metal-organic compounds
Acta Cryst. (2010). E66, m103-m104
https://doi.org/10.1107/S1600536809054580
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G. Brewer, R. J. Butcher and J. P. Jasinski
The title compound, [Ni(C2H8N2)3]I2, crystallizes with an [Ni(en)32+] cation (en is ethane-1,2-diamine) and two iodide ions in the asymmetric unit. Two of the en ligands surrrounding the Ni2+ ion have disordered C atoms, while the third exhibits extensive weak N—HI interactions with the two iodide ions that extend throughout the crystalline lattice, producing an infinite network along (011).
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Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809054580/pb2013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536809054580/pb2013Isup2.hkl |
CCDC reference: 766702
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean
(C-C) = 0.005 Å
- Disorder in main residue
- R factor = 0.034
- wR factor = 0.091
- Data-to-parameter ratio = 32.7
checkCIF/PLATON results
No syntax errors foundAlert level BPLAT910_ALERT_3_B Missing # of FCF Reflections Below Th(Min) ..... 17PLAT923_ALERT_1_B S values in the CIF and FCF Differ by ....... 0.03
Alert level CPLAT230_ALERT_2_C Hirshfeld Test Diff for C11A -- C12A .. 6.64 suPLAT420_ALERT_2_C D-H Without Acceptor >N11A - >H11A ... ?PLAT420_ALERT_2_C D-H Without Acceptor >N12A - >H12C ... ?PLAT420_ALERT_2_C D-H Without Acceptor >N22A - >H22C ... ?PLAT420_ALERT_2_C D-H Without Acceptor >N22A - >H22D ... ?PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 12PLAT480_ALERT_4_C Long H...A H-Bond Reported H12C .. I2 .. 3.15 Ang.PLAT480_ALERT_4_C Long H...A H-Bond Reported H11F .. I2 .. 3.15 Ang.PLAT480_ALERT_4_C Long H...A H-Bond Reported H12G .. I2 .. 3.07 Ang.PLAT480_ALERT_4_C Long H...A H-Bond Reported H12H .. I1 .. 3.27 Ang.PLAT480_ALERT_4_C Long H...A H-Bond Reported H22D .. I1 .. 3.19 Ang.PLAT480_ALERT_4_C Long H...A H-Bond Reported H21F .. I1 .. 3.22 Ang.PLAT480_ALERT_4_C Long H...A H-Bond Reported H22G .. I2 .. 3.21 Ang.PLAT481_ALERT_4_C Long D...A H-Bond Reported N22B .. I2 .. 4.06 Ang.PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 433PLAT922_ALERT_1_C wR2 * 100.0 in the CIF and FCF Differ by ....... 0.26
Alert level GPLAT301_ALERT_3_G Note: Main Residue Disorder ................... 35.00 Perc.PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 36PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 4 N21A-NI -N31 -C31 -34.10 1.40 1.555 1.555 1.555 1.555PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 13 N12A-NI -N32 -C32 -25.70 1.50 1.555 1.555 1.555 1.555PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 30 N22B-NI -N11A-C11A -76.00 4.00 1.555 1.555 1.555 1.555PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 39 N32 -NI -N12A-C12A -66.10 1.80 1.555 1.555 1.555 1.555PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 44 N22A-NI -N11B-C11B 41.00 3.00 1.555 1.555 1.555 1.555PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 51 N22B-NI -N11B-C11B 94.00 4.00 1.555 1.555 1.555 1.555PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 64 N31 -NI -N21A-C21A -63.50 1.60 1.555 1.555 1.555 1.555PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 77 N11B-NI -N22A-C22A -134.00 3.00 1.555 1.555 1.555 1.555PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 99 N11B-NI -N22B-C22B -161.00 3.00 1.555 1.555 1.555 1.555PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 104 N11A-NI -N22B-C22B -27.00 5.00 1.555 1.555 1.555 1.555PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms .... ! 0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 16 ALERT level C = Check and explain 13 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 19 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Comment top
Recent work has shown that an iron(II) Schiff base complex oftris(2-aminoethyl)amine(tren) with imidazole-2-carboxaldehyde form double saltswith metal (K+, Rb+, Cs+ and NH4+) perchlorates (Brewer etal., 2007) and metal (M = Na+, K+, Rb+, Cs+ andNH4+)tetrafluoroborates (Alvarado et al., 2009). Thus thissystem shows size selectivity for alkali metal cations. Structural studies ofthe thiocyanate salts reveal a linear polymeric anion,[(M(SCN)3)2-]n. [Ni(en)3]2+and [Zn(en)3]2+ react with MX (M = K+ or NH4+,X=SCN- or SeCN-–) to form double salts,[Ni(en)3](SCN)2.NH4(SCN) (Dvorkin et al., 1991) and[Ni(en)3](SeCN)2.K(SeCN) (Farago et al., 1967) or[Zn(en)3](SCN)2.K(SCN) (Dvorkin et al., 1989). Many of thesestructures also reveal a linear polymeric anion,[(MX3)2-]n (X=ClO4- or BF4–), similar to thatobserved above suggesting that anions of this type are stable in certainsettings and may be used in other reactions. The anions in all ofthe above complexes are tethered to the cations through hydogen bondsinvolving either amine, –NH2 or the bidentate hydrogen bonding donor,-N=Cimine(H)—Cimidazole—Nimidazole(H).In an effort to determine the nature of the interactionsbetween the amine, –NH2 (in the cation building unit used in the formationof double salts) and the anion in stabilizing these salts we report thecrystal structure of the title compound, C6H24N6NiI2, (I).
