2-[({[Bis(pyridin-2-yl)methylidene]hydrazinecarbonyl}hydrazinylidene)(pyridin-2-yl)methyl]pyridinium tetra-fluoro-borate.

In the title compound, C(23)H(19)N(8)O(+)·BF(4) (-), one pyridine N atom is protonated. Two intra-molecular N-H⋯N hydrogen bonds occur. In the crystal, inter-molecular N-H⋯N hydrogen bond links neighboring C(23)H(19)N(8)O(+) units into cyclic supra-molecular dimers while C-H⋯O hydrogen bonds link the C(23)H(19)N(8)O(+) units into a two-dimensional supra-molecular network structure.

Related literature

For the synthesis and crystal structure of the precursor ligand, 1,3-bis­(bis­(2-pyrid­yl)methyl­ene)amino)­urea, see: Manoj et al. (2005 ▶). For a tetra­nuclear iron(II) complex based on a deriv­ative of the title compound, see: Wu et al. (2009 ▶).

Experimental

Crystal data

C23H19N8O+·BF4 −

M = 510.27

Triclinic,

a = 7.9187 (16) Å

b = 10.626 (2) Å

c = 13.623 (3) Å

α = 90.03 (3)°

β = 91.50 (3)°

γ = 97.85 (3)°

V = 1135.1 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 123 K

0.22 × 0.19 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.974, T max = 0.981

18299 measured reflections

5175 independent reflections

4025 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.151

S = 0.98

5175 reflections

346 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.68 e Å−3

Δρmin = −0.49 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811025359/ez2251sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811025359/ez2251Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811025359/ez2251Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C23H19N8O+·BF4−	Z = 2
Mr = 510.27	F(000) = 524
Triclinic, P1	Dx = 1.493 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9187 (16) Å	Cell parameters from 3505 reflections
b = 10.626 (2) Å	θ = 2.3–26.7°
c = 13.623 (3) Å	µ = 0.12 mm−1
α = 90.03 (3)°	T = 123 K
β = 91.50 (3)°	Block, colorless
γ = 97.85 (3)°	0.22 × 0.19 × 0.16 mm
V = 1135.1 (4) Å3

Bruker APEXII CCD area-detector diffractometer	5175 independent reflections
Radiation source: fine-focus sealed tube	4025 reflections with I > 2σ(I)
graphite	Rint = 0.032
φ and ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→10
Tmin = 0.974, Tmax = 0.981	k = −13→13
18299 measured reflections	l = −17→17

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ2(Fo2) + (0.1033P)2 + 0.3032P] where P = (Fo2 + 2Fc2)/3
5175 reflections	(Δ/σ)max < 0.001
346 parameters	Δρmax = 0.68 e Å−3
0 restraints	Δρmin = −0.49 e Å−3

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.

