Crystal structures of [18]aneN₆H₂K[Co(CN)₆].4H₂O, [16]aneN₄H₂K[Co(CN)₆] and [12]aneN₄H₃[Co(CN)₆].2H₂O. Insight into the electrostatic and hydrogen-bonding interaction in self-assembling supercomplexes

The crystal structures of [18]aneN₆H₂K[Co(CN)₆].4H₂O [potassium dihydrogen hexacyanocobaltate-1,4,7,­10,13,16-hexa­aza­cyclo­octa­decane-water (1/1/4)], [16]aneN₄H₂K[Co(CN)₆] [potassium dihydrogen hexa­cyano­cobaltate-1,5,9,13-tetra­aza­cyclo­hexa­decane (1/1)] and [12]aneN₄H₃[Co(CN)₆].2H₂O [trihydrogen hexa­cyano­cobaltate-1,4,7,­10-tetra­aza­cyclodo­dec­ane-­water (1/1/2)] have been determined. For these supercomplexes, the [Co(CN)₆]^3- binding with protonated polyammonium macrocycles is dominant in the binding competition between K⁺ and [Co(CN)₆]^3-. It is suggested that the binding of [Co(CN)₆]^3- with protonated polyammonium macrocycles is independent of the cavity size of the macrocycle, whereas that of K⁺ is size-match selective. For [18]aneN₆H₂K[Co(CN)₆].4H₂O, the formation of a two-dimensional lamella may be derived from a chain-like arrangement of four-, five- and eight-membered rings in the network through the mutual balance between electrostatic and hydrogen-bonding interactions. [16]aneN₄H₂K[Co(CN)₆] is a novel example demonstrating the anchoring of cobalticyanide through hydrogen-bonding interactions inside a zeolite-type cavity in the three-dimensional network formed by K⁺ and the macrocycles through Coulombic interactions. Also, a three-dimensional network was formed mainly through hydrogen-bonding interactions between [Co(CN)₆]^3-, protonated macrocycles and water molecules in [12]aneN₄H₃[Co(CN)₆].2H₂O.

Computing details

Data collection: Siemens XSCANS ver. 2.10b for (1), (3); MSC/AFC Diffractometer Control for (2). Cell refinement: Siemens XSCANS ver. 2.10b for (1), (3); MSC/AFC Diffractometer Control for (2). Data reduction: Siemens XSCANS ver. 2.10b for (1), (3); MSC/AFC Diffractometer Control for (2). For all compounds, program(s) used to solve structure: SHELXS86 (Sheldrick, 1990). Program(s) used to refine structure: SHELXL93 (Sheldrick, 1993) for (1); SHELXTL-PC (Sheldrick, 1990) for (2), (3). For all compounds, molecular graphics: SHELXTL-PC (Sheldrick, 1990).

(1)

Crystal data

KH2[Co(CN)6](C12H30N6).4(H2O)	Z = 2
Mr = 586.65	F(000) = 620
Triclinic, P1	Dx = 1.324 Mg m^−3
a = 10.125 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.133 (2) Å	Cell parameters from 25 reflections
c = 15.014 (2) Å	θ = 5–15°
α = 73.78 (1)°	µ = 0.77 mm^−1
β = 71.68 (1)°	T = 293 K
γ = 68.87 (2)°	Plate, colorless
V = 1472.0 (6) Å^3	0.30 × 0.30 × 0.10 mm

Data collection

Siemens P4 diffractometer	3032 reflections with > 4σ(F)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 24.0°, θmin = 1.5°
ω scans	h = 0→11
Absorption correction: empirical	k = −11→12
Tmin = 0.833, Tmax = 0.946	l = −16→17
4910 measured reflections	3 standard reflections every 100 reflections
4617 independent reflections	intensity decay: −1.3%

Refinement

Refinement on F	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.059	H-atom parameters not defined?
wR(F^2) = 0.075	Calculated w = 1/[σ^2(Fo) + 0.0005Fo^2]
3023 reflections	(Δ/σ)max = 0.001
325 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.62 e Å^−3
Primary atom site location: structure-invariant direct methods

