Bis(diethyl­enetriamine)cobalt(III) hexa­cyano­cobaltate(III) dihydrate

Ou, G.-C.; Chen, H.-Y.; Zhang, M..; Yuan, X.-Y.

doi:10.1107/S1600536806051051

Bis(diethylenetriamine)cobalt(III) hexacyanocobaltate(III) dihydrate

G.-C. Ou, H.-Y. Chen, M. Zhang and X.-Y. Yuan

The title compound, [Co(C₄H₁₃N₃)₂][Co(CN)₆]·2H₂O, comprises one [Co(dien)₂]³⁺ cation (dien is diethylenetriamine), one [Co(CN)₆]^3- anion and two water molecules. The Co³⁺ atom of the [Co(dien)₂]³⁺ cation is six-coordinated by six N atoms from two diethylenetriamine groups. The Co³⁺ atom of the [Co(CN)₆]^3- anion is six-coordinated by six C atoms from six cyanide ions. Neighboring cations and anions are connected by hydrogen bonds to each other and to the water molecules. The metal atoms lie on inversion sites.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806051051/ng2168sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536806051051/ng2168Isup2.hkl Contains datablock I

CCDC reference: 633966

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.005 Å
R factor = 0.032
wR factor = 0.095
Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.13
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co2    -   C3      ..       7.00 su
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          5
            N2  -CO1 -N2  -C6     -8.20  0.20   3.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            N3  -CO1 -N3  -C4      2.00  0.00   3.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         11
            N3  -CO1 -N3  -C5     14.00  0.00   3.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         16
            C2  -CO2 -C1  -N6    -29.00  7.00   3.656   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         17
            C2  -CO2 -C1  -N6    151.00  7.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            C3  -CO2 -C1  -N6   -118.00  7.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         19
            C3  -CO2 -C1  -N6     62.00  7.00   3.656   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         20
            C1  -CO2 -C1  -N6     14.00  0.00   3.656   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         23
            N1  -CO1 -N1  -C7      5.00  0.00   3.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         26
            C2  -CO2 -C2  -N4      1.00  0.00   3.656   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         27
            C3  -CO2 -C2  -N4    127.00  6.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         28
            C3  -CO2 -C2  -N4    -53.00  6.00   3.656   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         29
            C1  -CO2 -C2  -N4   -142.00  6.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         30
            C1  -CO2 -C2  -N4     38.00  6.00   3.656   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         31
            C2  -CO2 -C3  -N5      2.00  0.00   3.656   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         32
            C2  -CO2 -C3  -N5     17.00  0.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         33
            C3  -CO2 -C3  -N5     10.00  0.00   3.656   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         34
            C1  -CO2 -C3  -N5     10.00  0.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         35
            C1  -CO2 -C3  -N5      8.00  0.00   3.656   1.555   1.555   1.555

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
  20 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Bis(diethylenetriamine)cobalt(III) hexacyanocobaltate(III) monohydrate top

Crystal data top

[Co(C₄H₁₃N₃)₂][Co(CN)₆]·2H₂O	F(000) = 536
M_r = 516.36	D_x = 1.582 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.148 (3) Å	Cell parameters from 739 reflections
b = 12.217 (4) Å	θ = 2.5–27.2°
c = 10.935 (4) Å	µ = 1.57 mm⁻¹
β = 94.973 (7)°	T = 293 K
V = 1084.3 (6) Å³	Block, yellow
Z = 2	0.48 × 0.31 × 0.13 mm

Data collection top

Bruker APEX area-detector diffractometer	2375 independent reflections
Radiation source: fine-focus sealed tube	1473 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 27.2°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
T_min = 0.520, T_max = 0.822	k = −15→15
6186 measured reflections	l = −8→14

Refinement top

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0501P)² + 0.0602P] where P = (F_o² + 2F_c²)/3
2375 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

