Bis[hexa­amminecobalt(III)] penta­chloride nitrate

The title compound, [Co(NH₃)₆]₂Cl₅(NO₃), was obtained under hydro­thermal conditions. The asymmetric unit contains three Co³⁺ ions, one lying on an inversion center and the other two located at 2/m positions. All Co³⁺ ions are six-coordinated by NH₃ mol­ecules, forming [Co(NH₃)₆]³⁺ octahedra, with Co—N distances in the range 1.945 (4)–1.967 (3) Å. The nitrate N atom and one of the O atoms lie at a mirror plane. Among the Cl⁻ anions, one lies in a general position, one on a twofold axis and two on a mirror plane. N—H...O and N—H...Cl hydrogen bonds link the cations and anions into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](O-N) = 0.005 Å
• R factor = 0.050
• wR factor = 0.140
• Data-to-parameter ratio = 23.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Co2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Co1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N8
PLAT416_ALERT_2_C Short Intra D-H..H-D       H6A    ..  H7A     ..       1.95 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3B    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N6     -   H6B    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N7     -   H7B    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N7     -   H7C    ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1A    ..  CL1     ..       2.89 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1A    ..  CL3     ..       2.90 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5A    ..  CL4     ..       2.91 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6C    ..  CL3     ..       2.93 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7B    ..  CL3     ..       2.87 Ang.
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          7
PLAT975_ALERT_2_C Positive Residual Density at 0.99A from N7     .       0.57 eA-3
PLAT975_ALERT_2_C Positive Residual Density at 0.83A from N2     .       0.47 eA-3
PLAT975_ALERT_2_C Positive Residual Density at 0.96A from N7     .       0.44 eA-3
PLAT975_ALERT_2_C Positive Residual Density at 1.05A from N6     .       0.42 eA-3
PLAT975_ALERT_2_C Positive Residual Density at 1.06A from N3     .       0.41 eA-3
PLAT975_ALERT_2_C Positive Residual Density at 0.87A from N3     .       0.40 eA-3
PLAT976_ALERT_2_C Negative Residual Density at 0.93A from N7     .      -0.66 eA-3
PLAT976_ALERT_2_C Negative Residual Density at 0.99A from N7     .      -0.61 eA-3
PLAT976_ALERT_2_C Negative Residual Density at 0.79A from N3     .      -0.55 eA-3
PLAT976_ALERT_2_C Negative Residual Density at 0.76A from N6     .      -0.55 eA-3
PLAT976_ALERT_2_C Negative Residual Density at 0.88A from N7     .      -0.48 eA-3
PLAT976_ALERT_2_C Negative Residual Density at 1.09A from N4     .      -0.45 eA-3

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............         19

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
  27 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  21 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
   6 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

---

S1. Comment

Rencently, more attention has been paid to transition metal complexes, because they can to be employed as templates in the synthesis of various open-framework materials, including metal phosphates (Wang et al., 2003a,b) and germanates (Pan et al., 2005,2008). Our continued interest has been focused on the synthesis of microporous open-framework metal-organic hybride materials by introducing transition metal complexes as templates (Pan et al., 2010a,b, 2011; Tong & Pan, 2011; Liang et al., 2011). Unexpectedly, the title compound, [Co(NH₃)₆]₂(NO₃)Cl₅, was obtained.

The title compound is composed of [Co(NH₃)₆]³⁺ cations and the counterions Cl^- and NO₃^-, as shown in Fig. 1. The asymmetric part of this crystal structure contains three Co³⁺ ions; one is located on an inversion center, and the other two are positioned on the twofold rotation axis with center of symmetry (2/m). All Co(III) ions are six coordinated by NH₃ molecules to form [Co(NH₃)₆]³⁺ cations, having a slightly distorted octahedral geometry, as in the structure of [Co(NH₃)₆]₃[Zn₈(HPO₄)₈(PO₄)₂](PO₄) (Han et al., 2012). The Co—N bond distances are in the range from 1.945 (4) to 1.967 (3) Å. For the counterions, the N8 atom of NO₃^- anion is located on mirror plane and displays a trigonal geometry by bonded to three O atoms with the N—O distances of 1.234 (6)–1.253 (4) Å. The Cl^- anions are located in different positions: inversion center for Cl2, mirror plane for Cl1 and Cl4, and general position for Cl3. The [Co(NH₃)₆]³⁺ cations interact with the counterions Cl^- and NO₃^- via hydrogen bonds; the distances of N—H···O hydrogen bonds are in the range 3.048 (5)–3.155 (6) Å, and the distances of N—H···Cl hydrogen bonds lie in the range from 3.287 (4) to 3.484 (4) Å (Table 1), to form an extensive three-dimensional hydrogen-bonding network.

