Preparation and characterization of tetrachlorocobaltates(II) of α,ω-alkylenediammonium. Magnetic and thermal properties. Crystal structure of [NH₃(CH₂)₅NH₃]CoCl₄

Tetrachlorocobaltates(II) of diprotonated α,ω-diamino­alkanes with the formula [NH₃(CH₂)_nNH₃]CoCl₄, where n = 5 (cadaverine; 1,5-pentanediammonium tetra­chloro­cobaltate), 8 (1,8-octanediammonium tetra­chloro­co­baltate) and 10 (1,10-decanediammonium tetra­chloro­cobaltate), were prepared. The compounds were studied by mass spectrometry, FT-IR and visible spectroscopy, magnetic susceptibility techniques and thermal analysis. The compounds contain the tetra­hedral tetrachlorocobaltate(II) ion and the corresponding diprotonated diamine (cadaverine, 1,8-octa­methylenediamine and 1,10-decamethylenedi­amine). The compound corresponding to cadaverine crystallizes in the monoclinic space group P2₁/c, with lattice parameters a = 7.1633 (7), b = 15.940 (3), c = 11.137 (2) Å, β = 98.44 (1)° and Z = 4. Its crystal structure contains slightly distorted tetrahedral CoCl ions: the largest difference in Co—Cl bond lengths is 0.029 Å and the largest difference in Cl—Co—Cl angles is 7.76°. The compound also contains diprotonated cadaverine ions. An extensive hydrogen-bonding network connects these ions. The slightly positive deviations of the magnetic susceptibility from the Curie–Weiss law are in agreement with the ⁴A₂ ground state for the tetrachlorocobaltate anion. The compounds with eight and ten C atoms show phase transitions in the solid state and a greater complexity is observed in their differential scanning calorimetry curves. Unfortunately, no suitable single crystals of these could be obtained.

Computing details

Program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEP; software used to prepare material for publication: SHELXL93 (Sheldrick, 1993).

1,5-pentanediammonium tetrachlorocobaltate

Crystal data

[(NH3)2C5H10]·CoCl4	F(000) = 620
Mr = 304.93	Dx = 1.610 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.5418 Å
a = 7.1633 (7) Å	Cell parameters from 54 reflections
b = 15.940 (3) Å	θ = 4.9–66.1°
c = 11.137 (2) Å	µ = 18.18 mm^−1
β = 98.44 (1)°	T = 293 K
V = 1257.9 (3) Å^3	Rectangular, blue
Z = 4	0.47 × 0.27 × 0.13 mm

Data collection

Seifert XRD 3000 diffractometer	1586 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.086
Graphite monochromator	θmax = 66.1°, θmin = 4.9°
2θ–ω scans	h = −8→8
Absorption correction: empirical (using intensity measurements)	k = 0→19
Tmin = 0.073, Tmax = 0.203	l = 0→13
2148 measured reflections	2 standard reflections every 100 reflections
2147 independent reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.178	Iso
S = 1.01	Calculated w = 1/[σ^2(Fo^2) + (0.123P)^2] where P = (Fo^2 + 2Fc^2)/3
2147 reflections	(Δ/σ)max = −0.111
157 parameters	Δρmax = 0.85 e Å^−3
0 restraints	Δρmin = −0.79 e Å^−3

Special details

Experimental. The large bond distances N(1)—H(112), N(2)—H(221), N(2)—H(222) and N(2)—H(223) were distorted by the hydrogen bond involved.