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	Occ. (<1)
Co1	0.2607 (1)	0.2764 (1)	0.2894 (1)	0.025 (1)
C1	0.1670 (7)	0.1451 (6)	0.3620 (4)	0.035 (3)
N1	0.1076 (6)	0.0702 (5)	0.4054 (4)	0.048 (3)
C2	0.3494 (7)	0.4107 (6)	0.2223 (4)	0.038 (3)
N2	0.3998 (7)	0.4926 (6)	0.1854 (4)	0.061 (3)
C3	0.0782 (7)	0.4080 (6)	0.3063 (4)	0.036 (3)
N3	−0.0325 (7)	0.4876 (6)	0.3142 (4)	0.054 (3)
C4	0.2940 (7)	0.2896 (6)	0.4040 (5)	0.037 (3)
N4	0.3185 (7)	0.2939 (6)	0.4724 (4)	0.054 (3)
C5	0.4467 (7)	0.1490 (6)	0.2665 (4)	0.035 (3)
N5	0.5575 (6)	0.0730 (6)	0.2514 (4)	0.050 (3)
C6	0.2325 (7)	0.2547 (6)	0.1756 (5)	0.038 (3)
N6	0.2167 (7)	0.2382 (6)	0.1083 (4)	0.061 (3)
K1	−0.0057 (2)	−0.0181 (2)	0.1273 (1)	0.056 (1)
N11	−0.2878 (5)	0.1178 (5)	0.0404 (4)	0.039 (2)
H11M	−0.1964	0.1003	0.0034	0.050*
H11N	−0.2855	0.0906	0.1024	0.050*	0.5
N12	−0.1567 (6)	0.3214 (5)	−0.0442 (4)	0.045 (3)
H12M	−0.1919	0.3493	−0.0969	0.050*
N13	0.1399 (5)	0.1870 (5)	−0.0389 (3)	0.036 (2)
H13M	0.1504	0.1848	0.0201	0.050*
H13N	0.0752	0.1494	−0.0491	0.050*	0.5
C11	−0.3514 (7)	0.0193 (6)	0.0349 (5)	0.043 (3)
H11A	−0.3322	0.0144	−0.0310	0.060*
H11B	−0.4552	0.0487	0.0589	0.060*
C12	−0.3747 (7)	0.2553 (6)	0.0151 (5)	0.047 (3)
H12A	−0.4701	0.2709	0.0573	0.060*
H12B	−0.3850	0.2713	−0.0490	0.060*
C13	−0.2992 (8)	0.3453 (7)	0.0214 (5)	0.050 (3)
H13A	−0.3567	0.4351	0.0073	0.060*
H13B	−0.2857	0.3278	0.0848	0.060*
C14	−0.0642 (7)	0.3888 (6)	−0.0356 (5)	0.048 (3)
H14A	−0.0682	0.3776	0.0309	0.060*
H14B	−0.0962	0.4809	−0.0609	0.060*
C15	0.0901 (8)	0.3273 (6)	−0.0866 (5)	0.046 (3)
H15A	0.0925	0.3316	−0.1518	0.060*
H15B	0.1538	0.3732	−0.0859	0.060*
C16	0.2899 (7)	0.1173 (6)	−0.0884 (4)	0.041 (3)
H16A	0.3534	0.1688	−0.0984	0.060*
H16B	0.2868	0.1098	−0.1498	0.060*
N21	0.1576 (6)	−0.3043 (5)	0.4705 (4)	0.050 (3)
H21M	0.1216	−0.3646	0.5156	0.060*
N22	−0.0101 (7)	−0.1100 (5)	0.3476 (4)	0.049 (3)
H22M	0.0417	−0.0901	0.3773	0.060*
N23	−0.2200 (6)	0.1586 (5)	0.4304 (4)	0.043 (3)
H23M	−0.1322	0.1403	0.4422	0.050*
H23N	−0.3041	0.1493	0.4709	0.050*
C21	0.2979 (8)	−0.3494 (7)	0.4924 (6)	0.057 (4)
H21A	0.3355	−0.4431	0.5000	0.080*
H21B	0.3640	−0.3122	0.4402	0.080*
C22	0.1608 (9)	−0.3290 (7)	0.3774 (5)	0.061 (4)
H22A	0.2365	−0.3001	0.3285	0.080*
H22B	0.1804	−0.4209	0.3806	0.080*
C23	0.0202 (8)	−0.2534 (6)	0.3533 (5)	0.054 (4)
H23A	−0.0551	−0.2829	0.4022	0.080*
H23B	0.0186	−0.2674	0.2934	0.080*
C24	−0.1668 (8)	−0.0391 (7)	0.3622 (5)	0.050 (4)
H24A	−0.2034	−0.0627	0.3199	0.080*
H24B	−0.2166	−0.0667	0.4265	0.080*
C25	−0.2009 (9)	0.1085 (7)	0.3438 (5)	0.052 (4)
H25A	−0.2880	0.1499	0.3206	0.080*
H25B	−0.1218	0.1320	0.2951	0.080*
C26	−0.2851 (8)	0.3060 (7)	0.4179 (5)	0.055 (4)
H26A	−0.3797	0.3314	0.4053	0.080*
H26B	−0.2242	0.3473	0.3646	0.080*
O1W	0.5410 (6)	0.0953 (7)	0.5561 (4)	0.109 (4)
H1WA	0.4748	0.1553	0.5318	0.100*