Related literature

For metal phosphates and germanates prepared using metal complexes as templates, see: Wang et al. (2003a,b); Pan et al. (2005, 2008). For our continued research interest focused on the synthesis of microporous open-framework

metal-organic hybride materials by introducing transition metal complexes as

templates, see: Pan et al. (2010a,b, 2011); Tong & Pan (2011); Liang et al. (2011). For a structure containing a [Co(NH₃)₆]³⁺ cation, see: Han et al. (2012).

S2. Experimental

In a typical synthesis, a mixture of Cd(NO₃)₂.4H₂O (0.231 g), pyromellitic acid (0.0254 g), [Co(NH₃)₆]Cl₃ (0.03 g), NaOH (0.016 g) and H₂O (10 ml) were added in a 20 ml Teflon-lined reactor under autogenous pressure at 100°C for 3 days. Yellow rod-like crystals were obtained.

S3. Refinement

All H atoms were positioned geometrically (N—H = 0.89 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.2U_eq(parent atom).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. A view of the asymmetric unit of title compound showing the atom labelling scheme. Ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x, 1 - y, -z; (ii) -x, y, -z; (iii) x, 1 - y, z; (iv) 1 - x, 1 - y, -z; (v) 1 - x, y, -z; (vi) 1/2 - x, 1/2 - y, 1 - z]. (iv) x, -y + 1, z; (v) -x, -y + 1, -z; (vi) -x, y, -z.

Bis[hexaamminecobalt(III)] pentachloride nitrate

Crystal data

[Co(NH3)6]2Cl5(NO3)	F(000) = 1160
Mr = 561.53	Dx = 1.722 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 7927 reflections
a = 21.118 (4) Å	θ = 1.7–28.4°
b = 14.985 (3) Å	µ = 2.18 mm^−1
c = 6.8491 (11) Å	T = 296 K
β = 92.147 (3)°	Rod, yellow
V = 2165.8 (6) Å^3	0.2 × 0.12 × 0.10 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	2813 independent reflections
Radiation source: fine-focus sealed tube	1870 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 83.66 pixels mm^-1	θmax = 28.4°, θmin = 1.7°
ϕ and ω scans	h = −27→28
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −19→20
Tmin = 0.738, Tmax = 0.770	l = −6→9
7927 measured 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0641P)^2 + 4.8344P] where P = (Fo^2 + 2Fc^2)/3
2813 reflections	(Δ/σ)max < 0.001
119 parameters	Δρmax = 0.65 e Å^−3
0 restraints	Δρmin = −0.71 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.2500	0.2500	0.5000	0.0193 (2)
N7	0.25395 (17)	0.3197 (3)	0.7422 (5)	0.0329 (9)
H7A	0.2923	0.3440	0.7585	0.040*
H7B	0.2465	0.2842	0.8429	0.040*
