2-Amino­pyridinium (2-amino­pyridine)trichloridonickelate(II)

In the title compound, (C₅H₇N₂)[NiCl₃(C₅H₆N₂)], the Ni^II atom is four-coordinated by three chloride anions and one N atom of a 2-amino­pyridine ligand, forming a distorted tetra­hedral coordination. In the crystal structure, cations and complex anions are linked into chains along the a, b and c axes by N—H...Cl hydrogen bonds, leading to the formation of a three-dimensional framework.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.035
• wR factor = 0.080
• Data-to-parameter ratio = 38.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ni1    -   Cl1     ..      12.73 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ni1    -   Cl2     ..      17.69 su

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT141_ALERT_4_C su on a - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT143_ALERT_4_C su on c - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)         10 Ang.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          4
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   Cl3     ..       9.94 su
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           40.64
           From the CIF: _reflns_number_total               6427
           Count of symmetry unique reflns         4507
           Completeness (_total/calc)            142.60%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1920
           Fraction of Friedel pairs measured     0.426
           Are heavy atom types Z>Si present        yes
PLAT033_ALERT_2_G Flack Parameter Value Deviates from zero .......       0.06
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

2-Aminopyridine is used in the manufacture of pharmaceuticals, especially antihistaminic drugs (Windholz, 1976). As a part of our investigations on the binding modes of 2-aminopyridine with metals, we report here the crystal structure of 2-aminopyridinium (2-aminopyridine)trichloronickel(II).

The asymmetric unit of the title compound contains one 2-aminopyridinium cation and one (2-aminopyridine)trichloronickel(II) anion. Protonation of atom N3 of the uncomplexed 2-aminopyridine results in the widening of the C6—N3—C10 angle to 123.3 (2)°, which is 117.7 (1)° in neutral 2-aminopyridine (Chao et al., 1975). The bond lengths and angles are comparable with those observed in related structures (Bis & Zaworotko, 2005; Smith et al., 2000; Jebas et al., 2006).

In the monomeric complex, the Ni^II ion is four-coordinated by three Cl anions and the N atom of the 2-aminopyridine ligand, forming a distorted tetrahedral coordination (Fig 1). The Ni—Cl bond lengths (Table 1) are comparable with that reported in the literature (Valdés-Martínez et al., 2001; Batsanov et al., 2001; Sletten & Kovacs, 1993; Corain et al., 1985; Stibrany et al., 2004). The Cl—Ni—Cl bond angles (107.77 (2)° and 108.62 (2)°) are close to the values reported in the literature (Smith et al., 2001; Wei et al., 1995). The dihedral angle between the pyridine and pyridinium rings is 0.9 (2)°.

In the crystal structure, the cations and anionic complexes are stacked into chains along the a, b and c axes and are linked into a three-dimensional framework by N—H···Cl hydrogen bonds (Fig 2).

Related literature

For related literature, see: Batsanov & Howard (2001); Bis & Zaworotko (2005); Chao et al. (1975); Corain et al. (1985); Jebas et al. (2006); Valdés-Martínez et al. (2001); Sletten & Kovacs (1993); Smith et al. (2000, 2001); Stibrany et al. (2004); Wei & Willett (1995); Windholz (1976).

S2. Experimental

Solutions of 2-aminopyridine and NiCl₂.2H₂O in water were mixed in a molar ratio of 2:1. Few drops of dilute hydrochloric acid were added to the solution and heated at 363 K for 2 h. Blue crystals of the title compound were obtained by slow evaporation after a period of one week.

S3. Refinement

After checking their presence in a difference map, all H atoms except H1N3 were placed in calculated positions, with C—H = 0.93 Å and N—H = 0.86 Å and refined using a riding model, with U_iso(H) = 1.2U_eq(C,N). Atom H1N3 was refined isotropically.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures

	Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering.
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines.

2-Aminopyridinium (2-aminopyridine)trichloridonickelate(II)

Crystal data

(C5H7N2)[NiCl3(C5H6N2)]	F(000) = 720
Mr = 354.3	Dx = 1.68 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 8411 reflections
a = 12.9265 (1) Å	θ = 3.0–30.6°
b = 8.0644 (1) Å	µ = 1.94 mm^−1
c = 13.9893 (1) Å	T = 100 K
β = 106.163 (1)°	Block, blue
V = 1400.67 (2) Å^3	0.37 × 0.08 × 0.07 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	5088 reflections with I > 2σ(I)
Detector resolution: 8.33 pixels mm^-1	Rint = 0.031
ω scans	θmax = 40.6°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −23→23
Tmin = 0.533, Tmax = 0.876	k = −14→14
19539 measured reflections	l = −25→16
6427 independent reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.034P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.035	(Δ/σ)max < 0.001
wR(F^2) = 0.079	Δρmax = 0.52 e Å^−3
S = 1.05	Δρmin = −0.64 e Å^−3
6427 reflections	Absolute structure: Flack (1983), 1953 Friedel pairs
167 parameters	Absolute structure parameter: 0.065 (9)
2 restraints

Special details

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.