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

	x	y	z	Uiso*/Ueq
Co1	0.38109 (15)	0.37752 (6)	−0.19215 (9)	0.0272 (3)
Cl1	0.4432 (3)	0.47207 (10)	−0.3351 (2)	0.0392 (5)
Cl2	0.4330 (3)	0.24663 (10)	−0.2661 (2)	0.0403 (5)
Cl3	0.0821 (2)	0.38592 (11)	−0.1477 (2)	0.0395 (5)
Cl4	0.5827 (2)	0.38967 (10)	−0.0163 (2)	0.0353 (4)
N1	0.6059 (10)	0.3216 (5)	0.5061 (7)	0.040 (2)
N2	1.2147 (9)	0.4502 (4)	0.1282 (6)	0.043 (2)
C1	0.8109 (12)	0.3114 (6)	0.5539 (8)	0.045 (2)
C2	0.9315 (13)	0.3705 (5)	0.4952 (7)	0.046 (2)
C3	0.9344 (11)	0.3554 (4)	0.3613 (7)	0.038 (2)
C4	1.0719 (11)	0.4118 (5)	0.3095 (7)	0.034 (2)
C5	1.0692 (11)	0.3984 (4)	0.1769 (7)	0.032 (2)
H11	0.825 (18)	0.253 (8)	0.543 (12)	0.12 (5)*
H12	0.830 (12)	0.316 (6)	0.632 (9)	0.06 (3)*
H21	1.054 (13)	0.369 (5)	0.532 (8)	0.05 (3)*
H22	0.8926	0.4301	0.5102	0.09 (4)*
H31	0.8044	0.3607	0.3131	0.10 (4)*
H32	0.965 (14)	0.288 (7)	0.350 (10)	0.09 (3)*
H41	1.175 (19)	0.407 (8)	0.357 (12)	0.12 (5)*
H42	1.039 (12)	0.474 (6)	0.317 (8)	0.06 (3)*
H51	1.102 (12)	0.352 (6)	0.167 (8)	0.05 (3)*
H52	0.931 (13)	0.411 (5)	0.141 (8)	0.06 (3)*
H111	0.591 (8)	0.307 (4)	0.426 (6)	0.018 (16)*
H112	0.575 (13)	0.378 (6)	0.538 (9)	0.07 (3)*
H113	0.564 (17)	0.290 (9)	0.550 (12)	0.11 (5)*
H221	1.3440	0.4340	0.1704	0.044*
H222	1.1931	0.5108	0.1417	0.12 (5)*
H223	1.2130	0.4405	0.0382	0.08 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0298 (6)	0.0143 (5)	0.0339 (6)	−0.0009 (4)	−0.0074 (4)	0.0006 (4)
Cl1	0.0523 (11)	0.0213 (8)	0.0399 (9)	−0.0038 (7)	−0.0072 (7)	0.0099 (7)
Cl2	0.0587 (12)	0.0162 (8)	0.0441 (10)	−0.0042 (7)	0.0012 (8)	−0.0066 (7)
Cl3	0.0266 (9)	0.0377 (10)	0.0506 (11)	−0.0002 (7)	−0.0061 (7)	−0.0077 (8)
Cl4	0.0354 (9)	0.0220 (8)	0.0420 (9)	−0.0017 (6)	−0.0161 (7)	0.0026 (7)
N1	0.044 (4)	0.037 (4)	0.036 (4)	−0.011 (3)	0.001 (3)	−0.005 (3)
N2	0.035 (3)	0.049 (4)	0.043 (4)	−0.013 (3)	−0.003 (3)	−0.003 (3)
C1	0.042 (5)	0.044 (5)	0.044 (5)	−0.012 (4)	−0.010 (4)	0.016 (4)
C2	0.052 (5)	0.033 (4)	0.045 (5)	−0.017 (4)	−0.015 (4)	0.003 (3)
C3	0.045 (4)	0.019 (3)	0.044 (4)	−0.006 (3)	−0.011 (3)	0.000 (3)
C4	0.036 (4)	0.025 (4)	0.038 (4)	−0.005 (3)	−0.003 (3)	−0.005 (3)
C5	0.032 (4)	0.017 (3)	0.044 (4)	−0.003 (3)	−0.006 (3)	−0.001 (3)

Geometric parameters (Å, º)

Co1—Cl1	2.283 (2)	N1—H113	0.79 (13)
Co1—Cl2	2.293 (2)	N2—H221	1.009 (6)
Co1—Cl3	2.271 (2)	N2—H222	0.993 (7)
Co1—Cl4	2.264 (2)	N2—H223	1.012 (6)
Co1—Cl4	2.264 (2)	C1—H11	0.95 (13)
Co1—Cl3	2.271 (2)	C1—H12	0.86 (9)
N1—C1	1.495 (10)	C2—H21	0.91 (9)
N2—C5	1.492 (9)	C2—H22	1.010 (9)
C1—C2	1.492 (11)	C3—H31	1.008 (8)
C2—C3	1.514 (11)	C3—H32	1.10 (11)
C3—C4	1.510 (10)	C4—H41	0.85 (13)
C4—C5	1.489 (10)	C4—H42	1.02 (10)
N1—H111	0.92 (7)	C5—H51	0.79 (9)
N1—H112	1.01 (10)	C5—H52	1.03 (9)
Cl4—Co1—Cl3	107.97 (8)	N1—C1—H11	100 (8)
Cl4—Co1—Cl1	112.44 (7)	C2—C1—H12	112 (6)
Cl3—Co1—Cl1	113.55 (8)	N1—C1—H12	111 (6)
Cl4—Co1—Cl2	105.79 (7)	H11—C1—H12	102 (10)
Cl3—Co1—Cl2	109.84 (8)	C1—C2—H21	111 (5)
Cl1—Co1—Cl2	106.96 (8)	C3—C2—H21	107 (6)
C2—C1—N1	112.2 (7)	C1—C2—H22	109.3 (9)
C1—C2—C3	115.0 (7)	C3—C2—H22	110.9 (7)
C4—C3—C2	112.7 (6)	H21—C2—H22	103 (5)
C5—C4—C3	112.3 (6)	C4—C3—H31	110.5 (7)
C4—C5—N2	111.9 (6)	C2—C3—H31	111.5 (7)
C1—N1—H111	107 (4)	C4—C3—H32	112 (5)
C1—N1—H112	103 (5)	C2—C3—H32	108 (6)
H111—N1—H112	125 (7)	H31—C3—H32	102 (6)
C1—N1—H113	99 (9)	C5—C4—H41	120 (9)
H111—N1—H113	116 (10)	C3—C4—H41	105 (9)
H112—N1—H113	103 (10)	C5—C4—H42	105 (5)
C5—N2—H221	109.4 (6)	C3—C4—H42	112 (5)
C5—N2—H222	110.5 (6)	H41—C4—H42	104 (10)
H221—N2—H222	109.3 (6)	C4—C5—H51	108 (6)
C5—N2—H223	111.6 (6)	N2—C5—H51	103 (6)
H221—N2—H223	107.4 (6)	C4—C5—H52	104 (5)
H222—N2—H223	108.6 (6)	N2—C5—H52	115 (5)
C2—C1—H11	119 (8)	H51—C5—H52	115 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H111···Cl2^i	0.92 (7)	2.42 (6)	3.29 (1)	155
N1—H112···Cl1^ii	1.00 (10)	2.3 (1)	3.29 (1)	157
N1—H113···Cl2^ii	0.79 (13)	2.5 (1)	3.21 (1)	155
N2—H223···Cl3^iii	1.01	2.31	3.25 (1)	152

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