	x	y	z	Uiso*/Ueq
H1	−0.020 (3)	0.896 (2)	0.6632 (16)	0.033 (6)*
H30	0.224 (3)	0.592 (2)	0.5650 (17)	0.041 (6)*
H40	0.141 (3)	0.567 (2)	0.3285 (17)	0.038 (6)*
O1	0.07813 (16)	0.75955 (10)	0.40804 (8)	0.0215 (3)
N1	0.05189 (17)	0.93425 (12)	0.70991 (9)	0.0151 (3)
N2	0.16150 (16)	0.75693 (12)	0.60077 (9)	0.0149 (3)
N3	0.17522 (17)	0.65646 (12)	0.54249 (9)	0.0147 (3)
N4	0.16693 (18)	0.56751 (12)	0.38758 (10)	0.0164 (3)
N6	0.15116 (17)	0.43582 (12)	0.22247 (9)	0.0178 (3)
N7	0.20613 (16)	0.14392 (12)	0.42932 (9)	0.0154 (3)
N8	0.32921 (18)	0.55934 (13)	0.69471 (10)	0.0210 (3)
N5	0.21894 (16)	0.46491 (12)	0.43220 (9)	0.0147 (3)
C13	0.24217 (19)	0.36556 (14)	0.38154 (11)	0.0143 (3)
C8	0.27284 (19)	0.65124 (14)	0.74875 (11)	0.0163 (3)
C19	0.22420 (19)	0.34758 (14)	0.27322 (11)	0.0152 (3)
C14	0.29165 (19)	0.26067 (14)	0.44455 (11)	0.0142 (3)
C20	0.2835 (2)	0.24569 (15)	0.22615 (12)	0.0193 (3)
H20	0.3378	0.1878	0.2621	0.023*
C15	0.4159 (2)	0.28667 (15)	0.51871 (11)	0.0175 (3)
H15	0.4729	0.3685	0.5276	0.021*
C5	0.2903 (2)	0.93506 (16)	0.81632 (12)	0.0219 (4)
H5	0.3817	0.8971	0.8408	0.026*
C1	0.13426 (19)	0.66862 (14)	0.44403 (11)	0.0152 (3)
C16	0.4535 (2)	0.18811 (15)	0.57937 (11)	0.0185 (3)
H16	0.5366	0.2026	0.6291	0.022*
C6	0.1830 (2)	0.87492 (14)	0.74368 (11)	0.0158 (3)
C17	0.3646 (2)	0.06836 (15)	0.56384 (11)	0.0183 (3)
H17	0.3867	0.0008	0.6033	0.022*
C9	0.2753 (2)	0.64769 (16)	0.85125 (12)	0.0207 (3)
H9	0.2326	0.7102	0.8871	0.025*
C18	0.2421 (2)	0.05004 (14)	0.48887 (11)	0.0174 (3)
H18	0.1821	−0.0308	0.4794	0.021*
C7	0.20552 (19)	0.75424 (14)	0.69332 (11)	0.0151 (3)
C12	0.3918 (2)	0.46578 (17)	0.74277 (13)	0.0261 (4)
H12	0.4309	0.4025	0.7059	0.031*
C2	0.0211 (2)	1.04672 (15)	0.74398 (12)	0.0208 (3)
H2	−0.0712	1.0831	0.7189	0.025*
C23	0.1328 (2)	0.42228 (16)	0.12492 (12)	0.0218 (4)
H23	0.0845	0.4838	0.0896	0.026*
C22	0.1824 (2)	0.32125 (17)	0.07416 (12)	0.0245 (4)
H22	0.1634	0.3135	0.0066	0.029*
C10	0.3423 (2)	0.54963 (16)	0.89862 (12)	0.0237 (4)
H10	0.3467	0.5465	0.9669	0.028*
C11	0.4023 (2)	0.45699 (16)	0.84425 (13)	0.0254 (4)
H11	0.4485	0.3905	0.8745	0.030*
C21	0.2605 (2)	0.23194 (16)	0.12549 (12)	0.0239 (4)
H21	0.2970	0.1639	0.0930	0.029*
C3	0.1261 (2)	1.10889 (17)	0.81633 (13)	0.0276 (4)
H3	0.1061	1.1874	0.8401	0.033*
C4	0.2611 (2)	1.05221 (18)	0.85257 (13)	0.0284 (4)
H4	0.3330	1.0925	0.9015	0.034*
B1	0.2959 (3)	0.8076 (2)	0.10945 (17)	0.0306 (5)
F1	0.3407 (2)	0.7618 (2)	0.20065 (11)	0.0788 (5)
F2	0.42071 (15)	0.78336 (12)	0.04479 (8)	0.0381 (3)
F3	0.14286 (17)	0.73994 (14)	0.07990 (12)	0.0618 (4)
F4	0.2908 (2)	0.93300 (14)	0.11734 (17)	0.0898 (7)