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

	x	y	z	Uiso*/Ueq
Ni1	0.245028 (18)	0.65589 (3)	0.188212 (18)	0.01865 (6)
Cl1	0.40142 (4)	0.66552 (7)	0.14504 (4)	0.01889 (9)
Cl2	0.19741 (4)	0.38637 (6)	0.19116 (4)	0.02255 (10)
Cl3	0.10912 (4)	0.79387 (7)	0.07906 (4)	0.02299 (10)
N1	0.26459 (13)	0.7760 (2)	0.31947 (12)	0.0157 (3)
N2	0.30301 (15)	0.5422 (2)	0.41934 (14)	0.0228 (4)
H2B	0.2895	0.4816	0.3667	0.027*
H2C	0.322	0.4966	0.4772	0.027*
N3	0.55299 (14)	0.0900 (2)	0.44965 (14)	0.0191 (3)
N4	0.53731 (16)	−0.1509 (2)	0.35719 (15)	0.0228 (4)
H4B	0.5574	−0.2072	0.4114	0.027*
H4C	0.5224	−0.2007	0.3006	0.027*
C1	0.29457 (15)	0.7074 (3)	0.41122 (15)	0.0181 (4)
C2	0.31669 (17)	0.8074 (3)	0.49792 (16)	0.0213 (4)
H2A	0.3384	0.7591	0.5607	0.026*
C3	0.30568 (17)	0.9761 (3)	0.48792 (18)	0.0254 (4)
H3A	0.3199	1.0431	0.5442	0.03*
C4	0.27352 (17)	1.0463 (3)	0.39438 (18)	0.0245 (4)
H4A	0.2652	1.1605	0.3867	0.029*
C5	0.25411 (16)	0.9441 (3)	0.31322 (17)	0.0198 (4)
H5A	0.2326	0.992	0.2503	0.024*
C6	0.52944 (15)	0.0123 (2)	0.36071 (15)	0.0173 (3)
C7	0.49768 (16)	0.1116 (3)	0.27449 (16)	0.0203 (4)
H7A	0.4813	0.0628	0.2118	0.024*
C8	0.49108 (16)	0.2795 (3)	0.28322 (16)	0.0217 (4)
H8A	0.4704	0.3447	0.2262	0.026*
C9	0.51508 (17)	0.3550 (3)	0.37731 (18)	0.0229 (4)
H9A	0.5093	0.4693	0.3832	0.027*
C10	0.54691 (16)	0.2575 (3)	0.45963 (17)	0.0222 (4)
H10A	0.5645	0.3051	0.5227	0.027*
H1N3	0.571 (2)	0.030 (3)	0.499 (2)	0.023 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02016 (11)	0.02167 (12)	0.01419 (12)	−0.00140 (10)	0.00489 (9)	−0.00168 (10)
Cl1	0.0188 (2)	0.0211 (2)	0.0179 (2)	−0.00022 (15)	0.00699 (18)	−0.00025 (16)
Cl2	0.0285 (2)	0.0194 (2)	0.0211 (2)	−0.00610 (19)	0.0092 (2)	−0.00511 (18)
Cl3	0.0208 (2)	0.0324 (3)	0.0142 (2)	0.00279 (19)	0.00214 (17)	0.00196 (19)
N1	0.0151 (7)	0.0181 (7)	0.0133 (7)	−0.0002 (6)	0.0030 (6)	0.0000 (6)
N2	0.0313 (9)	0.0201 (9)	0.0150 (8)	0.0021 (7)	0.0032 (7)	0.0003 (6)
N3	0.0170 (7)	0.0273 (9)	0.0132 (8)	0.0013 (6)	0.0043 (6)	0.0020 (7)
N4	0.0283 (9)	0.0220 (8)	0.0168 (9)	−0.0019 (7)	0.0038 (7)	0.0029 (6)
C1	0.0146 (8)	0.0238 (10)	0.0165 (9)	0.0012 (6)	0.0053 (7)	0.0011 (7)
C2	0.0180 (8)	0.0307 (11)	0.0149 (9)	−0.0009 (7)	0.0043 (7)	−0.0018 (8)
C3	0.0224 (9)	0.0269 (11)	0.0278 (12)	−0.0030 (8)	0.0087 (9)	−0.0105 (9)
C4	0.0251 (10)	0.0189 (9)	0.0309 (12)	−0.0026 (8)	0.0099 (9)	−0.0067 (9)
C5	0.0195 (8)	0.0179 (9)	0.0224 (10)	−0.0007 (7)	0.0065 (8)	−0.0002 (8)
C6	0.0153 (8)	0.0220 (9)	0.0142 (9)	−0.0021 (7)	0.0035 (7)	0.0011 (7)
C7	0.0183 (8)	0.0269 (10)	0.0145 (9)	0.0001 (7)	0.0023 (7)	0.0026 (8)
C8	0.0201 (9)	0.0261 (10)	0.0185 (10)	0.0034 (8)	0.0050 (8)	0.0059 (8)
C9	0.0204 (9)	0.0225 (10)	0.0272 (12)	0.0019 (7)	0.0092 (9)	−0.0010 (8)
C10	0.0183 (8)	0.0288 (11)	0.0200 (10)	0.0008 (8)	0.0062 (8)	−0.0052 (8)

