[N-(2-Amino­ethyl)-N,N-bis(3-amino­propyl)­amine]­dichlorocobalt(III) chloride, [Co(abap)Cl₂]Cl

Structural analysis of the title compound, [Co(abap)Cl₂]Cl, where abap is N-(2-amino­ethyl)-N,N-bis(3-amino­propyl)­amine (C₈H₂₂N₄), confirms that the asymmetric amine ligand is oriented such that the N atoms of the five-membered chelate ring are in the same plane as the chloride ligands.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.023
• wR factor = 0.051
• Data-to-parameter ratio = 19.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_420  Alert C D-H without acceptor       N(12)  -   H(12A)            ?

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.935
          Tmax scaled      0.722 Tmin scaled      0.619

REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.00
         From the CIF: _reflns_number_total               2850
         Count of symmetry unique reflns         1740
         Completeness (_total/calc)            163.79%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1110
         Fraction of Friedel pairs measured     0.638
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The asymmetric tetraamine ligand abap {abap is N-(2-aminoethyl)-N,N-bis(3-aminopropyl)amine} can coordinate to four mututally cis sites of a six-coordinate metal complex in two ways. Coordination such that the N atoms of a six-membered chelate ring lie in the same plane as the remaining ligand(s) gives the `6' isomer, as found in the structurally characterized complex [Co(abap)O<sub>2</sub>NO](ClO<sub>4</sub>)<sub>2</sub> (Fanshawe & Blackman, 1995), while the `5' isomer results on coordination of the ligand so that the five-membered chelate ring lies in the same plane as the ancillary ligand(s). The structure of [Co(abap)Cl₂]Cl described herein confirms assignment of this complex as the `5' isomer. The structure consists of a Co<sup>III</sup> ion coordinated to four N atoms of the abap ligand, with coordination completed by two chloride ligands. A single chloride counter-ion balances the charge. Co—N bond lengths are typical of Co<sup>III</sup> complexes, with the bond to the tertiary N atom of the abap ligand being the longest [2.030 (2) Å]. Similarly lengthened Co—N (tertiary) bonds have been observed in [Co(abap)(NO<sub>2</sub>)<sub>2</sub>]X (X = Cl<sup>-</sup>, ClO<sub>4</sub><sup>-</sup>·H<sub>2</sub>O, PF<sub>6</sub><sup>-</sup>·H<sub>2</sub>O, I<sup>-</sup>·H<sub>2</sub>O), all of which crystallize as the `5' isomer (Bernal et al., 1996). The six-membered chelate rings adopt chair conformations, while the conformation of the five-membered ring is λ. The bond angles involving the primary N atoms of the six-membered chelate rings (C5—N12—Co1 and C8—N13—Co1) are 122.10 (16) and 121.92 (15)°, respectively. The expansion of these angles, when compared to the corresponding angle in the five-membered chelate ring [C1—N11—Co1 109.89 (15)°] presumably reflects the inherently greater strain present in a six-membered ring having one angle significantly larger than 90°.

S2. Experimental

[Co(abap)(O₂NO)](ClO₄)₂ (1.0 g) was dissolved in water and loaded onto a Dowex 50 W x 2 cation-exchange column. The column was washed with water and 1 M HCl before the complex was eluted with 2 M HCl. The purple eluate was collected and taken to dryness by rotary evaporation to give a blue solid which was crystallized from dilute HCl. X-ray quality crystals were obtained on slow evaporation of a concentrated solution of the product in 5 M HCl.

Computing details

Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: WinGX.

Figures

Fig. 1. The cation of (I) with displacement ellipsoids at the 50% probability level.

