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Structural analysis of the title compound, [N-(2-amino­ethyl)-1,2-ethanedi­amine]­azido(2-hydroxy-1,3-propane­di­amine)­cobalt(III) tetra­chloro­zincate(II), unsym-fac-(exo-OH)-[Co(dien)(dapo)N3]ZnCl4 or [Co(N3)(C4H13N3)(C3H10N2O)][ZnCl4], confirms both the facial configuration of the N-(2-amino­ethyl)-1,2-ethanedi­amine (dien) ligand and the exo stereochemistry of the OH substituent of the 2-hydroxy-1,3-propane­di­amine (dapo) ligand relative to the azide ligand.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802003070/tk6054sup1.cif
Contains datablocks dapaz, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802003070/tk6054Isup2.hkl
Contains datablock I

CCDC reference: 182590

Key indicators

  • Single-crystal X-ray study
  • T = 168 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.027
  • wR factor = 0.061
  • Data-to-parameter ratio = 18.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.843 1.000 Tmin and Tmax expected: 0.361 0.541 RR = 1.266 Please check that your absorption correction is appropriate. PLAT_420 Alert C D-H Without Acceptor N(4) - H(4B) ? PLAT_420 Alert C D-H Without Acceptor N(6) - H(6B) ? 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 0.541 Tmax scaled 0.541 Tmin scaled 0.456
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check

Comment top

[Co(dien)(dapo)(N3)]2+ complexes are rapidly hydrolyzed in weakly alkaline solution at room temperature. The mer(exo)- and mer(endo)- forms of the [Co(dien)(dapo)OH]2+ product quickly equilibrate [t1/2 = 0.20 s, 298 K, I = 1.0 M (NaClO4)], and at longer times (1–2 h, pH 9), significant production of unsym(fac) isomers occurs. The title complex, (I), was obtained by anation with azide ion and was isolated using a combination of ion-exchange chromatography and fractional crystallization (Browne et al., 2002). The structure of the cation consists of a central Co atom coordinated to a tridentate dien ligand bound in a facial configuration, a bidentate dapo ligand, and a monodentate azide ligand. As can be seen in Fig. 1, the dapo –OH group adopts an exo configuration with respect to the azide ligand. The geometry about the Co atom is approximately octahedral, with the greatest deviations from 90° being found in the five-membered chelate rings of the dien ligand. The Co—N distances lie in the range 1.943 (2)–1.986 (2) Å, with the bond to the azide ligand being significantly shorter than the others. This contrasts with the three previous structurally characterized [Co(dien)(dapo)N3]2+ complexes, namely Λ(-)436-mer(exo)-[Co(dien)(dapo)N3](di-O-benzoyl-L-tartH)2·4H2O, Λ(-)436-Λ(-)436-mer(endo)-[Co(dien)(dapo)N3](di-O-benzoyl-L– tartH)2·2.75H2O and Δ(+)436-mer(endo)-[Co(dien)(dapo)N3](di-O-benzoyl-L-tartH)2·5.75H2O (Comba et al., 1992) in which the bond between the Co atom and the secondary N atom of the dien ligand is the shortest of the Co—N distances.

Experimental top

A solution of mer-(exo)- and mer-(endo)-[Co(dien)(dapo)N3]ZnCl4 (1.1 g) in water (5 ml) containing NaN3 (0.55 g) was allowed to stand for 1 h at pH 7.85, then for a further 1 h at pH 9.3. Precipitated Zn(OH)2 was removed by filtration, the filtrate was acidified (HOAc, pH 4.5) and complexes separated by ion-exchange chromatography (Dowex 50Wx2, 1 M NaCl, pH 4.2). The slower moving of the two major bands was collected and evaporated to near dryness at room temperature. MeOH was added and solid NaCl removed by filtration. This treatment was repeated until all the NaCl was removed. The final filtrate was evaporated to dryness, and the residue in water (4 ml) was treated with aqueous Li2ZnCl4 (2 M, 1 ml). The first two fractions to crystallize (ice cooling) deposited rapidly and consisted mainly of mer-(exo)-[Co(dien)(dapo)N3]ZnCl4. The third fraction which was obtained on storage overnight at 277 K (0.3 g, unsym-fac(exo-OH plus endo-OH)-[Co(dien)(dapo)N3]ZnCl4) was dissolved in the minimum volume of hot water to give large rhombohedral crystals of the unsym-fac(exo-OH)- isomer on slow cooling at room temperature.