H1WB	0.5514	0.0486	0.5168	0.100*
O2W	0.5361 (7)	0.6723 (7)	0.2006 (5)	0.115 (5)
H2WA	0.4972	0.6191	0.1956	0.120*
H2WB	0.4752	0.7100	0.2456	0.120*
O3W	−0.3176 (6)	0.6593 (6)	0.3319 (4)	0.097 (4)
H3WA	−0.2313	0.6072	0.3261	0.100*
H3WB	−0.3374	0.6901	0.3819	0.100*
O4W	0.3133 (9)	0.9111 (7)	0.2125 (6)	0.142 (6)
H4WA	0.2233	0.9258	0.2404	0.150*
H4WB	0.3860	0.8558	0.2328	0.150*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.026 (1)	0.026 (1)	0.023 (1)	−0.004 (1)	−0.005 (1)	−0.010 (1)
C1	0.028 (4)	0.034 (4)	0.041 (4)	−0.007 (3)	−0.014 (3)	−0.003 (3)
N1	0.045 (4)	0.042 (3)	0.062 (4)	0.001 (3)	−0.013 (3)	−0.027 (3)
C2	0.045 (4)	0.040 (4)	0.030 (4)	−0.009 (3)	−0.003 (3)	−0.017 (4)
N2	0.072 (5)	0.060 (4)	0.046 (4)	−0.03 (3)	0.003 (3)	−0.036 (4)
C3	0.038 (4)	0.030 (4)	0.043 (4)	−0.004 (3)	−0.009 (3)	−0.017 (3)
N3	0.045 (4)	0.044 (4)	0.067 (4)	−0.010 (3)	−0.016 (3)	−0.004 (3)
C4	0.036 (4)	0.034 (4)	0.040 (4)	−0.006 (3)	−0.005 (3)	−0.013 (3)
N4	0.061 (4)	0.068 (4)	0.036 (4)	−0.016 (3)	−0.013 (3)	−0.017 (3)
C5	0.042 (4)	0.042 (4)	0.024 (3)	−0.006 (3)	−0.010 (3)	−0.016 (4)
N5	0.035 (4)	0.060 (4)	0.048 (4)	−0.015 (3)	−0.016 (3)	0.004 (3)
C6	0.040 (4)	0.040 (4)	0.036 (4)	−0.005 (3)	−0.014 (3)	−0.009 (3)
N6	0.086 (5)	0.060 (4)	0.051 (4)	−0.012 (3)	−0.033 (4)	−0.022 (4)
K1	0.059 (1)	0.069 (1)	0.040 (1)	−0.007 (1)	−0.008 (1)	−0.024 (1)
N11	0.031 (3)	0.046 (3)	0.039 (3)	−0.003 (3)	−0.010 (2)	−0.012 (3)
N12	0.046 (4)	0.042 (3)	0.045 (3)	−0.008 (3)	−0.012 (3)	−0.010 (3)
N13	0.040 (3)	0.037 (3)	0.038 (3)	−0.006 (2)	−0.011 (3)	−0.019 (3)
C11	0.029 (4)	0.053 (4)	0.046 (4)	−0.011 (3)	−0.007 (3)	−0.012 (3)
C12	0.032 (4)	0.039 (4)	0.060 (5)	−0.006 (3)	−0.008 (3)	−0.004 (3)
C13	0.053 (5)	0.040 (4)	0.046 (4)	−0.013 (3)	−0.003 (4)	−0.006 (4)
C14	0.053 (5)	0.028 (4)	0.066 (5)	−0.006 (3)	−0.019 (4)	−0.014 (3)
C15	0.058 (5)	0.039 (4)	0.044 (4)	0.000 (3)	−0.011 (4)	−0.025 (4)
C16	0.036 (4)	0.052 (4)	0.039 (4)	−0.012 (3)	−0.001 (3)	−0.023 (3)
N21	0.055 (4)	0.046 (3)	0.055 (4)	−0.015 (3)	−0.010 (3)	−0.021 (3)
N22	0.065 (4)	0.040 (3)	0.058 (4)	−0.008 (3)	−0.029 (3)	−0.023 (3)
N23	0.036 (3)	0.052 (4)	0.047 (3)	−0.004 (3)	−0.017 (3)	−0.018 (3)
C21	0.048 (5)	0.048 (4)	0.077 (6)	−0.023 (4)	−0.009 (4)	−0.012 (4)
C22	0.077 (6)	0.048 (5)	0.063 (5)	−0.027 (4)	−0.005 (4)	−0.021 (4)
C23	0.073 (6)	0.046 (4)	0.053 (5)	−0.012 (4)	−0.022 (4)	−0.022 (4)
C24	0.072 (5)	0.054 (5)	0.039 (4)	−0.03 (3)	−0.021 (4)	−0.031 (4)
C25	0.076 (5)	0.061 (5)	0.036 (4)	−0.003 (3)	−0.025 (4)	−0.034 (4)
C26	0.053 (5)	0.044 (4)	0.066 (5)	0.001 (4)	−0.020 (4)	−0.016 (4)
O1W	0.063 (4)	0.129 (6)	0.105 (5)	0.050 (4)	−0.033 (4)	−0.036 (4)
O2W	0.116 (6)	0.113 (6)	0.141 (6)	0.004 (5)	−0.033 (5)	−0.083 (5)
O3W	0.069 (4)	0.114 (5)	0.089 (4)	−0.046 (4)	−0.021 (4)	0.016 (4)
O4W	0.153 (8)	0.115 (6)	0.164 (8)	−0.020 (6)	−0.063 (6)	−0.029 (6)