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

	x	y	z	U_iso*/U_eq
Co1	0.0000	0.0000	0.0000	0.02655 (14)
Co2	0.5000	0.0000	0.5000	0.03055 (15)
N2	0.0715 (3)	0.11345 (17)	0.12131 (19)	0.0367 (5)
H2A	0.1822	0.1162	0.1297	0.044*
H2B	0.0341	0.1791	0.0939	0.044*
N5	0.4247 (3)	0.06444 (19)	0.2321 (2)	0.0467 (6)
N3	0.1235 (3)	0.06265 (17)	−0.12925 (19)	0.0360 (5)
H3A	0.2253	0.0819	−0.0952	0.043*
C1	0.3830 (3)	0.1246 (2)	0.5507 (2)	0.0377 (6)
N1	0.1847 (2)	−0.09322 (17)	0.06332 (19)	0.0368 (5)
H1A	0.2057	−0.1430	0.0061	0.044*
H1B	0.2754	−0.0518	0.0790	0.044*
C2	0.3061 (3)	−0.0870 (2)	0.4933 (2)	0.0379 (6)
C3	0.4522 (3)	0.0401 (2)	0.3325 (3)	0.0356 (6)
C4	0.1435 (4)	−0.0223 (2)	−0.2228 (3)	0.0509 (8)
H4A	0.2362	−0.0688	−0.1961	0.061*
H4B	0.1668	0.0123	−0.2993	0.061*
N4	0.1920 (3)	−0.1426 (2)	0.4907 (2)	0.0582 (7)
N6	0.3179 (3)	0.1998 (2)	0.5828 (2)	0.0549 (7)
C5	0.0369 (4)	0.1642 (2)	−0.1764 (3)	0.0474 (7)
H5A	0.0662	0.1796	−0.2587	0.057*
H5B	0.0719	0.2257	−0.1243	0.057*
C6	0.0090 (4)	0.0908 (3)	0.2439 (3)	0.0496 (8)
H6A	0.0919	0.0522	0.2962	0.060*
H6B	−0.0161	0.1590	0.2837	0.060*
C7	0.1460 (3)	−0.1508 (2)	0.1782 (3)	0.0478 (7)
H7A	0.1869	−0.1084	0.2494	0.057*
H7B	0.1991	−0.2219	0.1829	0.057*
O1W	0.4440 (3)	0.14114 (18)	−0.0152 (2)	0.0616 (6)
H1C	0.4445	0.1199	0.0600	0.074*
H1D	0.4182	0.2086	−0.0085	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0266 (2)	0.0281 (3)	0.0250 (3)	−0.00121 (19)	0.00239 (19)	−0.0012 (2)
Co2	0.0348 (3)	0.0294 (3)	0.0272 (3)	−0.0029 (2)	0.0010 (2)	0.0009 (2)
N2	0.0343 (12)	0.0381 (13)	0.0376 (13)	−0.0030 (9)	0.0022 (10)	−0.0069 (10)
N5	0.0491 (14)	0.0543 (17)	0.0354 (14)	−0.0038 (12)	−0.0039 (11)	0.0030 (12)
N3	0.0370 (12)	0.0409 (14)	0.0306 (11)	−0.0061 (10)	0.0050 (10)	−0.0001 (10)
C1	0.0456 (16)	0.0344 (16)	0.0337 (15)	−0.0027 (13)	0.0078 (13)	0.0052 (13)
N1	0.0348 (12)	0.0351 (13)	0.0400 (13)	0.0023 (10)	−0.0007 (10)	−0.0015 (10)
C2	0.0418 (16)	0.0420 (17)	0.0295 (14)	−0.0048 (13)	−0.0005 (12)	−0.0006 (12)
C3	0.0336 (14)	0.0368 (14)	0.0366 (16)	−0.0018 (12)	0.0041 (12)	−0.0010 (13)
C4	0.0506 (18)	0.059 (2)	0.0455 (17)	0.0006 (14)	0.0196 (15)	−0.0047 (15)
N4	0.0603 (17)	0.0658 (19)	0.0483 (16)	−0.0197 (14)	0.0030 (13)	−0.0019 (13)
N6	0.0690 (18)	0.0362 (15)	0.0621 (18)	0.0001 (13)	0.0208 (15)	0.0034 (13)
C5	0.062 (2)	0.0379 (17)	0.0423 (17)	−0.0068 (14)	0.0061 (15)	0.0076 (13)
C6	0.0568 (19)	0.0556 (19)	0.0371 (17)	−0.0026 (15)	0.0070 (14)	−0.0078 (14)
C7	0.0543 (19)	0.0442 (18)	0.0427 (18)	0.0029 (14)	−0.0074 (15)	0.0047 (14)
O1W	0.0590 (13)	0.0648 (15)	0.0610 (14)	−0.0014 (11)	0.0057 (11)	0.0007 (11)

