The title compound, (H
3O)[Ni(C
2H
6N
4O
2)
3]I
3 or (H
3O)[Ni(H
2oxado)
3]I
3, where H
2oxado = oxamide dioxime, contains six [Ni(H
2oxado)
3]
2+ cations, six H
3O
+ cations and eighteen I
− anions in the unit cell. The Ni atom lies on a position of site symmetry 32 and the hydronium cation is disordered on a position of site symmetry
. The crystal packing is consolidated by O—H
O hydrogen bonds that link the cations along
c into positively charged pillars. The proton balancing the charge of the iodide ions is attached to the water molecule of crystallization, thus forming a hydronium ion.
Supporting information
CCDC reference: 624958
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- R factor = 0.027
- wR factor = 0.059
- Data-to-parameter ratio = 26.0
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D H1 .. H3 .. 2.01 Ang.
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ...... 3.20 Sigma
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........ O2
PLAT733_ALERT_1_C Torsion Calc 44.4(4), Rep 44.38(16) ...... 2.50 su-Ra
N1 -NI -N1 -C 5.555 1.555 1.555 1.555
Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
From the CIF: _diffrn_reflns_theta_max 35.08
From the CIF: _reflns_number_total 1557
From the CIF: _diffrn_reflns_limit_ max hkl 24. 25. 23.
From the CIF: _diffrn_reflns_limit_ min hkl -24. -25. -23.
TEST1: Expected hkl limits for theta max
Calculated maximum hkl 26. 26. 23.
Calculated minimum hkl -26. -26. -23.
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
3 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
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: WinXpose (Stoe & Cie, 2002); cell refinement: RECIPE (Stoe & Cie, 2002); data reduction: INTEGRATE (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 and DIAMOND.
Hydronium tris(oxamide dioxime-
κ2N,
N')nickel(II) triiodide
top
Crystal data top
(H3O)[Ni(C2H6N2O2)3]I3 | Dx = 2.488 Mg m−3 |
Mr = 812.76 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3c | Cell parameters from 2000 reflections |
Hall symbol: -R 3 2"c | θ = 2.0–35.1° |
a = 16.105 (2) Å | µ = 5.22 mm−1 |
c = 14.488 (3) Å | T = 100 K |
V = 3254.4 (9) Å3 | Hexagonal, pink–red |
Z = 6 | 0.11 × 0.09 × 0.05 mm |
F(000) = 2304 | |
Data collection top
Stoe IPDS-II diffractometer | 1557 independent reflections |
Radiation source: fine-focus sealed tube | 1461 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ω scans | θmax = 35.1°, θmin = 4.1° |
Absorption correction: numerical [X-RED32 (Stoe & Cie, 2001);
crystal description using FACEIT (Stoe & Cie, 2002);
optimization using equivalent reflections
(X-SHAPE; Stoe & Cie, 1999)] | h = −24→24 |
Tmin = 0.450, Tmax = 0.678 | k = −25→25 |
13652 measured reflections | l = −23→23 |
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)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.059 |
w = [1-exp(-10(sinθ/λ)2)]/
[σ2(Fo2) + 30.9996*P + (0.0144P)2]
where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max = 0.001 |
1557 reflections | Δρmax = 1.49 e Å−3 |
60 parameters | Δρmin = −1.19 e Å−3 |
4 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00016 (5) |
Special details top
Experimental. collection of intensity data: φ = 0 and ω oscillation scans, Δω = 0.8°,
crystal to detector distance (60 mm), lattice parameters from Stoe
IPDS-II diffraction data using Mo Kα radiation |
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 | Occ. (<1) |
I | 0.452326 (12) | 0.452326 (12) | 0.2500 | 0.01007 (7) | |
Ni | 0.0000 | 0.0000 | 0.2500 | 0.00642 (12) | |
N1 | 0.07560 (14) | 0.12434 (14) | 0.32316 (11) | 0.0082 (3) | |
N2 | 0.22242 (15) | 0.26688 (15) | 0.33919 (13) | 0.0116 (3) | |
H2A | 0.207 (3) | 0.278 (3) | 0.397 (2) | 0.014* | |