	U11	U22	U33	U12	U13	U23
O1	0.0329 (7)	0.0149 (6)	0.0180 (6)	0.0091 (5)	−0.0041 (5)	−0.0001 (4)
N1	0.0181 (7)	0.0144 (6)	0.0127 (6)	0.0024 (5)	−0.0015 (5)	−0.0014 (5)
N2	0.0157 (6)	0.0142 (6)	0.0147 (6)	0.0021 (5)	0.0002 (5)	−0.0019 (5)
N3	0.0194 (7)	0.0118 (6)	0.0135 (6)	0.0049 (5)	−0.0013 (5)	−0.0010 (5)
N4	0.0245 (7)	0.0134 (6)	0.0120 (6)	0.0052 (5)	−0.0028 (5)	−0.0002 (5)
N6	0.0194 (7)	0.0182 (7)	0.0157 (6)	0.0022 (5)	−0.0008 (5)	−0.0007 (5)
N7	0.0172 (6)	0.0135 (6)	0.0157 (6)	0.0031 (5)	0.0009 (5)	−0.0016 (5)
N8	0.0269 (8)	0.0194 (7)	0.0181 (7)	0.0082 (6)	−0.0022 (6)	−0.0005 (5)
N5	0.0164 (6)	0.0116 (6)	0.0160 (6)	0.0017 (5)	−0.0014 (5)	0.0013 (5)
C13	0.0139 (7)	0.0139 (7)	0.0147 (7)	0.0008 (6)	−0.0005 (6)	−0.0006 (6)
C8	0.0141 (7)	0.0181 (8)	0.0165 (7)	0.0019 (6)	−0.0017 (6)	0.0001 (6)
C19	0.0150 (7)	0.0151 (7)	0.0147 (7)	−0.0008 (6)	0.0006 (6)	−0.0001 (6)
C14	0.0158 (7)	0.0130 (7)	0.0145 (7)	0.0037 (6)	0.0028 (6)	−0.0017 (5)
C20	0.0224 (8)	0.0177 (8)	0.0180 (8)	0.0028 (6)	0.0036 (6)	0.0002 (6)
C15	0.0176 (8)	0.0151 (7)	0.0194 (8)	0.0012 (6)	−0.0011 (6)	−0.0011 (6)
C5	0.0204 (8)	0.0261 (9)	0.0191 (8)	0.0040 (7)	−0.0034 (6)	−0.0050 (6)
C1	0.0165 (7)	0.0138 (7)	0.0150 (7)	0.0015 (6)	−0.0007 (6)	−0.0008 (6)
C16	0.0180 (8)	0.0226 (8)	0.0158 (7)	0.0058 (6)	−0.0024 (6)	−0.0003 (6)
C6	0.0167 (7)	0.0172 (7)	0.0135 (7)	0.0025 (6)	0.0015 (6)	−0.0004 (6)
C17	0.0205 (8)	0.0181 (8)	0.0175 (7)	0.0064 (6)	0.0025 (6)	0.0050 (6)
C9	0.0222 (8)	0.0231 (8)	0.0172 (8)	0.0049 (7)	0.0000 (6)	0.0001 (6)
C18	0.0199 (8)	0.0130 (7)	0.0196 (8)	0.0028 (6)	0.0027 (6)	−0.0007 (6)
C7	0.0139 (7)	0.0157 (7)	0.0158 (7)	0.0020 (6)	0.0008 (6)	−0.0005 (6)
C12	0.0361 (10)	0.0214 (8)	0.0229 (9)	0.0128 (7)	−0.0034 (7)	−0.0009 (7)
C2	0.0259 (9)	0.0180 (8)	0.0196 (8)	0.0070 (6)	0.0004 (7)	−0.0017 (6)
C23	0.0246 (9)	0.0244 (8)	0.0159 (8)	0.0025 (7)	−0.0027 (6)	0.0009 (6)
C22	0.0321 (10)	0.0275 (9)	0.0125 (8)	−0.0011 (7)	0.0006 (7)	−0.0027 (6)
C10	0.0281 (9)	0.0266 (9)	0.0158 (8)	0.0020 (7)	−0.0031 (7)	0.0044 (6)
C11	0.0306 (9)	0.0218 (8)	0.0246 (9)	0.0080 (7)	−0.0058 (7)	0.0057 (7)
C21	0.0310 (9)	0.0212 (8)	0.0195 (8)	0.0024 (7)	0.0068 (7)	−0.0050 (6)
C3	0.0351 (10)	0.0214 (9)	0.0266 (9)	0.0056 (7)	−0.0011 (8)	−0.0122 (7)
C4	0.0287 (9)	0.0302 (9)	0.0252 (9)	0.0013 (7)	−0.0055 (7)	−0.0130 (7)
B1	0.0283 (11)	0.0281 (11)	0.0357 (12)	0.0049 (9)	−0.0021 (9)	−0.0079 (9)
F1	0.0849 (13)	0.1169 (15)	0.0361 (8)	0.0202 (11)	−0.0023 (8)	0.0033 (9)
F2	0.0329 (6)	0.0449 (7)	0.0360 (6)	0.0037 (5)	−0.0016 (5)	−0.0140 (5)
F3	0.0313 (7)	0.0607 (9)	0.0918 (12)	0.0014 (6)	−0.0033 (7)	−0.0231 (8)
F4	0.0708 (12)	0.0280 (8)	0.174 (2)	0.0124 (7)	0.0381 (12)	−0.0134 (10)