Geometric parameters (Å, º) top

Co1—N3	1.960 (2)	C1—N6	1.132 (3)
Co1—N3ⁱ	1.960 (2)	N1—C7	1.496 (3)
Co1—N1ⁱ	1.965 (2)	N1—H1A	0.9000
Co1—N1	1.965 (2)	N1—H1B	0.9000
Co1—N2	1.971 (2)	C2—N4	1.150 (3)
Co1—N2ⁱ	1.971 (2)	C4—C6ⁱ	1.499 (4)
Co2—C2ⁱⁱ	1.900 (3)	C4—H4A	0.9700
Co2—C2	1.900 (3)	C4—H4B	0.9700
Co2—C3	1.903 (3)	C5—C7ⁱ	1.498 (4)
Co2—C3ⁱⁱ	1.903 (3)	C5—H5A	0.9700
Co2—C1	1.903 (3)	C5—H5B	0.9700
Co2—C1ⁱⁱ	1.903 (3)	C6—C4ⁱ	1.499 (4)
N2—C6	1.500 (3)	C6—H6A	0.9700
N2—H2A	0.9000	C6—H6B	0.9700
N2—H2B	0.9000	C7—C5ⁱ	1.498 (4)
N5—C3	1.141 (3)	C7—H7A	0.9700
N3—C4	1.476 (4)	C7—H7B	0.9700
N3—C5	1.496 (3)	O1W—H1C	0.8618
N3—H3A	0.9100	O1W—H1D	0.8554

N3—Co1—N3ⁱ	180.00 (16)	C5—N3—Co1	108.42 (16)
N3—Co1—N1ⁱ	86.83 (9)	C4—N3—H3A	108.2
N3ⁱ—Co1—N1ⁱ	93.17 (9)	C5—N3—H3A	108.2
N3—Co1—N1	93.17 (9)	Co1—N3—H3A	108.2
N3ⁱ—Co1—N1	86.83 (9)	N6—C1—Co2	177.8 (3)
N1ⁱ—Co1—N1	180.00 (15)	C7—N1—Co1	110.95 (16)
N3—Co1—N2	94.05 (9)	C7—N1—H1A	109.4
N3ⁱ—Co1—N2	85.95 (9)	Co1—N1—H1A	109.4
N1ⁱ—Co1—N2	90.12 (9)	C7—N1—H1B	109.4
N1—Co1—N2	89.88 (9)	Co1—N1—H1B	109.4
N3—Co1—N2ⁱ	85.95 (9)	H1A—N1—H1B	108.0
N3ⁱ—Co1—N2ⁱ	94.05 (9)	N4—C2—Co2	177.7 (3)
N1ⁱ—Co1—N2ⁱ	89.88 (9)	N5—C3—Co2	179.5 (3)
N1—Co1—N2ⁱ	90.12 (9)	N3—C4—C6ⁱ	111.0 (2)
N2—Co1—N2ⁱ	180.00 (17)	N3—C4—H4A	109.4
C2ⁱⁱ—Co2—C2	180.00 (13)	C6ⁱ—C4—H4A	109.4
C2ⁱⁱ—Co2—C3	89.62 (11)	N3—C4—H4B	109.4
C2—Co2—C3	90.38 (11)	C6ⁱ—C4—H4B	109.4
C2ⁱⁱ—Co2—C3ⁱⁱ	90.38 (11)	H4A—C4—H4B	108.0
C2—Co2—C3ⁱⁱ	89.62 (11)	N3—C5—C7ⁱ	110.6 (2)
C3—Co2—C3ⁱⁱ	180.00 (6)	N3—C5—H5A	109.5
C2ⁱⁱ—Co2—C1	88.69 (11)	C7ⁱ—C5—H5A	109.5
C2—Co2—C1	91.31 (11)	N3—C5—H5B	109.5
C3—Co2—C1	90.50 (11)	C7ⁱ—C5—H5B	109.5
C3ⁱⁱ—Co2—C1	89.50 (11)	H5A—C5—H5B	108.1
C2ⁱⁱ—Co2—C1ⁱⁱ	91.31 (11)	C4ⁱ—C6—N2	107.9 (2)
C2—Co2—C1ⁱⁱ	88.69 (11)	C4ⁱ—C6—H6A	110.1
C3—Co2—C1ⁱⁱ	89.50 (11)	N2—C6—H6A	110.1
C3ⁱⁱ—Co2—C1ⁱⁱ	90.50 (11)	C4ⁱ—C6—H6B	110.1
C1—Co2—C1ⁱⁱ	180.00 (15)	N2—C6—H6B	110.1
C6—N2—Co1	111.62 (16)	H6A—C6—H6B	108.4
C6—N2—H2A	109.3	N1—C7—C5ⁱ	108.8 (2)
Co1—N2—H2A	109.3	N1—C7—H7A	109.9
C6—N2—H2B	109.3	C5ⁱ—C7—H7A	109.9
Co1—N2—H2B	109.3	N1—C7—H7B	109.9
H2A—N2—H2B	108.0	C5ⁱ—C7—H7B	109.9
C4—N3—C5	114.9 (2)	H7A—C7—H7B	108.3
C4—N3—Co1	108.65 (16)	H1C—O1W—H1D	101.0

