The hydrothermal reaction of ethylenediamine with CoCl
2·6H
2O yielded tris(ethylenediamine-κ
2N,
N′)cobalt(III) chloride diiodide monohydrate, [Co(C
2H
8N
2)
3](Cl)(I)
2·H
2O, which consists of [Co(en)
3]
3+ cations, Cl
− and I
− anions, and solvent water molecules. The Cl
− anions bridge the [Co(en)
3]
3+ complexes to form two-dimensional honeycomb-like layers through N—H
Cl hydrogen bonds, which stack along the
c direction to form channels hosting I
− ions and water molecules.
Supporting information
CCDC reference: 262250
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.053
- wR factor = 0.097
- Data-to-parameter ratio = 19.1
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for N11 - C11 .. 14.64 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Co2 - N21 .. 17.42 su
PLAT415_ALERT_2_B Short Inter D-H..H-X H1 .. H21D .. 1.94 Ang.
PLAT420_ALERT_2_B D-H Without Acceptor O1W - H1 ... ?
PLAT601_ALERT_2_B Structure Contains Solvent Accessible VOIDS of . 177.00 A 3
Alert level C
ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
Tmin and Tmax reported: 0.288 0.404
Tmin and Tmax expected: 0.209 0.404
RR = 1.379
Please check that your absorption correction is appropriate.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.35
PLAT213_ALERT_2_C Atom Cl1 has ADP max/min Ratio ............. 3.90 prolat
PLAT751_ALERT_4_C Bond Calc 0.00000, Rep 0.0000(16) ...... Senseless su
CL1 -CL1 1.555 1.555
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.12 Ratio
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1
C6 H24 Co N6
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2
C6 H24 Co N6
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3
H2 O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 4
I
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 5
Cl
Alert level G
REFLT03_ALERT_4_G 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.
From the CIF: _diffrn_reflns_theta_max 25.03
From the CIF: _reflns_number_total 1588
Count of symmetry unique reflns 1027
Completeness (_total/calc) 154.63%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 561
Fraction of Friedel pairs measured 0.546
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
5 ALERT level B = Potentially serious problem
11 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
6 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
8 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL; molecular graphics: Please provide missing details; software used to prepare material for publication: SHELXTL.
tris(ethylenediamine-
κ2N,
N')cobalt(III) chloride diiodide
monohydrate
top
Crystal data top
[Co(C2H8N2)3](Cl)(I)2·H2O | Dx = 2.020 Mg m−3 |
Mr = 546.51 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P6322 | Cell parameters from 425 reflections |
Hall symbol: P 6c 2c | θ = 3.2–27.5° |
a = 11.2374 (8) Å | µ = 4.54 mm−1 |
c = 24.648 (3) Å | T = 293 K |
V = 2695.5 (4) Å3 | Prism, orange |
Z = 6 | 0.40 × 0.30 × 0.20 mm |
F(000) = 1572 | |
