	0.100 (2)	−0.015 (2)	−0.0376 (19)	0.033 (2)
O4	0.110 (2)	0.0592 (14)	0.146 (2)	−0.0086 (13)	0.0669 (19)	−0.0168 (14)
N1	0.085 (2)	0.0397 (14)	0.0638 (17)	−0.0161 (13)	−0.0115 (14)	0.0090 (12)
N2	0.0416 (11)	0.0380 (11)	0.0323 (10)	0.0009 (8)	0.0091 (9)	−0.0001 (8)
N3	0.0490 (15)	0.0591 (14)	0.0590 (16)	−0.0010 (12)	0.0067 (12)	0.0109 (11)
N4	0.0530 (17)	0.0823 (18)	0.0798 (19)	−0.0008 (14)	0.0086 (14)	−0.0245 (15)
C1	0.0694 (19)	0.0429 (14)	0.0537 (17)	0.0038 (13)	−0.0025 (14)	−0.0040 (13)
C2	0.0471 (15)	0.0410 (13)	0.0428 (14)	0.0002 (11)	0.0066 (11)	0.0007 (11)
C3	0.0357 (13)	0.0419 (13)	0.0311 (12)	−0.0025 (10)	−0.0008 (10)	0.0036 (10)
C4	0.0467 (15)	0.0604 (17)	0.0414 (14)	−0.0088 (13)	0.0072 (12)	0.0060 (12)
C5	0.065 (2)	0.0637 (19)	0.0522 (18)	−0.0256 (16)	−0.0009 (15)	0.0164 (15)
C6	0.0382 (13)	0.0368 (12)	0.0392 (13)	−0.0039 (10)	0.0071 (11)	0.0007 (10)
C7	0.0461 (14)	0.0470 (14)	0.0357 (13)	−0.0023 (11)	0.0100 (11)	0.0040 (10)
C8	0.0473 (16)	0.0427 (13)	0.0371 (14)	−0.0080 (12)	0.0050 (12)	0.0073 (11)
C9	0.0424 (14)	0.0505 (14)	0.0357 (13)	0.0078 (11)	0.0046 (11)	−0.0020 (11)
C10	0.0481 (15)	0.0584 (16)	0.0362 (14)	0.0081 (12)	0.0073 (12)	−0.0041 (12)
C11	0.0535 (18)	0.0588 (17)	0.0411 (16)	0.0115 (14)	0.0039 (13)	−0.0124 (12)

Geometric parameters (Å, º)

Cl1—O1	1.403 (2)	C3—C4	1.413 (3)
Cl1—O3	1.406 (3)	C4—C5	1.343 (4)
Cl1—O4	1.426 (2)	C4—H4	0.9300
Cl1—O2	1.430 (2)	C5—H5	0.9300
N1—C5	1.329 (4)	C6—C7	1.524 (3)
N1—C1	1.331 (4)	C6—H6A	0.9700
N1—H11	0.84 (3)	C6—H6B	0.9700
N2—C3	1.340 (3)	C7—C8	1.463 (4)
N2—C9	1.460 (3)	C7—H7A	0.9700
N2—C6	1.463 (3)	C7—H7B	0.9700
N3—C8	1.134 (3)	C9—C10	1.528 (3)
N4—C11	1.134 (4)	C9—H9A	0.9700
C1—C2	1.351 (3)	C9—H9B	0.9700
C1—H1	0.9300	C10—C11	1.462 (4)
C2—C3	1.410 (3)	C10—H10A	0.9700
C2—H2	0.9300	C10—H10B	0.9700
O1—Cl1—O3	111.29 (18)	N2—C6—C7	112.58 (19)
O1—Cl1—O4	108.99 (15)	N2—C6—H6A	109.1
O3—Cl1—O4	108.6 (2)	C7—C6—H6A	109.1
O1—Cl1—O2	110.28 (14)	N2—C6—H6B	109.1
O3—Cl1—O2	109.26 (19)	C7—C6—H6B	109.1
O4—Cl1—O2	108.38 (14)	H6A—C6—H6B	107.8
C5—N1—C1	120.8 (3)	C8—C7—C6	111.9 (2)
C5—N1—H11	118 (2)	C8—C7—H7A	109.2
C1—N1—H11	121 (2)	C6—C7—H7A	109.2
C3—N2—C9	121.3 (2)	C8—C7—H7B	109.2
C3—N2—C6	121.92 (19)	C6—C7—H7B	109.2
C9—N2—C6	116.71 (19)	H7A—C7—H7B	107.9
N1—C1—C2	121.1 (3)	N3—C8—C7	177.6 (3)
N1—C1—H1	119.4	N2—C9—C10	113.06 (19)
C2—C1—H1	119.4	N2—C9—H9A	109.0
C1—C2—C3	120.2 (3)	C10—C9—H9A	109.0
C1—C2—H2	119.9	N2—C9—H9B	109.0
C3—C2—H2	119.9	C10—C9—H9B	109.0
N2—C3—C2	122.1 (2)	H9A—C9—H9B	107.8
N2—C3—C4	121.8 (2)	C11—C10—C9	110.8 (2)
C2—C3—C4	116.1 (2)	C11—C10—H10A	109.5
C5—C4—C3	120.1 (3)	C9—C10—H10A	109.5
C5—C4—H4	119.9	C11—C10—H10B	109.5
C3—C4—H4	119.9	C9—C10—H10B	109.5
N1—C5—C4	121.6 (3)	H10A—C10—H10B	108.1
N1—C5—H5	119.2	N4—C11—C10	176.7 (3)
C4—C5—H5	119.2

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2	0.84 (3)	2.09 (3)	2.913 (4)	164 (3)
C1—H1···O4^i	0.93	2.69	3.326 (4)	126
C2—H2···O1^i	0.93	2.66	3.579 (3)	168
C5—H5···O4	0.93	2.44	3.169 (4)	135
C6—H6b···N4^ii	0.97	2.65	3.487 (3)	145
C7—H7a···N3^iii	0.97	2.73	3.407 (4)	127
C9—H9a···N4^iv	0.97	2.65	3.163 (4)	113
C10—H10a···N4^iv	0.97	2.57	3.257 (4)	128

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