Refinement top

H atoms were included in calculated positions and refined in the riding approximation with individual (or group, if appropriate) isotropic displacement parameters.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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 top
[Figure 1] Fig. 1. The structure of the cation of (I) with displacement ellipsoids drawn at the 50% probability level (Farrugia, 1999).
[N-(2-aminoethyl)-1,2-ethanediamine]azido(2-hydroxy-1,3-propanediamine)cobalt tetrachlorozinc top
Crystal data top
[Co(N3)(C4H13N3)(C3H10N2O)][ZnCl4]F(000) = 1016
Mr = 501.43Dx = 1.891 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.119 (3) ÅCell parameters from 3138 reflections
b = 21.373 (6) Åθ = 2.2–26.5°
c = 10.249 (3) ŵ = 2.92 mm1
β = 98.071 (4)°T = 168 K
V = 1760.8 (9) Å3Irregular-b, red
Z = 40.79 × 0.30 × 0.21 mm
Data collection top
CCD area detector
diffractometer
3138 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ϕ and ω scansθmax = 26.5°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1010
Tmin = 0.843, Tmax = 1k = 2026
22443 measured reflectionsl = 1212
3600 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0243P)2 + 1.8355P]
where P = (Fo2 + 2Fc2)/3
3600 reflections(Δ/σ)max = 0.001
200 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.41 e Å3
Crystal data top
[Co(N3)(C4H13N3)(C3H10N2O)][ZnCl4]V = 1760.8 (9) Å3
Mr = 501.43Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.119 (3) ŵ = 2.92 mm1
b = 21.373 (6) ÅT = 168 K
c = 10.249 (3) Å0.79 × 0.30 × 0.21 mm
β = 98.071 (4)°
Data collection top
CCD area detector
diffractometer
3600 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
3138 reflections with I > 2σ(I)
Tmin = 0.843, Tmax = 1Rint = 0.032
22443 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.061H-atom parameters constrained
S = 1.10Δρmax = 0.58 e Å3
3600 reflectionsΔρmin = 0.41 e Å3
200 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Co10.84605 (4)0.128749 (15)0.28525 (3)0.01706 (8)
N10.6209 (3)0.15998 (10)0.2824 (2)0.0284 (5)
N20.5804 (3)0.21329 (11)0.2793 (2)0.0260 (5)
N30.5276 (4)0.26386 (13)0.2759 (4)0.0527 (8)
N40.7781 (3)0.10520 (10)0.0997 (2)0.0304 (5)
H4A0.81840.0660.08530.037*
H4B0.66380.10360.08270.037*
N50.9339 (3)0.20546 (10)0.2147 (2)0.0231 (4)
H50.89910.2390.26170.028*
N61.0726 (3)0.09394 (10)0.2853 (2)0.0272 (5)
H6A1.11860.0850.37050.033*
H6B1.06550.05710.23830.033*
N70.9044 (3)0.15863 (10)0.4695 (2)0.0227 (4)
H7A1.00570.14150.50260.027*
H7B0.91880.20130.46680.027*
N80.7678 (3)0.04839 (9)0.3456 (2)0.0232 (5)
H8A0.70810.02910.27390.028*
H8B0.86010.0240.37130.028*
C10.8405 (4)0.15027 (13)0.0085 (3)0.0324 (6)
H1A0.76220.15280.07460.039*
H1B0.95010.13650.01270.039*
C20.8560 (4)0.21262 (13)0.0743 (3)0.0326 (6)
H2A0.74450.23180.07090.039*
H2B0.92530.24050.02730.039*
C31.1208 (4)0.20315 (14)0.2420 (3)0.0375 (7)
H3A1.16830.23130.18030.045*
H3B1.15840.2180.33280.045*
C41.1820 (3)0.13816 (14)0.2267 (3)0.0330 (6)
H4C1.1810.12850.13210.04*
H4D1.29780.13410.27160.04*
C50.7860 (3)0.14528 (12)0.5656 (3)0.0285 (6)
H5A0.67930.16690.53670.034*
H5B0.83240.1620.65310.034*
C60.7547 (3)0.07632 (13)0.5771 (3)0.0288 (6)
H60.68680.06960.65010.035*
C70.6648 (3)0.04716 (13)0.4534 (3)0.0281 (6)
H7C0.63610.00330.47170.034*
H7D0.55990.07020.42570.034*
O10.9084 (3)0.04301 (9)0.6082 (2)0.0344 (5)
H10.9570.05490.68180.052*
Zn10.84880 (4)0.402393 (14)0.32047 (3)0.02397 (9)
Cl11.05089 (8)0.47604 (3)0.34137 (6)0.02903 (15)
Cl20.80150 (8)0.37407 (3)0.10145 (6)0.02809 (14)
Cl30.61875 (8)0.45042 (3)0.38439 (7)0.02862 (15)
Cl40.91206 (10)0.31615 (3)0.44702 (7)0.03424 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.01748 (16)0.01275 (16)0.02010 (16)0.00075 (12)0.00029 (12)0.00054 (12)