Data collection top
Rigaku Mercury CCD area-detector diffractometer | 1588 independent reflections |
Radiation source: rotating-anode generator | 1081 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.099 |
ω scans | θmax = 25.0°, θmin = 3.2° |
Absorption correction: multi-scan (SPHERE in CrystalClear; Rigaku, 2002) | h = −13→13 |
Tmin = 0.288, Tmax = 0.404 | k = −13→13 |
16790 measured reflections | l = −29→29 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.053 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0013P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.003 |
1588 reflections | Δρmax = 1.72 e Å−3 |
83 parameters | Δρmin = −0.93 e Å−3 |
7 restraints | Absolute structure: Flack (1983), with 578 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.09 (14) |
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 | Uiso*/Ueq | |
Co1 | 1.6667 | 0.3333 | 0.40998 (4) | 0.0263 (3) | |
Co2 | 1.3333 | 0.6667 | 0.2500 | 0.0213 (4) | |
I1 | 1.57471 (3) | 0.69829 (3) | 0.42180 (1) | 0.03430 (8) | |
Cl1 | 1.55319 (7) | 1.10638 (14) | 0.2500 | 0.0384 (5) | |
N11 | 1.7259 (3) | 0.4990 (3) | 0.36442 (12) | 0.0331 (12) | |
H11A | 1.7202 | 0.4767 | 0.3291 | 0.040* | |
H11B | 1.6711 | 0.5348 | 0.3705 | 0.040* | |
N12 | 1.5471 (3) | 0.3732 (3) | 0.45566 (12) | 0.0272 (11) | |
H12A | 1.5584 | 0.3603 | 0.4909 | 0.033* | |
H12B | 1.5674 | 0.4608 | 0.4510 | 0.033* | |
N21 | 1.4782 (3) | 0.8025 (3) | 0.29543 (11) | 0.0313 (12) | |
H21A | 1.4852 | 0.8851 | 0.2903 | 0.038* | |
H21B | 1.4578 | 0.7794 | 0.3306 | 0.038* | |
C11 | 1.8665 (3) | 0.5981 (3) | 0.37847 (14) | 0.0249 (14) | |
H11C | 1.8904 | 0.6888 | 0.3654 | 0.030* | |
H11D | 1.9293 | 0.5722 | 0.3626 | 0.030* | |
C12 | 1.4026 (4) | 0.2762 (4) | 0.43824 (13) | 0.0307 (14) | |
H12C | 1.3708 | 0.1860 | 0.4538 | 0.037* | |
H12D | 1.3422 | 0.3094 | 0.4503 | 0.037* | |
C21 | 1.6117 (4) | 0.8106 (4) | 0.28177 (14) | 0.0347 (14) | |
H21C | 1.6174 | 0.7352 | 0.2982 | 0.042* | |
H21D | 1.6885 | 0.8967 | 0.2943 | 0.042* | |
O1W | 1.8830 (2) | 1.1170 (2) | 0.2500 | 0.091 (2) | |
H1 | 1.842 (3) | 1.0216 (4) | 0.2491 (16) | 0.071 (16)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0317 (4) | 0.0317 (4) | 0.0154 (5) | 0.01584 (18) | 0.000 | 0.000 |
Co2 | 0.0283 (5) | 0.0283 (5) | 0.0072 (6) | 0.0142 (3) | 0.000 | 0.000 |
I1 | 0.05131 (11) | 0.04222 (11) | 0.01606 (10) | 0.02839 (9) | −0.00053 (15) | 0.00084 (13) |
Cl1 | 0.0749 (10) | 0.0123 (8) | 0.0071 (7) | 0.0062 (4) | 0.0071 (7) | 0.000 |
N11 | 0.0456 (17) | 0.0441 (16) | 0.0195 (18) | 0.0299 (12) | 0.0100 (15) | 0.0064 (15) |
N12 | 0.0375 (16) | 0.0212 (14) | 0.0304 (18) | 0.0203 (11) | 0.0030 (15) | 0.0068 (14) |
N21 | 0.0544 (18) | 0.0367 (16) | 0.0118 (16) | 0.0294 (12) | 0.0125 (14) | 0.0112 (14) |
C11 | 0.0165 (19) | 0.014 (2) | 0.027 (2) | −0.0047 (15) | 0.0035 (17) | 0.0063 (16) |
C12 | 0.037 (2) | 0.0243 (18) | 0.027 (2) | 0.0126 (14) | −0.0129 (18) | 0.0065 (16) |