Geometric parameters (Å, º)

Co1—C1	1.920 (7)	N11—K1^i	3.298 (5)
Co1—C2	1.901 (7)	N12—C13	1.449 (8)
Co1—C3	1.894 (6)	N12—C14	1.447 (11)
Co1—C4	1.909 (8)	N13—C15	1.496 (7)
Co1—C5	1.902 (6)	N13—C16	1.492 (7)
Co1—C6	1.909 (8)	N13—K1^i	3.393 (7)
C1—N1	1.137 (9)	C11—C16^i	1.514 (8)
C2—N2	1.129 (10)	C12—C13	1.500 (13)
C3—N3	1.147 (8)	C14—C15	1.505 (9)
C4—N4	1.146 (11)	C16—C11^i	1.514 (8)
C5—N5	1.135 (8)	N21—C21	1.437 (11)
C6—N6	1.143 (11)	N21—C22	1.486 (11)
K1—N11	3.205 (6)	N22—C23	1.496 (9)
K1—N13	3.247 (5)	N22—C24	1.471 (9)
K1—N22	3.168 (6)	N23—C25	1.486 (10)
K1—C24	3.369 (7)	N23—C26	1.513 (8)
K1—K1^i	3.699 (4)	C21—C26^ii	1.508 (13)
K1—N11^i	3.298 (5)	C22—C23	1.469 (11)
K1—N13^i	3.393 (7)	C24—C25	1.513 (10)
N11—C11	1.489 (11)	C26—C21^ii	1.508 (13)
N11—C12	1.475 (7)
N22···N1	3.089 (9)	N23···N1	3.030 (9)
O2W···N2	2.898 (9)	O3W···N3	2.807 (9)
O1W···N4	2.860 (9)	N11^iii···N5	3.049 (9)
N13···N6	2.814 (9)	O1W···N23^iii	2.745 (9)
O2W···O4W	2.807 (9)	O2W···O3W^iii	2.761 (9)
C1—Co1—C2	177.3 (3)	N13—K1—N13^i	112.3 (1)
C1—Co1—C3	90.1 (3)	N22—K1—N13^i	115.5 (2)
C2—Co1—C3	88.4 (3)	C24—K1—N13^i	107.3 (2)
C1—Co1—C4	89.1 (3)	K1^i—K1—N13^i	54.3 (1)
C2—Co1—C4	88.8 (3)	N11^i—K1—N13^i	82.4 (1)
C3—Co1—C4	92.3 (3)	K1—N11—C11	111.8 (3)
C1—Co1—C5	92.2 (3)	K1—N11—C12	133.5 (5)
C2—Co1—C5	89.4 (3)	C11—N11—C12	114.4 (6)
C3—Co1—C5	177.3 (2)	K1—N11—K1^i	69.3 (1)
C4—Co1—C5	89.2 (3)	C11—N11—K1^i	92.1 (3)
C1—Co1—C6	89.6 (3)	C12—N11—K1^i	114.0 (3)
C2—Co1—C6	92.6 (3)	C13—N12—C14	114.7 (6)
C3—Co1—C6	90.0 (3)	K1—N13—C15	136.8 (3)
C4—Co1—C6	177.3 (2)	K1—N13—C16	110.4 (3)
C5—Co1—C6	88.5 (3)	C15—N13—C16	112.2 (4)
Co1—C1—N1	177.9 (5)	K1—N13—K1^i	67.7 (1)
Co1—C2—N2	177.4 (6)	C15—N13—K1^i	106.2 (5)
Co1—C3—N3	178.1 (7)	C16—N13—K1^i	88.9 (4)
Co1—C4—N4	177.5 (5)	N11—C11—C16^i	114.0 (6)
Co1—C5—N5	178.9 (6)	N11—C12—C13	109.7 (6)
Co1—C6—N6	178.2 (6)	N12—C13—C12	109.1 (6)
N11—K1—N13	86.1 (1)	N12—C14—C15	108.6 (6)
N11—K1—N22	125.4 (1)	N13—C15—C14	109.0 (5)
N13—K1—N22	131.7 (2)	N13—C16—C11^i	113.5 (5)
N11—K1—C24	99.9 (2)	C21—N21—C22	114.1 (6)
N13—K1—C24	136.1 (2)	K1—N22—C23	97.7 (4)
N22—K1—C24	25.8 (2)	K1—N22—C24	84.8 (4)
N11—K1—K1^i	56.5 (1)	C23—N22—C24	112.1 (6)
N13—K1—K1^i	58.0 (1)	C25—N23—C26	112.5 (5)
N22—K1—K1^i	168.2 (1)	N21—C21—C26^i	109.7 (6)
C24—K1—K1^i	154.8 (2)	N21—C22—C23	108.7 (6)
N11—K1—N11^i	110.7 (1)	N22—C23—C22	111.0 (8)
N13—K1—N11^i	58.1 (1)	K1—C24—N22	69.5 (3)
N22—K1—N11^i	122.3 (1)	K1—C24—C25	86.2 (3)
C24—K1—N11^i	147.9 (2)	N22—C24—C25	113.9 (7)
K1B—K1—N11^i	54.2 (1)	N23—C25—C24	112.7 (5)
N11—K1—N13^i	57.6 (1)	N23—C26—C21^i	109.3 (6)

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

(2)

Crystal data

KH2[Co(CN)6](C12H28N4)	F(000) = 1016
Mr = 484.55	Dx = 1.363 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 10.675 (2) Å	θ = 5–15°
b = 10.516 (2) Å	µ = 0.93 mm^−1
c = 21.051 (4) Å	T = 293 K
β = 91.89 (3)°	Block, yellow
V = 2361.9 (8) Å^3	0.35 × 0.30 × 0.22 mm
Z = 4

Data collection

Rigaku AFC7R diffractometer	3133 reflections with > 4σ(F)
Radiation source: Rigaku RU-200 rotating-anode generator powered at 50kV and 90mA	Rint = 0.021
Graphite monochromator	θmax = 27.5°, θmin = 1.9°
ω scans	h = 0→13
Absorption correction: empirical	k = 0→13
Tmin = 0.942, Tmax = 1.000	l = −27→27
5713 measured reflections	3 standard reflections every 150 reflections
5425 independent reflections	intensity decay: −1.7%

Refinement

Refinement on F	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.049	H-atom parameters not defined?
wR(F^2) = 0.063	Calculated w = 1/[σ^2(Fo) + 0.0002Fo^2]
3133 reflections	(Δ/σ)max = 0.082
272 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.69 e Å^−3
Primary atom site location: structure-invariant direct methods