H7C	0.2249	0.3627	0.7353	0.040*
N6	0.16170 (16)	0.2158 (3)	0.5415 (5)	0.0342 (9)
H6A	0.1477	0.1812	0.4434	0.041*
H6B	0.1378	0.2646	0.5463	0.041*
H6C	0.1596	0.1861	0.6535	0.041*
N5	0.27844 (19)	0.1439 (3)	0.6414 (6)	0.0401 (10)
H5A	0.2811	0.0984	0.5585	0.048*
H5B	0.2509	0.1306	0.7323	0.048*
H5C	0.3164	0.1541	0.6982	0.048*
Co2	0.5000	0.5000	0.0000	0.0212 (3)
Cl4	0.66930 (8)	0.5000	0.4229 (2)	0.0350 (4)
N4	0.55640 (18)	0.5926 (3)	0.1076 (6)	0.0411 (10)
H4A	0.5852	0.6062	0.0208	0.049*
H4B	0.5758	0.5727	0.2168	0.049*
H4C	0.5339	0.6410	0.1341	0.049*
N3	0.4522 (2)	0.5000	0.2394 (7)	0.0329 (12)
H3A	0.4278	0.4517	0.2435	0.040*
H3B	0.4787	0.5000	0.3435	0.040*
Co3	0.0000	0.5000	0.0000	0.0208 (3)
N2	−0.0927 (2)	0.5000	−0.0085 (7)	0.0289 (11)
H2A	−0.1072	0.4517	−0.0712	0.035*
H2B	−0.1075	0.5000	0.1114	0.035*
N1	0.00050 (17)	0.5934 (3)	0.2019 (5)	0.0330 (9)
H1A	0.0403	0.6075	0.2360	0.040*
H1B	−0.0191	0.5734	0.3061	0.040*
H1C	−0.0195	0.6415	0.1551	0.040*
Cl3	0.12244 (5)	0.28432 (8)	0.00154 (16)	0.0351 (3)
Cl2	0.0000	0.19040 (14)	0.5000	0.0485 (5)
Cl1	0.11173 (8)	0.5000	0.5167 (2)	0.0459 (5)
O2	0.68054 (15)	0.5722 (2)	0.9173 (5)	0.0392 (8)
N8	0.7099 (2)	0.5000	0.9396 (7)	0.0291 (11)
O1	0.7671 (2)	0.5000	0.9832 (8)	0.0507 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0190 (4)	0.0185 (4)	0.0206 (4)	0.0001 (3)	0.0021 (3)	0.0002 (3)
N7	0.032 (2)	0.039 (2)	0.028 (2)	−0.0044 (17)	0.0031 (15)	−0.0072 (15)
N6	0.0265 (19)	0.036 (2)	0.041 (2)	−0.0052 (17)	0.0084 (16)	−0.0079 (18)
N5	0.046 (2)	0.032 (2)	0.042 (2)	0.0034 (19)	−0.0037 (18)	0.0093 (17)
Co2	0.0179 (5)	0.0211 (6)	0.0247 (6)	0.000	0.0025 (4)	0.000
Cl4	0.0419 (9)	0.0284 (8)	0.0347 (9)	0.000	−0.0006 (7)	0.000
N4	0.033 (2)	0.044 (3)	0.047 (2)	−0.0102 (19)	0.0093 (18)	−0.0124 (19)
N3	0.027 (3)	0.043 (3)	0.028 (3)	0.000	0.005 (2)	0.000
Co3	0.0165 (5)	0.0220 (6)	0.0239 (6)	0.000	0.0019 (4)	0.000
N2	0.017 (2)	0.029 (3)	0.040 (3)	0.000	−0.001 (2)	0.000
N1	0.030 (2)	0.035 (2)	0.034 (2)	0.0027 (17)	−0.0011 (16)	−0.0044 (16)
Cl3	0.0334 (6)	0.0315 (6)	0.0405 (7)	0.0048 (5)	0.0037 (5)	0.0012 (5)
Cl2	0.0462 (10)	0.0521 (12)	0.0478 (11)	0.000	0.0079 (8)	0.000
Cl1	0.0361 (9)	0.0683 (13)	0.0337 (9)	0.000	0.0056 (7)	0.000
O2	0.0395 (19)	0.036 (2)	0.043 (2)	0.0092 (15)	0.0046 (15)	−0.0019 (14)
N8	0.024 (3)	0.037 (3)	0.027 (3)	0.000	0.004 (2)	0.000
O1	0.022 (2)	0.053 (4)	0.077 (4)	0.000	−0.005 (2)	0.000