N10.0187 (11)0.0231 (12)0.0417 (13)0.0024 (9)0.0015 (9)0.0058 (10)
N20.0186 (10)0.0318 (13)0.0271 (12)0.0002 (10)0.0012 (9)0.0004 (10)
N30.0382 (16)0.0308 (15)0.089 (2)0.0124 (12)0.0085 (15)0.0056 (15)
N40.0456 (14)0.0195 (11)0.0238 (11)0.0002 (10)0.0035 (10)0.0021 (9)
N50.0271 (11)0.0152 (10)0.0265 (11)0.0007 (9)0.0026 (9)0.0013 (9)
N60.0263 (11)0.0209 (11)0.0351 (13)0.0035 (9)0.0067 (9)0.0011 (10)
N70.0267 (11)0.0168 (10)0.0235 (11)0.0016 (9)0.0005 (9)0.0010 (8)
N80.0261 (11)0.0164 (10)0.0268 (11)0.0030 (9)0.0026 (9)0.0001 (9)
C10.0428 (17)0.0320 (15)0.0233 (14)0.0014 (13)0.0078 (12)0.0001 (12)
C20.0456 (17)0.0248 (14)0.0279 (14)0.0013 (13)0.0070 (12)0.0051 (12)
C30.0288 (15)0.0310 (16)0.0541 (19)0.0087 (12)0.0102 (14)0.0028 (14)
C40.0224 (13)0.0358 (16)0.0424 (17)0.0015 (12)0.0100 (12)0.0089 (13)
C50.0352 (15)0.0257 (14)0.0253 (13)0.0036 (12)0.0071 (11)0.0019 (11)
C60.0321 (14)0.0269 (14)0.0300 (14)0.0041 (11)0.0133 (11)0.0052 (11)
C70.0239 (13)0.0222 (13)0.0395 (16)0.0026 (11)0.0088 (11)0.0064 (12)
O10.0392 (12)0.0288 (11)0.0334 (11)0.0086 (9)0.0011 (9)0.0024 (9)
Zn10.02795 (16)0.02072 (16)0.02279 (16)0.00238 (12)0.00204 (12)0.00018 (12)
Cl10.0301 (3)0.0306 (3)0.0259 (3)0.0028 (3)0.0023 (3)0.0044 (3)
Cl20.0285 (3)0.0303 (3)0.0245 (3)0.0029 (3)0.0005 (2)0.0041 (3)
Cl30.0293 (3)0.0261 (3)0.0315 (3)0.0003 (3)0.0082 (3)0.0017 (3)
Cl40.0511 (4)0.0205 (3)0.0286 (3)0.0021 (3)0.0032 (3)0.0023 (3)
Geometric parameters (Å, º) top
Co1—N11.943 (2)C1—C21.491 (4)
Co1—N41.970 (2)C1—H1A0.9900
Co1—N51.966 (2)C1—H1B0.9900
Co1—N61.984 (2)C2—H2A0.9900
Co1—N71.986 (2)C2—H2B0.9900
Co1—N81.961 (2)C3—C41.491 (4)
N1—N21.185 (3)C3—H3A0.9900
N2—N31.162 (3)C3—H3B0.9900
N4—C11.481 (4)C4—H4C0.9900
N4—H4A0.9200C4—H4D0.9900
N4—H4B0.9200C5—C61.503 (4)
N5—C21.497 (3)C5—H5A0.9900
N5—C31.505 (3)C5—H5B0.9900
N5—H50.9300C6—O11.433 (3)
N6—C41.481 (3)C6—C71.506 (4)
N6—H6A0.9200C6—H61.0000
N6—H6B0.9200C7—H7C0.9900
N7—C51.497 (3)C7—H7D0.9900
N7—H7A0.9200O1—H10.8400
N7—H7B0.9200Zn1—Cl12.2621 (9)
N8—C71.477 (3)Zn1—Cl22.3045 (9)
N8—H8A0.9200Zn1—Cl32.3054 (9)
N8—H8B0.9200Zn1—Cl42.2709 (9)
N1—Co1—N486.44 (10)N4—C1—H1A110.1
N1—Co1—N595.59 (9)C2—C1—H1A110.1
N1—Co1—N6177.91 (9)N4—C1—H1B110.1
N1—Co1—N790.12 (9)C2—C1—H1B110.1
N1—Co1—N887.71 (9)H1A—C1—H1B108.4
N4—Co1—N692.21 (10)C1—C2—N5109.9 (2)
N4—Co1—N7175.51 (9)C1—C2—H2A109.7
N5—Co1—N485.71 (9)N5—C2—H2A109.7
N5—Co1—N685.90 (9)C1—C2—H2B109.7
N5—Co1—N791.76 (9)N5—C2—H2B109.7
N6—Co1—N791.31 (9)H2A—C2—H2B108.2
N8—Co1—N491.23 (9)C4—C3—N5110.7 (2)
N8—Co1—N5175.34 (9)C4—C3—H3A109.5
N8—Co1—N690.73 (9)N5—C3—H3A109.5
N8—Co1—N791.52 (9)C4—C3—H3B109.5
N2—N1—Co1125.99 (18)N5—C3—H3B109.5
N3—N2—N1174.5 (3)H3A—C3—H3B108.1
C1—N4—Co1111.66 (17)N6—C4—C3108.9 (2)
C1—N4—H4A109.3N6—C4—H4C109.9
Co1—N4—H4A109.3C3—C4—H4C109.9
C1—N4—H4B109.3N6—C4—H4D109.9
Co1—N4—H4B109.3C3—C4—H4D109.9
H4A—N4—H4B107.9H4C—C4—H4D108.3
C2—N5—C3117.5 (2)N7—C5—C6111.7 (2)
C2—N5—Co1108.21 (16)N7—C5—H5A109.3
C3—N5—Co1108.23 (16)C6—C5—H5A109.3
C2—N5—H5107.5N7—C5—H5B109.3
C3—N5—H5107.5C6—C5—H5B109.3
Co1—N5—H5107.5H5A—C5—H5B107.9
C4—N6—Co1111.68 (16)O1—C6—C5110.7 (2)
C4—N6—H6A109.3O1—C6—C7106.6 (2)
Co1—N6—H6A109.3C5—C6—C7114.0 (2)
C4—N6—H6B109.3O1—C6—H6108.5
Co1—N6—H6B109.3C5—C6—H6108.5
H6A—N6—H6B107.9C7—C6—H6108.5
C5—N7—Co1118.34 (16)N8—C7—C6111.3 (2)
C5—N7—H7A107.7N8—C7—H7C109.4
Co1—N7—H7A107.7C6—C7—H7C109.4
C5—N7—H7B107.7N8—C7—H7D109.4
Co1—N7—H7B107.7C6—C7—H7D109.4
H7A—N7—H7B107.1H7C—C7—H7D108.0
C7—N8—Co1119.61 (16)C6—O1—H1109.5
C7—N8—H8A107.4Cl1—Zn1—Cl4114.07 (3)
Co1—N8—H8A107.4Cl1—Zn1—Cl2107.13 (3)
C7—N8—H8B107.4Cl4—Zn1—Cl2109.66 (3)
Co1—N8—H8B107.4Cl1—Zn1—Cl3105.61 (3)
H8A—N8—H8B106.9Cl4—Zn1—Cl3109.05 (3)
N4—C1—C2108.1 (2)Cl2—Zn1—Cl3111.28 (3)