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	Occ. (<1)
K1	0.1883 (1)	0.4827 (1)	−0.1228 (1)	0.050 (1)
Co1	0.2773 (1)	0.7967 (1)	0.1154 (1)	0.024 (1)
C1	0.2340 (3)	0.6309 (3)	0.0861 (2)	0.034 (1)
N1	0.2133 (3)	0.5307 (3)	0.0676 (2)	0.054 (1)
C2	0.2784 (3)	0.7396 (3)	0.2007 (2)	0.030 (1)
N2	0.2797 (3)	0.7090 (3)	0.2528 (2)	0.043 (1)
C3	0.3258 (3)	0.9590 (3)	0.1457 (2)	0.031 (1)
N3	0.3537 (3)	1.0568 (3)	0.1662 (2)	0.050 (1)
C4	0.2689 (3)	0.8551 (3)	0.0294 (2)	0.032 (1)
N4	0.2573 (3)	0.8862 (3)	−0.0228 (2)	0.043 (1)
C5	0.4495 (3)	0.7521 (3)	0.1106 (2)	0.032 (1)
N5	0.5526 (3)	0.7239 (3)	0.1106 (2)	0.050 (1)
C6	0.1073 (3)	0.8442 (3)	0.1248 (2)	0.031 (1)
N6	0.0073 (3)	0.8767 (3)	0.1333 (2)	0.039 (1)
N7	0.2863 (3)	0.3083 (3)	−0.0036 (2)	0.031 (1)
H(7)	0.2496	0.3735	0.0163	0.050*
H(7N)	0.3238	0.3241	−0.0405	0.050*	0.5
N8	−0.0723 (3)	0.2521 (3)	0.1003 (2)	0.039 (1)
H(8)	−0.1264	0.1966	0.0818	0.050*
H(8N)	−0.1253	0.3173	0.1060	0.050*	0.5
N9	0.1996 (3)	0.2945 (3)	0.2989 (2)	0.037 (1)
H(9)	0.2369	0.2500	0.3308	0.050*
H(9N)	0.1315	0.3148	0.3208	0.050*	0.5
N10	0.5733 (3)	0.3938 (3)	0.1733 (2)	0.039 (1)
H(10)	0.6145	0.4637	0.1608	0.050*
H(10N)	0.6226	0.3490	0.2006	0.050*	0.5
C7	0.1846 (3)	0.2164 (3)	−0.0234 (2)	0.035 (1)
H(7A)	0.2233	0.1414	−0.0399	0.100*
H(7B)	0.1345	0.2538	−0.0572	0.100*
C8	0.0981 (3)	0.1784 (3)	0.0293 (2)	0.034 (1)
H(8A)	0.1481	0.1482	0.0649	0.100*
H(8B)	0.0441	0.1105	0.0151	0.100*
C9	0.0189 (3)	0.2885 (3)	0.0505 (2)	0.037 (1)
H(9A)	0.0730	0.3539	0.0675	0.100*
H(9B)	−0.0260	0.3226	0.0141	0.100*
C10	−0.0193 (3)	0.1949 (3)	0.1598 (2)	0.042 (1)
H(10A)	0.0311	0.1226	0.1496	0.100*
H(10B)	−0.0862	0.1658	0.1855	0.100*
C11	0.0614 (3)	0.2887 (3)	0.1987 (2)	0.042 (1)
H(11A)	0.0097	0.3523	0.2174	0.100*
H(11B)	0.1201	0.3298	0.1718	0.100*
C12	0.1301 (3)	0.2131 (3)	0.2505 (2)	0.042 (1)
H(12A)	0.0705	0.1608	0.2715	0.100*
H(12B)	0.1889	0.1577	0.2308	0.100*
C13	0.2822 (3)	0.3959 (3)	0.2744 (2)	0.037 (1)
H(13A)	0.3186	0.4436	0.3092	0.100*
H(13B)	0.2326	0.4530	0.2484	0.100*
C14	0.3870 (3)	0.3410 (3)	0.2350 (2)	0.036 (1)
H(14A)	0.3513	0.2857	0.2030	0.100*
H(14B)	0.4427	0.2919	0.2620	0.100*
C15	0.4606 (3)	0.4460 (3)	0.2040 (2)	0.037 (1)
H(15A)	0.4078	0.4870	0.1724	0.100*
H(15B)	0.4850	0.5081	0.2354	0.100*
C16	0.5530 (3)	0.2978 (3)	0.1215 (2)	0.039 (1)
H(16A)	0.5089	0.2265	0.1385	0.100*
H(16B)	0.6326	0.2681	0.1076	0.100*
C17	0.4772 (3)	0.3494 (3)	0.0643 (2)	0.043 (1)
H(17A)	0.5310	0.3653	0.0295	0.100*
H(17B)	0.4385	0.4281	0.0760	0.100*
C18	0.3773 (3)	0.2554 (3)	0.0448 (2)	0.048 (1)
H(18A)	0.4167	0.1815	0.0276	0.100*
H(18B)	0.3330	0.2298	0.0817	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K(1)	0.050 (1)	0.039 (1)	0.061 (1)	0.003 (1)	0.008 (1)	0.001 (1)
Co(1)	0.025 (1)	0.021 (1)	0.027 (1)	−0.005 (1)	0.002 (1)	0.000 (1)
C(1)	0.032 (1)	0.033 (1)	0.036 (1)	−0.007 (1)	−0.003 (1)	0.001 (1)
N(1)	0.051 (1)	0.036 (1)	0.074 (1)	−0.021 (1)	−0.001 (1)	0.000 (1)
C(2)	0.027 (1)	0.025 (1)	0.039 (1)	−0.005 (1)	0.002 (1)	−0.003 (1)
N(2)	0.045 (1)	0.047 (1)	0.038 (1)	0.005 (1)	0.002 (1)	−0.003 (1)
C(3)	0.034 (1)	0.030 (1)	0.029 (1)	0.004 (1)	0.004 (1)	−0.001 (1)
N(3)	0.065 (1)	0.031 (1)	0.055 (1)	−0.011 (1)	0.003 (1)	−0.009 (1)
C(4)	0.028 (1)	0.028 (1)	0.039 (1)	−0.010 (1)	0.001 (1)	−0.001 (1)
N(4)	0.052 (1)	0.047 (1)	0.030 (1)	−0.001 (1)	0.001 (1)	−0.002 (1)
C(5)	0.037 (1)	0.034 (1)	0.026 (1)	−0.005 (1)	0.005 (1)	0.003 (1)
N(5)	0.036 (1)	0.068 (1)	0.046 (1)	−0.004 (1)	0.006 (1)	0.015 (1)
C(6)	0.033 (1)	0.026 (1)	0.032 (1)	0.000 (1)	0.001 (1)	−0.002 (1)
N(6)	0.028 (1)	0.041 (1)	0.047 (1)	−0.002 (1)	0.008 (1)	0.000 (1)
N(7)	0.036 (1)	0.031 (1)	0.025 (1)	−0.002 (1)	0.002 (1)	−0.005 (1)
N(8)	0.028 (1)	0.037 (1)	0.051 (1)	−0.009 (1)	0.002 (1)	−0.005 (1)
N(9)	0.039 (1)	0.041 (1)	0.031 (1)	0.008 (1)	0.009 (1)	0.008 (1)
N(10)	0.031 (1)	0.048 (1)	0.038 (1)	−0.002 (1)	0.002 (1)	−0.008 (1)
C(7)	0.040 (1)	0.033 (1)	0.033 (1)	−0.007 (1)	0.000 (1)	−0.007 (1)
C(8)	0.035 (1)	0.025 (1)	0.042 (1)	0.004 (1)	0.005 (1)	−0.004 (1)
C(9)	0.035 (1)	0.033 (1)	0.041 (1)	0.004 (1)	0.000 (1)	−0.001 (1)
C(10)	0.047 (1)	0.032 (1)	0.048 (1)	−0.006 (1)	0.014 (1)	−0.008 (1)
C(11)	0.048 (1)	0.034 (1)	0.045 (1)	−0.001 (1)	−0.001 (1)	0.001 (1)
C(12)	0.049 (1)	0.036 (1)	0.043 (1)	0.004 (1)	0.010 (1)	0.003 (1)
C(13)	0.039 (1)	0.037 (1)	0.036 (1)	−0.004 (1)	0.004 (1)	0.000 (1)
C(14)	0.034 (1)	0.034 (1)	0.041 (1)	−0.002 (1)	0.007 (1)	0.003 (1)
C(15)	0.042 (1)	0.035 (1)	0.035 (1)	−0.003 (1)	0.004 (1)	−0.005 (1)
C(16)	0.031 (1)	0.045 (1)	0.042 (1)	−0.011 (1)	0.000 (1)	0.002 (1)
C(17)	0.043 (1)	0.044 (1)	0.042 (1)	0.002 (1)	−0.003 (1)	−0.004 (1)
C(18)	0.049 (1)	0.043 (1)	0.051 (1)	0.009 (1)	−0.016 (1)	−0.006 (1)