O1—C1	1.2157 (18)	C5—C4	1.389 (2)
N1—C2	1.337 (2)	C5—H5	0.9300
N1—C6	1.357 (2)	C16—C17	1.381 (2)
N1—H1	0.90 (2)	C16—H16	0.9300
N2—C7	1.301 (2)	C6—C7	1.488 (2)
N2—N3	1.3481 (18)	C17—C18	1.385 (2)
N3—C1	1.3820 (19)	C17—H17	0.9300
N3—H30	0.89 (2)	C9—C10	1.385 (2)
N4—N5	1.3557 (17)	C9—H9	0.9300
N4—C1	1.378 (2)	C18—H18	0.9300
N4—H40	0.82 (2)	C12—C11	1.387 (2)
N6—C23	1.339 (2)	C12—H12	0.9300
N6—C19	1.349 (2)	C2—C3	1.380 (2)
N7—C18	1.3418 (19)	C2—H2	0.9300
N7—C14	1.343 (2)	C23—C22	1.383 (2)
N8—C12	1.335 (2)	C23—H23	0.9300
N8—C8	1.353 (2)	C22—C21	1.383 (2)
N5—C13	1.297 (2)	C22—H22	0.9300
C13—C19	1.489 (2)	C10—C11	1.374 (3)
C13—C14	1.495 (2)	C10—H10	0.9300
C8—C9	1.396 (2)	C11—H11	0.9300
C8—C7	1.480 (2)	C21—H21	0.9300
C19—C20	1.399 (2)	C3—C4	1.378 (3)
C14—C15	1.392 (2)	C3—H3	0.9300
C20—C21	1.384 (2)	C4—H4	0.9300
C20—H20	0.9300	B1—F4	1.342 (3)
C15—C16	1.393 (2)	B1—F3	1.373 (3)
C15—H15	0.9300	B1—F1	1.390 (3)
C5—C6	1.384 (2)	B1—F2	1.391 (3)
C2—N1—C6	123.20 (14)	C16—C17—H17	120.4
C2—N1—H1	117.6 (14)	C18—C17—H17	120.4
C6—N1—H1	119.2 (14)	C10—C9—C8	118.98 (15)
C7—N2—N3	120.02 (13)	C10—C9—H9	120.5
N2—N3—C1	116.77 (13)	C8—C9—H9	120.5
N2—N3—H30	120.6 (15)	N7—C18—C17	122.81 (14)
C1—N3—H30	121.9 (15)	N7—C18—H18	118.6
N5—N4—C1	119.28 (13)	C17—C18—H18	118.6
N5—N4—H40	121.7 (16)	N2—C7—C8	128.54 (14)
C1—N4—H40	118.4 (16)	N2—C7—C6	111.30 (13)
C23—N6—C19	118.19 (14)	C8—C7—C6	120.15 (13)
C18—N7—C14	118.10 (13)	N8—C12—C11	124.13 (16)
C12—N8—C8	117.68 (14)	N8—C12—H12	117.9
C13—N5—N4	120.72 (13)	C11—C12—H12	117.9
N5—C13—C19	127.73 (14)	N1—C2—C3	120.10 (16)
N5—C13—C14	112.55 (13)	N1—C2—H2	119.9
C19—C13—C14	119.72 (13)	C3—C2—H2	119.9
N8—C8—C9	121.70 (14)	N6—C23—C22	123.18 (16)