Experimental details

Crystal data
Chemical formula[Co(N3)(C4H13N3)(C3H10N2O)][ZnCl4]
Mr501.43
Crystal system, space groupMonoclinic, P21/n
Temperature (K)168
a, b, c (Å)8.119 (3), 21.373 (6), 10.249 (3)
β (°) 98.071 (4)
V3)1760.8 (9)
Z4
Radiation typeMo Kα
µ (mm1)2.92
Crystal size (mm)0.79 × 0.30 × 0.21
Data collection
DiffractometerCCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.843, 1
No. of measured, independent and
observed [I > 2σ(I)] reflections
22443, 3600, 3138
Rint0.032
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.061, 1.10
No. of reflections3600
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.58, 0.41

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), WinGX (Farrugia, 1999), WinGX.

Selected geometric parameters (Å, º) top
Co1—N11.943 (2)N5—C31.505 (3)
Co1—N41.970 (2)N6—C41.481 (3)
Co1—N51.966 (2)N7—C51.497 (3)
Co1—N61.984 (2)N8—C71.477 (3)
Co1—N71.986 (2)C1—C21.491 (4)
Co1—N81.961 (2)C3—C41.491 (4)
N1—N21.185 (3)C5—C61.503 (4)
N2—N31.162 (3)C6—O11.433 (3)
N4—C11.481 (4)C6—C71.506 (4)
N5—C21.497 (3)
N1—Co1—N486.44 (10)N5—Co1—N791.76 (9)
N1—Co1—N595.59 (9)N6—Co1—N791.31 (9)
N1—Co1—N6177.91 (9)N8—Co1—N491.23 (9)
N1—Co1—N790.12 (9)N8—Co1—N5175.34 (9)
N1—Co1—N887.71 (9)N8—Co1—N690.73 (9)
N4—Co1—N692.21 (10)N8—Co1—N791.52 (9)
N4—Co1—N7175.51 (9)N2—N1—Co1125.99 (18)
N5—Co1—N485.71 (9)N3—N2—N1174.5 (3)
N5—Co1—N685.90 (9)
 

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