Geometric parameters (Å, º)

Ni1—N1	2.0287 (17)	C2—C3	1.371 (3)
Ni1—Cl2	2.2625 (6)	C2—H2A	0.93
Ni1—Cl1	2.2665 (5)	C3—C4	1.380 (3)
Ni1—Cl3	2.2722 (6)	C3—H3A	0.93
N1—C1	1.352 (3)	C4—C5	1.369 (3)
N1—C5	1.363 (3)	C4—H4A	0.93
N2—C1	1.339 (3)	C5—H5A	0.93
N2—H2B	0.86	C6—C7	1.410 (3)
N2—H2C	0.86	C7—C8	1.364 (3)
N3—C6	1.350 (3)	C7—H7A	0.93
N3—C10	1.362 (3)	C8—C9	1.404 (3)
N3—H1N3	0.82 (3)	C8—H8A	0.93
N4—C6	1.322 (3)	C9—C10	1.360 (3)
N4—H4B	0.86	C9—H9A	0.93
N4—H4C	0.86	C10—H10A	0.93
C1—C2	1.417 (3)
N1—Ni1—Cl2	114.10 (5)	C2—C3—C4	120.0 (2)
N1—Ni1—Cl1	109.21 (5)	C2—C3—H3A	120
Cl2—Ni1—Cl1	107.77 (2)	C4—C3—H3A	120
N1—Ni1—Cl3	104.63 (5)	C5—C4—C3	118.5 (2)
Cl2—Ni1—Cl3	108.62 (2)	C5—C4—H4A	120.8
Cl1—Ni1—Cl3	112.60 (2)	C3—C4—H4A	120.8
C1—N1—C5	117.72 (18)	N1—C5—C4	123.6 (2)
C1—N1—Ni1	126.48 (14)	N1—C5—H5A	118.2
C5—N1—Ni1	115.59 (13)	C4—C5—H5A	118.2
C1—N2—H2B	120	N4—C6—N3	119.8 (2)
C1—N2—H2C	120	N4—C6—C7	122.7 (2)
H2B—N2—H2C	120	N3—C6—C7	117.51 (19)
C6—N3—C10	123.36 (19)	C8—C7—C6	119.8 (2)
C6—N3—H1N3	115.9 (18)	C8—C7—H7A	120.1
C10—N3—H1N3	120.7 (18)	C6—C7—H7A	120.1
C6—N4—H4B	120	C7—C8—C9	120.7 (2)
C6—N4—H4C	120	C7—C8—H8A	119.6
H4B—N4—H4C	120	C9—C8—H8A	119.6
N2—C1—N1	118.88 (18)	C10—C9—C8	118.6 (2)
N2—C1—C2	120.05 (19)	C10—C9—H9A	120.7
N1—C1—C2	121.1 (2)	C8—C9—H9A	120.7
C3—C2—C1	119.1 (2)	C9—C10—N3	119.9 (2)
C3—C2—H2A	120.4	C9—C10—H10A	120
C1—C2—H2A	120.4	N3—C10—H10A	120
Cl2—Ni1—N1—C1	28.37 (17)	C2—C3—C4—C5	−0.5 (3)
Cl1—Ni1—N1—C1	−92.28 (15)	C1—N1—C5—C4	0.8 (3)
Cl3—Ni1—N1—C1	146.95 (15)	Ni1—N1—C5—C4	−174.29 (16)
Cl2—Ni1—N1—C5	−156.98 (11)	C3—C4—C5—N1	0.1 (3)
Cl1—Ni1—N1—C5	82.36 (13)	C10—N3—C6—N4	179.99 (18)
Cl3—Ni1—N1—C5	−38.41 (13)	C10—N3—C6—C7	0.4 (3)
C5—N1—C1—N2	178.47 (16)	N4—C6—C7—C8	179.96 (19)
Ni1—N1—C1—N2	−7.0 (3)	N3—C6—C7—C8	−0.5 (3)
C5—N1—C1—C2	−1.4 (3)	C6—C7—C8—C9	−0.3 (3)
Ni1—N1—C1—C2	173.14 (13)	C7—C8—C9—C10	1.1 (3)
N2—C1—C2—C3	−178.84 (18)	C8—C9—C10—N3	−1.2 (3)
N1—C1—C2—C3	1.0 (3)	C6—N3—C10—C9	0.5 (3)
C1—C2—C3—C4	0.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···Cl2^i	0.82 (3)	2.81 (3)	3.380 (2)	128 (2)
N2—H2B···Cl2	0.86	2.53	3.3475 (19)	159
N2—H2C···Cl1^ii	0.86	2.63	3.4866 (19)	172
N4—H4B···Cl3^i	0.86	2.36	3.197 (2)	165
N4—H4C···Cl1^iii	0.86	2.54	3.344 (2)	156

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