N3—Co1—N2—C6	−176.25 (18)	N3ⁱ—Co1—N1—C7	−5.96 (17)
N3ⁱ—Co1—N2—C6	3.75 (18)	N1ⁱ—Co1—N1—C7	−53 (51)
N1ⁱ—Co1—N2—C6	96.92 (18)	N2—Co1—N1—C7	79.99 (18)
N1—Co1—N2—C6	−83.08 (18)	N2ⁱ—Co1—N1—C7	−100.01 (18)
N2ⁱ—Co1—N2—C6	−8.2 (2)	C2ⁱⁱ—Co2—C2—N4	8 (68)
N3ⁱ—Co1—N3—C4	15 (100)	C3—Co2—C2—N4	127 (6)
N1ⁱ—Co1—N3—C4	−109.02 (19)	C3ⁱⁱ—Co2—C2—N4	−53 (6)
N1—Co1—N3—C4	70.98 (19)	C1—Co2—C2—N4	−142 (6)
N2—Co1—N3—C4	161.08 (18)	C1ⁱⁱ—Co2—C2—N4	38 (6)
N2ⁱ—Co1—N3—C4	−18.92 (18)	C2ⁱⁱ—Co2—C3—N5	15 (33)
N3ⁱ—Co1—N3—C5	140 (100)	C2—Co2—C3—N5	−165 (100)
N1ⁱ—Co1—N3—C5	16.51 (17)	C3ⁱⁱ—Co2—C3—N5	−100 (100)
N1—Co1—N3—C5	−163.49 (17)	C1—Co2—C3—N5	104 (33)
N2—Co1—N3—C5	−73.38 (17)	C1ⁱⁱ—Co2—C3—N5	−76 (33)
N2ⁱ—Co1—N3—C5	106.62 (17)	C5—N3—C4—C6ⁱ	−83.2 (3)
C2ⁱⁱ—Co2—C1—N6	−29 (7)	Co1—N3—C4—C6ⁱ	38.5 (3)
C2—Co2—C1—N6	151 (7)	C4—N3—C5—C7ⁱ	85.6 (3)
C3—Co2—C1—N6	−118 (7)	Co1—N3—C5—C7ⁱ	−36.1 (3)
C3ⁱⁱ—Co2—C1—N6	62 (7)	Co1—N2—C6—C4ⁱ	−25.1 (3)
C1ⁱⁱ—Co2—C1—N6	143 (33)	Co1—N1—C7—C5ⁱ	27.1 (3)
N3—Co1—N1—C7	174.04 (17)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N5	0.90	2.27	3.083 (3)	149
N2—H2B···N6ⁱⁱⁱ	0.90	2.30	3.082 (3)	146
O1W—H1D···N4^iv	0.86	2.04	2.886 (3)	168
N3—H3A···O1W	0.91	2.05	2.955 (3)	174
N1—H1A···N6^v	0.90	2.15	2.990 (3)	154
N1—H1B···N5	0.90	2.44	3.212 (3)	144
O1W—H1C···N5	0.86	2.02	2.879 (3)	175

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

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Bis(diethyl­enetriamine)cobalt(III) hexa­cyano­cobaltate(III) dihydrate

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Bis(diethylenetriamine)cobalt(III) hexacyanocobaltate(III) dihydrate