Geometric parameters (Å, º)

Co1—N5^i	1.945 (4)	Co2—N3^ii	1.958 (5)
Co1—N5	1.945 (4)	N4—H4A	0.8900
Co1—N7	1.960 (3)	N4—H4B	0.8900
Co1—N7^i	1.960 (3)	N4—H4C	0.8900
Co1—N6	1.965 (3)	N3—H3A	0.8900
Co1—N6^i	1.965 (3)	N3—H3B	0.8900
N7—H7A	0.8900	Co3—N2	1.956 (5)
N7—H7B	0.8900	Co3—N2^v	1.956 (5)
N7—H7C	0.8900	Co3—N1	1.967 (3)
N6—H6A	0.8900	Co3—N1^vi	1.967 (3)
N6—H6B	0.8900	Co3—N1^v	1.967 (3)
N6—H6C	0.8900	Co3—N1^iv	1.967 (3)
N5—H5A	0.8900	N2—H2A	0.8900
N5—H5B	0.8900	N2—H2B	0.8900
N5—H5C	0.8900	N1—H1A	0.8900
Co2—N4	1.955 (4)	N1—H1B	0.8900
Co2—N4^ii	1.955 (4)	N1—H1C	0.8900
Co2—N4^iii	1.955 (4)	O2—N8	1.253 (4)
Co2—N4^iv	1.955 (4)	N8—O1	1.234 (6)
Co2—N3	1.958 (5)	N8—O2^iv	1.253 (4)
N5^i—Co1—N5	180.000 (1)	N4^iv—Co2—N3	90.59 (16)
N5^i—Co1—N7	89.33 (16)	N4—Co2—N3^ii	89.41 (16)
N5—Co1—N7	90.67 (16)	N4^ii—Co2—N3^ii	90.59 (16)
N5^i—Co1—N7^i	90.67 (16)	N4^iii—Co2—N3^ii	90.59 (16)
N5—Co1—N7^i	89.33 (16)	N4^iv—Co2—N3^ii	89.41 (16)
N7—Co1—N7^i	180.0	N3—Co2—N3^ii	180.000 (1)
N5^i—Co1—N6	90.47 (17)	Co2—N4—H4A	109.5
N5—Co1—N6	89.53 (17)	Co2—N4—H4B	109.5
N7—Co1—N6	91.56 (15)	H4A—N4—H4B	109.5
N7^i—Co1—N6	88.44 (15)	Co2—N4—H4C	109.5
N5^i—Co1—N6^i	89.53 (17)	H4A—N4—H4C	109.5
N5—Co1—N6^i	90.47 (17)	H4B—N4—H4C	109.5
N7—Co1—N6^i	88.44 (15)	Co2—N3—H3A	110.1
N7^i—Co1—N6^i	91.56 (15)	Co2—N3—H3B	110.0
N6—Co1—N6^i	180.00 (6)	H3A—N3—H3B	108.9
Co1—N7—H7A	109.5	N2—Co3—N2^v	180.0
Co1—N7—H7B	109.5	N2—Co3—N1	90.00 (15)
H7A—N7—H7B	109.5	N2^v—Co3—N1	90.00 (15)
Co1—N7—H7C	109.5	N2—Co3—N1^vi	90.00 (15)
H7A—N7—H7C	109.5	N2^v—Co3—N1^vi	90.00 (15)
H7B—N7—H7C	109.5	N1—Co3—N1^vi	89.3 (2)
Co1—N6—H6A	109.5	N2—Co3—N1^v	90.00 (15)
Co1—N6—H6B	109.5	N2^v—Co3—N1^v	90.00 (15)
H6A—N6—H6B	109.5	N1—Co3—N1^v	180.0 (2)
Co1—N6—H6C	109.5	N1^vi—Co3—N1^v	90.7 (2)
H6A—N6—H6C	109.5	N2—Co3—N1^iv	90.00 (15)
H6B—N6—H6C	109.5	N2^v—Co3—N1^iv	90.00 (15)
Co1—N5—H5A	109.5	N1—Co3—N1^iv	90.7 (2)
Co1—N5—H5B	109.5	N1^vi—Co3—N1^iv	180.00 (16)
H5A—N5—H5B	109.5	N1^v—Co3—N1^iv	89.3 (2)
Co1—N5—H5C	109.5	Co3—N2—H2A	109.9
H5A—N5—H5C	109.5	Co3—N2—H2B	111.0
H5B—N5—H5C	109.5	H2A—N2—H2B	108.6
N4—Co2—N4^ii	180.0	Co3—N1—H1A	109.5
N4—Co2—N4^iii	89.6 (3)	Co3—N1—H1B	109.5
N4^ii—Co2—N4^iii	90.4 (3)	H1A—N1—H1B	109.5
N4—Co2—N4^iv	90.4 (3)	Co3—N1—H1C	109.5
N4^ii—Co2—N4^iv	89.6 (3)	H1A—N1—H1C	109.5
N4^iii—Co2—N4^iv	180.00 (17)	H1B—N1—H1C	109.5
N4—Co2—N3	90.59 (16)	O1—N8—O2^iv	120.3 (3)
N4^ii—Co2—N3	89.41 (16)	O1—N8—O2	120.3 (3)
N4^iii—Co2—N3	89.41 (16)	O2^iv—N8—O2	119.4 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.89	2.89	3.427 (4)	120
N1—H1A···Cl3^iv	0.89	2.90	3.484 (4)	125
N1—H1B···Cl1^vii	0.89	2.59	3.410 (4)	154
N1—H1C···Cl3^v	0.89	2.63	3.431 (4)	150
N3—H3A···O2^viii	0.89	2.53	3.155 (6)	128
N4—H4A···Cl3^ix	0.89	2.79	3.287 (4)	117
N4—H4B···Cl4	0.89	2.62	3.448 (5)	155
N4—H4C···Cl2^ix	0.89	2.73	3.321 (4)	125
N5—H5A···Cl1^i	0.89	2.77	3.375 (4)	127
N5—H5A···Cl4^x	0.89	2.91	3.456 (4)	122
N5—H5B···O2^x	0.89	2.17	3.048 (5)	168
N5—H5C···Cl3^i	0.89	2.56	3.337 (4)	146
N6—H6A···Cl4^x	0.89	2.76	3.339 (4)	124
N6—H6C···Cl3^xi	0.89	2.93	3.445 (4)	118
N7—H7A···Cl4^viii	0.89	2.78	3.368 (4)	125
N7—H7B···Cl3^xi	0.89	2.87	3.394 (4)	119

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (iv) x, −y+1, z; (v) −x, −y+1, −z; (vii) −x, −y+1, −z+1; (viii) −x+1, −y+1, −z+1; (ix) x+1/2, y+1/2, z; (x) x−1/2, y−1/2, z; (xi) x, y, z+1.