N8—C8—C7	116.38 (13)	N6—C23—H23	118.4
C9—C8—C7	121.90 (14)	C22—C23—H23	118.4
N6—C19—C20	121.65 (14)	C21—C22—C23	118.89 (15)
N6—C19—C13	116.70 (13)	C21—C22—H22	120.6
C20—C19—C13	121.63 (14)	C23—C22—H22	120.6
N7—C14—C15	122.42 (14)	C11—C10—C9	119.63 (15)
N7—C14—C13	117.28 (13)	C11—C10—H10	120.2
C15—C14—C13	120.22 (13)	C9—C10—H10	120.2
C21—C20—C19	119.31 (15)	C10—C11—C12	117.84 (15)
C21—C20—H20	120.3	C10—C11—H11	121.1
C19—C20—H20	120.3	C12—C11—H11	121.1
C14—C15—C16	118.96 (14)	C22—C21—C20	118.71 (15)
C14—C15—H15	120.5	C22—C21—H21	120.6
C16—C15—H15	120.5	C20—C21—H21	120.6
C6—C5—C4	119.88 (16)	C4—C3—C2	118.64 (16)
C6—C5—H5	120.1	C4—C3—H3	120.7
C4—C5—H5	120.1	C2—C3—H3	120.7
O1—C1—N4	121.74 (14)	C3—C4—C5	120.25 (16)
O1—C1—N3	124.77 (14)	C3—C4—H4	119.9
N4—C1—N3	113.48 (13)	C5—C4—H4	119.9
C17—C16—C15	118.44 (14)	F4—B1—F3	113.43 (19)
C17—C16—H16	120.8	F4—B1—F1	108.7 (2)
C15—C16—H16	120.8	F3—B1—F1	107.76 (19)
N1—C6—C5	117.93 (14)	F4—B1—F2	110.79 (19)
N1—C6—C7	116.20 (13)	F3—B1—F2	108.98 (17)
C5—C6—C7	125.70 (14)	F1—B1—F2	106.95 (17)
C16—C17—C18	119.25 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N7i	0.90 (2)	1.92 (2)	2.792 (2)	163.5 (15)
N3—H30···N8	0.88 (2)	1.99 (2)	2.658 (2)	132.1 (19)
N4—H40···N6	0.83 (2)	2.02 (2)	2.640 (2)	132 (2)
C2—H2···O1ii	0.93	2.41	3.083 (2)	129.(1)
C18—H18···O1iii	0.93	2.46	3.355 (2)	162.(1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N7i	0.90 (2)	1.92 (2)	2.792 (2)	163.5 (15)
N3—H30⋯N8	0.88 (2)	1.99 (2)	2.658 (2)	132.1 (19)
N4—H40⋯N6	0.83 (2)	2.02 (2)	2.640 (2)	132 (2)
C2—H2⋯O1ii	0.93	2.41	3.083 (2)	129 (1)
C18—H18⋯O1iii	0.93	2.46	3.355 (2)	162 (1)

Symmetry codes: (i) ; (ii) ; (iii) .