Geometric parameters (Å, º)

K1—N7	3.252 (3)	N7—C7	1.502 (5)
K1—C7	3.497 (4)	N7—C18	1.493 (5)
K1—N8^i	3.095 (3)	N8—C9	1.503 (5)
K1—N9^ii	3.352 (3)	N8—C10	1.486 (5)
K1—N10^iii	3.077 (3)	N9—C12	1.508 (5)
Co1—C1	1.901 (4)	N9—C13	1.487 (5)
Co1—C2	1.894 (4)	N10—C15	1.490 (5)
Co1—C3	1.889 (3)	N10—C16	1.496 (5)
Co1—C4	1.910 (4)	C7—C8	1.520 (5)
Co1—C5	1.903 (3)	C8—C9	1.510 (5)
Co1—C6	1.899 (3)	C10—C11	1.529 (5)
C1—N1	1.142 (5)	C11—C12	1.518 (6)
C2—N2	1.143 (5)	C13—C14	1.527 (5)
C3—N3	1.151 (5)	C14—C15	1.516 (5)
C4—N4	1.150 (5)	C16—C17	1.529 (6)
C5—N5	1.140 (5)	C17—C18	1.502 (5)
C6—N6	1.140 (5)
N1···N7	2.899 (6)	N2···N10^v	2.916 (6)
N4···N8^i	2.909 (6)	N5···N7^iii	2.898 (6)
N6···N9^iv	2.806 (6)
N7—K1—N8^i	120.6 (1)	Co1—C6—N6	176.2 (4)
N7—K1—N9^ii	82.7 (1)	K1—N7—C7	86.5 (2)
N8^i—K1—N9^ii	151.7 (1)	K1—N7—C18	157.3 (2)
N7—K1—N10^iii	104.8 (1)	C7—N7—C18	113.4 (3)
N8^i—K1—N10^iii	90.7 (1)	C9—N8—C10	117.0 (3)
N9^ii—K1—N10^iii	98.8 (1)	C9—N8—K1^i	98.6 (2)
C1—Co1—C2	90.6 (2)	C10—N8—K1^i	112.2 (2)
C1—Co1—C3	177.9 (1)	C12—N9—C13	117.2 (3)
C2—Co1—C3	88.4 (2)	C12—N9—K1^vi	79.3 (2)
C1—Co1—C4	89.2 (2)	C13—N9—K1^vi	145.7 (2)
C2—Co1—C4	177.7 (1)	C15—N10—C16	117.7 (3)
C3—Co1—C4	91.9 (2)	C15—N10—K1^iii	133.1 (2)
C1—Co1—C5	89.0 (1)	C16—N10—K1^iii	97.8 (2)
C2—Co1—C5	89.8 (2)	N7—C7—C8	114.7 (3)
C3—Co1—C5	89.2 (1)	C7—C8—C9	112.0 (3)
C4—Co1—C5	92.6 (2)	N8—C9—C8	113.1 (3)
C1—Co1—C6	93.0 (1)	N8—C10—C11	112.5 (3)
C2—Co1—C6	87.7 (2)	C10—C11—C12	107.2 (3)
C3—Co1—C6	88.8 (1)	N9—C12—C11	113.8 (3)
C4—Co1—C6	90.0 (2)	N9—C13—C14	111.7 (3)
C5—Co1—C6	176.8 (2)	C13—C14—C15	111.0 (3)
Co1—C1—N1	176.9 (3)	N10—C15—C14	110.9 (3)
Co1—C2—N2	177.9 (3)	N10—C16—C17	113.2 (3)
Co1—C3—N3	177.6 (4)	C16—C17—C18	109.5 (3)
Co1—C4—N4	175.9 (3)	N7—C18—C17	112.4 (3)
Co1—C5—N5	176.9 (4)

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

(3)

Crystal data

H3[Co(CN)6](C8H20N4)·2(H2O)	Z = 1
Mr = 426.37	F(000) = 224
Triclinic, P1	Dx = 1.423 Mg m^−3
a = 7.635 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.202 (5) Å	Cell parameters from 25 reflections
c = 9.442 (3) Å	θ = 5–15°
α = 109.08 (1)°	µ = 0.89 mm^−1
β = 103.46 (1)°	T = 293 K
γ = 107.03 (1)°	Plate, colorless
V = 497.7 (4) Å^3	0.30 × 0.30 × 0.08 mm