[N-(2-Aminoethyl)-N,N-bis(3-aminopropyl)amine]dichlorocobalt(III) chloride

Crystal data

[CoCl2(C8H22N4)]Cl	Dx = 1.638 Mg m^−3
Mr = 339.58	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 16 reflections
a = 8.405 (2) Å	θ = 5–12.5°
b = 10.2633 (14) Å	µ = 1.81 mm^−1
c = 15.9652 (15) Å	T = 173 K
V = 1377.2 (5) Å^3	Block, blue
Z = 4	0.42 × 0.20 × 0.18 mm
F(000) = 704

Data collection

Siemens P4 diffractometer	2717 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 27.0°, θmin = 2.4°
ω scans	h = −10→8
Absorption correction: ψ scan (SHELXTL-Plus; Sheldrick, 1990)	k = 0→13
Tmin = 0.662, Tmax = 0.772	l = 0→20
3058 measured reflections	3 standard reflections every 997 reflections
2850 independent reflections	intensity decay: <2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.023	H-atom parameters constrained
wR(F^2) = 0.051	w = 1/[σ^2(Fo^2) + (0.0258P)^2 + 0.2974P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2850 reflections	Δρmax = 0.25 e Å^−3
145 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Absolute structure: Flack (1983); 1110 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.004 (13)

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.

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.

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

	x	y	z	Uiso*/Ueq
Co1	0.83241 (3)	0.94312 (3)	0.904417 (19)	0.01263 (7)
Cl1	1.07387 (7)	1.00598 (6)	0.95605 (4)	0.02292 (13)
Cl2	0.75209 (7)	0.86582 (5)	1.02940 (3)	0.01936 (12)
Cl3	1.18810 (7)	0.81084 (6)	0.72166 (4)	0.02283 (13)
N11	0.9031 (2)	1.0042 (2)	0.79472 (11)	0.0174 (4)
H11A	0.8943	1.0934	0.7920	0.021*
H11B	1.0083	0.9825	0.7869	0.021*
N12	0.7618 (2)	1.11931 (19)	0.93904 (12)	0.0185 (4)
H12A	0.8282	1.1453	0.9817	0.022*
H12B	0.7811	1.1741	0.8946	0.022*
N13	0.9374 (2)	0.77486 (18)	0.88178 (12)	0.0152 (4)
H13A	0.9886	0.7831	0.8311	0.018*
H13B	1.0153	0.7648	0.9217	0.018*
N14	0.6235 (2)	0.89841 (18)	0.84746 (12)	0.0147 (4)
C1	0.8049 (3)	0.9440 (3)	0.72812 (14)	0.0215 (5)
H1A	0.8399	0.8533	0.7177	0.026*
H1B	0.8150	0.9940	0.6753	0.026*
C2	0.6358 (3)	0.9459 (3)	0.75831 (14)	0.0202 (5)
H2A	0.5700	0.8898	0.7217	0.024*
H2B	0.5937	1.0359	0.7547	0.024*
C3	0.4762 (3)	0.9593 (2)	0.88573 (15)	0.0198 (5)
H3A	0.4558	0.9161	0.9401	0.024*
H3B	0.3847	0.9397	0.8488	0.024*
C4	0.4800 (3)	1.1056 (2)	0.90051 (19)	0.0254 (5)
H4A	0.5085	1.1498	0.8475	0.030*
H4B	0.3723	1.1353	0.9167	0.030*
C5	0.5963 (3)	1.1457 (2)	0.96740 (17)	0.0237 (5)
H5A	0.5838	1.2398	0.9795	0.028*
H5B	0.5745	1.0966	1.0195	0.028*
C6	0.5835 (3)	0.7542 (2)	0.84920 (16)	0.0191 (5)
H6A	0.5558	0.7308	0.9076	0.023*
H6B	0.4868	0.7410	0.8149	0.023*
C7	0.7082 (3)	0.6590 (2)	0.81917 (16)	0.0214 (5)
H7A	0.6595	0.5717	0.8132	0.026*
H7B	0.7469	0.6865	0.7633	0.026*
C8	0.8472 (3)	0.6508 (2)	0.87878 (14)	0.0184 (5)
H8A	0.8078	0.6296	0.9356	0.022*
H8B	0.9191	0.5797	0.8608	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01138 (14)	0.01210 (13)	0.01442 (13)	−0.00034 (13)	0.00047 (12)	−0.00006 (12)
Cl1	0.0152 (3)	0.0213 (3)	0.0322 (3)	−0.0019 (2)	−0.0044 (2)	−0.0048 (3)
Cl2	0.0207 (3)	0.0223 (3)	0.0151 (2)	−0.0005 (2)	0.0019 (2)	0.0012 (2)
Cl3	0.0222 (3)	0.0175 (3)	0.0288 (3)	−0.0001 (2)	0.0054 (3)	−0.0045 (2)
N11	0.0158 (10)	0.0170 (9)	0.0194 (10)	0.0016 (9)	0.0026 (8)	0.0020 (8)
N12	0.0176 (10)	0.0156 (9)	0.0222 (10)	−0.0009 (9)	0.0009 (9)	−0.0027 (8)
N13	0.0121 (10)	0.0157 (9)	0.0178 (10)	0.0004 (8)	−0.0014 (8)	0.0002 (7)
N14	0.0134 (10)	0.0146 (9)	0.0162 (9)	0.0011 (7)	0.0005 (7)	0.0013 (7)
C1	0.0238 (13)	0.0249 (11)	0.0157 (10)	0.0028 (11)	−0.0006 (9)	0.0038 (11)
C2	0.0197 (12)	0.0248 (12)	0.0160 (10)	0.0032 (11)	−0.0044 (9)	0.0041 (10)
C3	0.0108 (11)	0.0207 (13)	0.0281 (13)	0.0024 (10)	0.0038 (9)	−0.0024 (10)
C4	0.0167 (12)	0.0221 (12)	0.0374 (14)	0.0068 (10)	0.0017 (12)	−0.0036 (12)
C5	0.0221 (13)	0.0178 (11)	0.0312 (13)	0.0056 (10)	0.0070 (11)	−0.0060 (11)
C6	0.0155 (12)	0.0153 (11)	0.0265 (13)	−0.0042 (10)	−0.0031 (10)	−0.0012 (10)
C7	0.0196 (13)	0.0173 (11)	0.0273 (13)	−0.0002 (10)	−0.0050 (10)	−0.0046 (10)
C8	0.0183 (12)	0.0130 (10)	0.0238 (11)	0.0008 (10)	−0.0017 (10)	0.0010 (9)