H2B | 0.2846 (19) | 0.300 (3) | 0.321 (3) | 0.014* | |
O1 | 0.05674 (13) | 0.14547 (13) | 0.41334 (10) | 0.0102 (3) | |
H1 | 0.013 (3) | 0.159 (3) | 0.406 (3) | 0.015* | |
O2 | 0.0000 | 0.0000 | 0.5000 | 0.0114 (7) | |
H3 | 0.034 (6) | −0.002 (8) | 0.452 (4) | 0.017* | 0.50 |
C | 0.16157 (15) | 0.18706 (15) | 0.29531 (13) | 0.0071 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I | 0.00996 (9) | 0.00996 (9) | 0.01000 (9) | 0.00477 (7) | −0.00081 (3) | 0.00081 (3) |
Ni | 0.00634 (17) | 0.00634 (17) | 0.0066 (2) | 0.00317 (9) | 0.000 | 0.000 |
N1 | 0.0084 (7) | 0.0091 (7) | 0.0061 (6) | 0.0037 (6) | 0.0021 (5) | −0.0014 (5) |
N2 | 0.0102 (8) | 0.0097 (8) | 0.0114 (7) | 0.0022 (6) | 0.0017 (6) | −0.0025 (6) |
O1 | 0.0116 (7) | 0.0124 (7) | 0.0068 (6) | 0.0062 (6) | 0.0025 (5) | −0.0011 (5) |
O2 | 0.0126 (9) | 0.0126 (9) | 0.0090 (10) | 0.0063 (4) | 0.000 | 0.000 |
C | 0.0080 (8) | 0.0067 (8) | 0.0070 (7) | 0.0040 (7) | 0.0005 (6) | −0.0002 (6) |
Geometric parameters (Å, º) top
Ni—N1 | 2.0440 (19) | N1—O1 | 1.421 (2) |
Ni—N1i | 2.0440 (18) | N2—C | 1.326 (3) |
Ni—N1ii | 2.0440 (18) | N2—H2A | 0.92 (2) |
Ni—N1iii | 2.0440 (19) | N2—H2B | 0.91 (3) |
Ni—N1iv | 2.0440 (18) | O1—H1 | 0.84 (3) |
Ni—N1v | 2.0440 (18) | O2—H3 | 0.89 (3) |
N1—C | 1.305 (3) | C—Ciii | 1.493 (4) |
| | | |
N1—Ni—N1i | 167.85 (11) | N1iii—Ni—N1v | 167.85 (11) |
N1—Ni—N1ii | 94.02 (11) | N1iv—Ni—N1v | 95.55 (7) |
N1i—Ni—N1ii | 95.55 (7) | C—N1—O1 | 111.73 (17) |
N1—Ni—N1iii | 76.06 (10) | C—N1—Ni | 118.68 (14) |
N1i—Ni—N1iii | 95.55 (7) | O1—N1—Ni | 128.14 (13) |
N1ii—Ni—N1iii | 95.55 (7) | C—N2—H2A | 119 (3) |
N1—Ni—N1iv | 95.55 (7) | C—N2—H2B | 120 (3) |
N1i—Ni—N1iv | 76.06 (10) | H2A—N2—H2B | 119 (4) |
N1ii—Ni—N1iv | 167.85 (11) | N1—O1—H1 | 105 (3) |
N1iii—Ni—N1iv | 94.02 (11) | N1—C—N2 | 125.90 (19) |
N1—Ni—N1v | 95.55 (7) | N1—C—Ciii | 112.98 (11) |
N1i—Ni—N1v | 94.02 (11) | N2—C—Ciii | 121.12 (12) |
N1ii—Ni—N1v | 76.06 (10) | | |
| | | |
N1i—Ni—N1—C | 44.38 (16) | N1iii—Ni—N1—O1 | −167.8 (2) |
N1ii—Ni—N1—C | −97.49 (17) | N1iv—Ni—N1—O1 | −75.04 (13) |
N1iii—Ni—N1—C | −2.77 (11) | N1v—Ni—N1—O1 | 21.10 (17) |
N1iv—Ni—N1—C | 90.0 (2) | O1—N1—C—N2 | −6.6 (3) |
N1v—Ni—N1—C | −173.85 (17) | Ni—N1—C—N2 | −173.99 (18) |
N1i—Ni—N1—O1 | −120.67 (17) | O1—N1—C—Ciii | 174.4 (2) |
N1ii—Ni—N1—O1 | 97.46 (18) | Ni—N1—C—Ciii | 7.0 (3) |
Symmetry codes: (i) x−y, −y, −z+1/2; (ii) −x, −x+y, −z+1/2; (iii) y, x, −z+1/2; (iv) −x+y, −x, z; (v) −y, x−y, z. |
Selected bond distances (Å) involving non H atoms in (I)* topNi—N1i-v | 2.044 (2) | [2.055 (5)] |
N1—C | 1.304 (3) | [1.293 (8)] |
N1—O1 | 1.420 (2) | [1.416 (7)] |
N2—C | 1.325 (3) | [1.310 (9)] |
C—Ciii | 1.494 (4) | [1.502 (8)] |
* Values in brackets are from [Endres, 1985]
Symmetry codes:
(i) -y, x-y, z
(ii) -x+y, -x, z
(iii) y, x, -z-1/2
(iv) x-y, -y, -z-1/2
(v) -x, -x+y, -z-1/2. |
Atomic coordinates and isotropic displacement parameters
(Ueq / Å2 × 104) for all H atoms in (I) topAtom | x | y | z | Uiso |
H1 | 0.013 (3) | 0.159 (3) | 0.406 (3) | 150 |
H2A | 0.207 (3) | 0.278 (3) | 0.397 (2) | 140 |
H2B | 0.285 (2) | 0.300 (3) | 0.321 (3) | 140 |
H3 | 0.034 (6) | -0.002 (8) | 0.452 (4) | 170 |
Selected torsion angles (°) for (I) topO1—N1—C—N2 | -6.6 (3) |
Ni—N1—C—N2 | -174.0 (2) |
O1—N1—C—Ciii | 174.4 (2) |
Ni—N1—C—Ciii | 6.97 (3) |
Symmetry code:
(iii) y, x, -z-1/2. |
Hydrogen-bond geometry (Å, °) topD—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Ivi | 0.92 (2) | 2.83 (3) | 3.717 (2) | 164 (4) |
N2—H2B···I | 0.91 (3) | 2.78 (3) | 3.639 (2) | 158 (4) |
O2—H3···O1vii | 0.89 (3) | 1.64 (6) | 2.400 (2) | 142 (9) |
Symmetry codes:
(vi) -y+2/3, x-y+1/3, z+1/3
(vii) -x+y, -x, z. |