Data collection

Siemens P4 diffractometer	2015 reflections with > 4σ(F)
Radiation source: fine-focus sealed tube	Rint = 0.187
Graphite monochromator	θmax = 27.5°, θmin = 2.5°
ω scans	h = 0→9
Absorption correction: empirical	k = −9→9
Tmin = 0.851, Tmax = 1.000	l = −12→11
2375 measured reflections	3 standard reflections every 100 reflections
2374 independent reflections	intensity decay: −1.5%

Refinement

Refinement on F	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	One H atom on O2W, and the acidic H atoms of the macrocycle can not be located from differential map
R[F^2 > 2σ(F^2)] = 0.061	Calculated w = 1/[σ^2(Fo) + 0.002(Fo^2)]
wR(F^2) = 0.082	(Δ/σ)max = 0.150
2015 reflections	Δρmax = 0.85 e Å^−3
242 parameters	Δρmin = −0.47 e Å^−3
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.10 (5)
Secondary atom site location: difference Fourier map

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. One H atom on O2W, and the acdic H atoms of the macrocycle can not be located from differential map.

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

	x	y	z	Uiso*/Ueq
Co1	0.0000	0.0000	0.0000	0.019 (1)
C1	−0.1068 (3)	−0.2125 (3)	0.0482 (3)	0.034 (1)
C2	0.2135 (3)	0.1290 (3)	0.2041 (3)	0.031 (1)
C3	0.0837 (3)	0.2040 (3)	−0.0433 (3)	0.032 (1)
C4	−0.1921 (3)	−0.1299 (3)	−0.2050 (3)	0.029 (1)
C5	−0.1527 (3)	0.1068 (3)	0.0987 (3)	0.036 (1)
C6	0.1643 (3)	−0.1085 (3)	−0.0755 (3)	0.033 (1)
N1	−0.1506 (3)	−0.3420 (3)	0.0647 (3)	0.066 (1)
N2	0.3225 (3)	0.1964 (3)	0.3223 (3)	0.057 (1)
N3	0.1400 (3)	0.3316 (3)	−0.0799 (3)	0.071 (1)
N4	−0.3315 (3)	−0.2175 (3)	−0.3367 (3)	0.051 (1)
N5	−0.2505 (3)	0.1810 (3)	0.1454 (3)	0.098 (1)
N6	0.2563 (3)	−0.1745 (3)	−0.1367 (3)	0.090 (1)
N7	−0.2931 (3)	0.2971 (3)	−0.1851 (3)	0.031 (1)
H7A	−0.2061	0.2938	−0.1044	0.080*
N8	−0.6327 (3)	−0.0621 (3)	−0.4367 (3)	0.073 (1)
H8A	−0.5160	−0.0714	−0.4098	0.080*
N9	−0.5935 (3)	−0.3615 (3)	−0.6614 (3)	0.033 (1)
N10	−0.3752 (3)	0.0608 (3)	−0.5720 (3)	0.062 (1)
H10A	−0.4926	0.0691	−0.5878	0.080*
C7	−0.4834 (3)	0.2559 (3)	−0.2048 (3)	0.086 (1)
H7B	−0.4999	0.3722	−0.1826	0.080*
H7C	−0.4989	0.2224	−0.1187	0.080*
C8	−0.6565 (3)	0.1117 (3)	−0.3447 (3)	0.046 (1)
H8B	−0.7687	0.0758	−0.3147	0.080*
H8C	−0.6848	0.1680	−0.4170	0.080*
C9	−0.7954 (3)	−0.2089 (3)	−0.5633 (3)	0.033 (1)
H9A	−0.8389	−0.1623	−0.6397	0.080*
H9B	−0.8971	−0.2389	−0.5208	0.080*
C10	−0.7823 (3)	−0.3874 (3)	−0.6521 (3)	0.073 (1)
H10B	−0.8114	−0.4692	−0.6000	0.080*
H10C	−0.8791	−0.4487	−0.7590	0.080*
C11	−0.5384 (3)	−0.2647 (3)	−0.7836 (3)	0.082 (1)
H11A	−0.6410	−0.2302	−0.8274	0.080*
H11B	−0.5182	−0.3487	−0.8703	0.080*
C12	−0.3536 (3)	−0.0938 (3)	−0.6700 (3)	0.053 (1)
H12A	−0.2700	−0.1295	−0.6044	0.080*
H12B	−0.2879	−0.0567	−0.7366	0.080*
C13	−0.1861 (3)	0.2185 (3)	−0.4356 (3)	0.041 (1)
H13A	−0.1024	0.2835	−0.4787	0.080*
H13B	−0.1154	0.1645	−0.3801	0.080*
C14	−0.2347 (3)	0.3568 (3)	−0.3220 (3)	0.091 (1)
H14A	−0.1222	0.4749	−0.2690	0.080*
H14B	−0.3409	0.3764	−0.3816	0.080*
O1W	−0.3372 (3)	−0.5152 (3)	−0.7439 (3)	0.072 (1)
H1WA	−0.2781	−0.4841	−0.6449	0.050*
H1WB	−0.2639	−0.4716	−0.7896	0.050*
O2W	0.2737 (3)	−0.5132 (3)	−0.3581 (3)	0.099 (1)
H2WA	0.3354	−0.4539	−0.2570	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.021 (1)	0.018 (1)	0.019 (1)	0.009 (1)	0.005 (1)	0.008 (1)
C1	0.055 (1)	0.028 (1)	0.015 (1)	0.013 (1)	0.015 (1)	0.005 (1)
C2	0.027 (1)	0.043 (1)	0.024 (1)	0.019 (1)	0.001 (1)	0.019 (1)
C3	0.041 (1)	0.019 (1)	0.022 (1)	0.001 (1)	0.008 (1)	0.005 (1)
C4	0.033 (1)	0.015 (1)	0.033 (1)	0.001 (1)	0.011 (1)	0.014 (1)
C5	0.044 (1)	0.031 (1)	0.020 (1)	−0.002 (1)	0.007 (1)	0.017 (1)
C6	0.026 (1)	0.045 (1)	0.026 (1)	0.007 (1)	0.008 (1)	0.021 (1)
N1	0.100 (1)	0.027 (1)	0.045 (1)	0.014 (1)	0.030 (1)	−0.008 (1)
N2	0.050 (1)	0.041 (1)	0.053 (1)	0.005 (1)	−0.012 (1)	0.022 (1)
N3	0.113 (1)	0.030 (1)	0.020 (1)	0.010 (1)	−0.013 (1)	−0.007 (1)
N4	0.054 (1)	0.061 (1)	0.014 (1)	−0.005 (1)	−0.011 (1)	0.031 (1)
N5	0.038 (1)	0.074 (1)	0.109 (1)	−0.033 (1)	0.011 (1)	0.017 (1)
N6	0.064 (1)	0.122 (1)	0.062 (1)	−0.007 (1)	0.021 (1)	0.063 (1)
N7	0.035 (1)	0.033 (1)	0.021 (1)	0.012 (1)	0.004 (1)	0.015 (1)
N8	0.011 (1)	0.044 (1)	0.127 (1)	0.034 (1)	−0.019 (1)	0.001 (1)
N9	0.030 (1)	0.035 (1)	0.029 (1)	0.009 (1)	0.005 (1)	0.014 (1)
N10	0.61 (1)	0.008 (1)	0.071 (1)	−0.005 (1)	−0.032 (1)	0.019 (1)
C7	0.056 (1)	0.044 (1)	0.111 (1)	0.037 (1)	−0.035 (1)	0.003 (1)
C8	0.046 (1)	0.048 (1)	0.026 (1)	0.003 (1)	0.013 (1)	0.010 (1)
C9	0.042 (1)	0.026 (1)	0.030 (1)	0.010 (1)	0.015 (1)	0.012 (1)
C10	0.012 (1)	0.006 (1)	0.135 (1)	−0.013 (1)	−0.019 (1)	0.004 (1)
C11	0.106 (1)	0.022 (1)	0.066 (1)	0.013 (1)	−0.042 (1)	0.020 (1)
C12	0.051 (1)	0.052 (1)	0.031 (1)	0.002 (1)	0.025 (1)	−0.003 (1)
C13	0.010 (1)	0.054 (1)	0.039 (1)	0.016 (1)	−0.001 (1)	−0.002 (1)
C14	0.092 (1)	0.022 (1)	0.099 (1)	−0.002 (1)	0.004 (1)	−0.001 (1)
O1W	0.098 (1)	0.058 (1)	0.118 (1)	0.058 (1)	0.080 (1)	0.054 (1)
O2W	0.110 (1)	0.065 (1)	0.154 (1)	0.046 (1)	0.092 (1)	0.046 (1)