Geometric parameters (Å, º)

Co1—N11	1.9528 (19)	N14—C2	1.508 (3)
Co1—N13	1.9728 (19)	N14—C3	1.516 (3)
Co1—N12	1.982 (2)	N14—C6	1.518 (3)
Co1—N14	2.030 (2)	C1—C2	1.501 (3)
Co1—Cl2	2.2510 (6)	C3—C4	1.520 (3)
Co1—Cl1	2.2835 (8)	C4—C5	1.505 (4)
N11—C1	1.481 (3)	C6—C7	1.510 (3)
N12—C5	1.487 (3)	C7—C8	1.510 (3)
N13—C8	1.482 (3)
N11—Co1—N13	88.88 (8)	C5—N12—Co1	122.10 (16)
N11—Co1—N12	92.78 (8)	C8—N13—Co1	121.92 (15)
N13—Co1—N12	169.68 (9)	C2—N14—C3	107.63 (18)
N11—Co1—N14	86.23 (8)	C2—N14—C6	110.35 (19)
N13—Co1—N14	96.15 (8)	C3—N14—C6	102.35 (17)
N12—Co1—N14	94.13 (8)	C2—N14—Co1	106.89 (14)
N11—Co1—Cl2	178.09 (6)	C3—N14—Co1	115.65 (14)
N13—Co1—Cl2	89.32 (6)	C6—N14—Co1	113.81 (14)
N12—Co1—Cl2	89.11 (6)	N11—C1—C2	106.97 (19)
N14—Co1—Cl2	93.33 (6)	C1—C2—N14	111.31 (19)
N11—Co1—Cl1	87.85 (6)	N14—C3—C4	116.9 (2)
N13—Co1—Cl1	85.17 (6)	C5—C4—C3	113.2 (2)
N12—Co1—Cl1	84.71 (6)	N12—C5—C4	110.0 (2)
N14—Co1—Cl1	173.90 (6)	C7—C6—N14	118.1 (2)
Cl2—Co1—Cl1	92.64 (3)	C8—C7—C6	111.9 (2)
C1—N11—Co1	109.89 (15)	N13—C8—C7	111.61 (18)