C21 | 0.0226 (18) | 0.048 (2) | 0.0231 (19) | 0.0104 (14) | −0.0104 (16) | −0.0064 (18) |
O1W | 0.0689 (18) | 0.0689 (18) | 0.134 (5) | 0.035 (2) | 0.025 (3) | 0.025 (3) |
Geometric parameters (Å, º) top
Co1—N12i | 1.968 (4) | N12—C12 | 1.497 (4) |
Co1—N12ii | 1.968 (4) | N12—H12A | 0.9000 |
Co1—N12 | 1.968 (4) | N12—H12B | 0.9000 |
Co1—N11ii | 1.983 (3) | N21—C21 | 1.496 (6) |
Co1—N11i | 1.983 (3) | N21—H21A | 0.9000 |
Co1—N11 | 1.983 (3) | N21—H21B | 0.9000 |
Co2—N21iii | 1.936 (3) | C11—C12ii | 1.476 (5) |
Co2—N21iv | 1.936 (3) | C11—H11C | 0.9700 |
Co2—N21v | 1.936 (3) | C11—H11D | 0.9700 |
Co2—N21 | 1.936 (3) | C12—C11i | 1.476 (5) |
Co2—N21vi | 1.936 (3) | C12—H12C | 0.9700 |
Co2—N21vii | 1.936 (3) | C12—H12D | 0.9700 |
Cl1—Cl1 | 0.0000 (16) | C21—C21vii | 1.570 (7) |
N11—C11 | 1.449 (4) | C21—H21C | 0.9700 |
N11—H11A | 0.9000 | C21—H21D | 0.9700 |
N11—H11B | 0.9000 | O1W—H1 | 0.932 (5) |
| | | |
N12i—Co1—N12ii | 90.52 (14) | C11—N11—H11B | 110.1 |
N12i—Co1—N12 | 90.52 (14) | Co1—N11—H11B | 110.1 |
N12ii—Co1—N12 | 90.52 (14) | H11A—N11—H11B | 108.4 |
N12i—Co1—N11ii | 85.39 (11) | C12—N12—Co1 | 106.6 (2) |
N12ii—Co1—N11ii | 93.27 (14) | C12—N12—H12A | 110.4 |
N12—Co1—N11ii | 174.44 (12) | Co1—N12—H12A | 110.4 |
N12i—Co1—N11i | 93.27 (14) | C12—N12—H12B | 110.4 |
N12ii—Co1—N11i | 174.44 (12) | Co1—N12—H12B | 110.4 |
N12—Co1—N11i | 85.39 (11) | H12A—N12—H12B | 108.6 |
N11ii—Co1—N11i | 91.08 (13) | C21—N21—Co2 | 109.9 (2) |
N12i—Co1—N11 | 174.44 (12) | C21—N21—H21A | 109.7 |
N12ii—Co1—N11 | 85.39 (11) | Co2—N21—H21A | 109.7 |
N12—Co1—N11 | 93.27 (14) | C21—N21—H21B | 109.7 |
N11ii—Co1—N11 | 91.08 (13) | Co2—N21—H21B | 109.7 |
N11i—Co1—N11 | 91.08 (13) | H21A—N21—H21B | 108.2 |
N21iii—Co2—N21iv | 86.6 (2) | N11—C11—C12ii | 106.0 (3) |
N21iii—Co2—N21v | 89.90 (11) | N11—C11—H11C | 110.5 |
N21iv—Co2—N21v | 93.9 (2) | C12ii—C11—H11C | 110.5 |
N21iii—Co2—N21 | 93.9 (2) | N11—C11—H11D | 110.5 |
N21iv—Co2—N21 | 89.90 (11) | C12ii—C11—H11D | 110.5 |
N21v—Co2—N21 | 174.8 (2) | H11C—C11—H11D | 108.7 |
N21iii—Co2—N21vi | 174.8 (2) | C11i—C12—N12 | 107.5 (3) |
N21iv—Co2—N21vi | 89.90 (11) | C11i—C12—H12C | 110.2 |
N21v—Co2—N21vi | 86.6 (2) | N12—C12—H12C | 110.2 |
N21—Co2—N21vi | 89.90 (11) | C11i—C12—H12D | 110.2 |
N21iii—Co2—N21vii | 89.90 (11) | N12—C12—H12D | 110.2 |
N21iv—Co2—N21vii | 174.8 (2) | H12C—C12—H12D | 108.5 |
N21v—Co2—N21vii | 89.90 (11) | N21—C21—C21vii | 104.7 (3) |
N21—Co2—N21vii | 86.6 (2) | N21—C21—H21C | 110.8 |
N21vi—Co2—N21vii | 93.9 (2) | C21vii—C21—H21C | 110.8 |
C11—N11—Co1 | 108.1 (3) | N21—C21—H21D | 110.8 |
C11—N11—H11A | 110.1 | C21vii—C21—H21D | 110.8 |
Co1—N11—H11A | 110.1 | H21C—C21—H21D | 108.9 |
Symmetry codes: (i) −y+2, x−y−1, z; (ii) −x+y+3, −x+2, z; (iii) −x+y+2, y, −z+1/2; (iv) −y+2, x−y, z; (v) −y+2, −x+2, −z+1/2; (vi) −x+y+2, −x+2, z; (vii) x, x−y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21A···Cl1 | 0.90 | 2.42 | 3.278 (4) | 160 |
N11—H11A···Cl1vi | 0.90 | 2.61 | 3.305 (3) | 135 |
Symmetry code: (vi) −x+y+2, −x+2, z. |