Geometric parameters (Å, º)

Co1—C1	1.942 (3)	N7—C7	1.344 (3)
Co1—C2	1.919 (2)	N7—C14	1.632 (4)
Co1—C3	1.822 (3)	N8—C8	1.495 (3)
Co1—C4	1.857 (2)	N8—C9	1.383 (2)
Co1—C5	1.889 (3)	N9—C10	1.423 (3)
Co1—C6	1.879 (3)	N9—C11	1.663 (4)
C1—N1	1.090 (4)	N10—C12	1.385 (3)
C2—N2	1.068 (3)	N10—C13	1.539 (2)
C3—N3	1.200 (4)	C7—C8	1.463 (2)
C4—N4	1.244 (3)	C9—C10	1.476 (3)
C5—N5	1.169 (4)	C11—C12	1.503 (2)
C6—N6	1.152 (4)	C13—C14	1.487 (3)
O1W···N9	2.745 (8)	O1W^ii···N9	2.707 (8)
O2W···N6	2.942 (8)	O1W^iii···N9	3.001 (8)
N7···N1^i	2.804 (8)	N8···N4	3.049 (8)
N9···N4	2.862 (8)	N10^iv···N2	2.952 (8)
C1—Co1—C2	91.2 (1)	Co1—C3—N3	176.1 (2)
C1—Co1—C3	175.4 (1)	Co1—C4—N4	175.1 (2)
C2—Co1—C3	90.3 (1)	Co1—C5—N5	171.7 (3)
C1—Co1—C4	89.8 (1)	Co1—C6—N6	172.9 (2)
C2—Co1—C4	175.3 (1)	C7—N7—C14	112.9 (2)
C3—Co1—C4	89.1 (1)	C8—N8—C9	118.1 (2)
C1—Co1—C5	87.5 (1)	C10—N9—C11	115.3 (2)
C2—Co1—C5	89.0 (1)	C12—N10—C13	116.0 (2)
C3—Co1—C5	88.3 (1)	N7—C7—C8	127.9 (2)
C4—Co1—C5	95.6 (1)	N8—C8—C7	115.5 (2)
C1—Co1—C6	88.6 (1)	N8—C9—C10	120.2 (2)
C2—Co1—C6	85.5 (1)	N9—C10—C9	113.0 (2)
C3—Co1—C6	95.8 (1)	N9—C11—C12	101.4 (2)
C4—Co1—C6	89.9 (1)	N10—C12—C11	117.1 (2)
C5—Co1—C6	173.2 (1)	N10—C13—C14	110.3 (2)
Co1—C1—N1	169.7 (2)	N7—C14—C13	114.5 (2)
Co1—C2—N2	174.7 (3)

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