C6H24N6NiI2, (I), crystallizes with a [Ni(en)32+] cation and twoI_ ions in the asymmetric unit (Fig. 1). In the cation, two of the1,2-ethanediamine-N,N' rings surrrounding the Ni2+ ion containdisordered carbon and nitrogen atoms while the third exhibits extensive weakN—H···I interactions with the two iodide ions (Table 1) thatextend throughout the crystalline lattice producing an infinitenetwork along the (011) plane of the unit cell (Fig. 2). The major componentsof the two disordered 5-membered Ni2+-1,2-ethanediamine-N,N' ringsadopt sightly distorted half-chair conformations (Cremer & Pople, 1975) withpuckering parameters Q(2), and Phi(2) of 0.403(2) Å, 86.767(6)° (ring 11 =Ni/N11/C11A/C12A/N12; 0.744) and 0.423(5) Å, 82.357(0)° (ring 21 =Ni/N21/C21A/C22A/N22; 0.684), respectively. The Q(2), and Phi(2) values forring 31 (Ni/N31/C31/C32/N32) are 0.438(4)Å and 270.967(6)°. For an idealhalf-chair, Phi(2) = k x 36° + 18° or 180° + Phi(2). The dihedralangle between the mean planes of the normal ring (31) and the major componentsof the disordered rings (11 & 21) measures 85.6(8)° and 83.5(0)°, whilebetween rings 11 and 21 themselves is 87.2(7)°. Bond distances within thecation are normal (Allen et al., 2002) and comparable to thoseinsimilar structures (Dvorkin et al., 1989, 1991; Faragoet al.,1967; Cramer et al. 1976; Cramer & Huneke,1978).
The presence of I1 and I2 in the crystal lattice allows for theformation of a collection of weak intermolecular N–H···I interactions whichthereby influences crystal stability (Table 1).
Related literature top
For related structures, see: Cramer et al. (1976); Cramer &Huneke(1978); Korp et al. (1980); Raston et al.(1978); Swink & Atoji(1960); Wieczorrek (2000).For double salts, see: Alvarado et al. (2009);Brewer et al. (2007);Dvorkin et al. (1989, 1991);Farago et al. (1967).For a description of the Cambridge Structural Database, see:Allen (2002). For puckering parameters, see: Cremer & Pople (1975).
Experimental top
Nickel(II) chloride hexahydrate was dissolved in water and excessethylenediamine was added to the green solution. The resulting violet/purplesolution was allowed to go to dryness. The crude [Ni(en)3]Cl2 wasredissolved in water saturated with potassium iodide. The dark blockishcrystals suitable for x-ray studies, in space group Pbca, werecollected by filtration on standing.
Refinement top
All of the H atoms were placed in their calculated positions and then refinedusing the riding model with N—H = 0.93 Å, C—H = 0.95–0.99 Å, and withUiso(H) = 1.18–1.51Ueq(C,N).
Computing details top
Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); 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 top
Fig. 1. Molecular structure of the title compound, C6H24N6NiI2, showingthe [Ni(en)32+] cation and two I_ ions in the asymmetric unit, the atomlabeling scheme and 50% probability displacement ellipsoids. Only the majorcomponents of disordered carbon atoms (C11A, C12A & C21A, C22A) in rings 11(Ni—N11—C11A—C12A—N12: 0.744(12)) and 21(Ni—N21—C21A—C22A—N22; 0.684(9)) are depicted. Dashed lines indicateweak N—H···I hydrogen bond interactions. | |
Fig. 2. Packing diagram of the title compound, (I), viewed down the aaxis. Dashed lines indicate weak intermolecular N—H···Iinteractions which produces a infinite weak bonding network arranged along the(011) plane of the unit cell. |
Crystal data
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[Ni(C2H8N2)3]I2 | F(000) = 1888 |
Mr = 492.82 | Dx = 2.061 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 8584 reflections |
a = 14.7502 (6) Å | θ = 4.6–32.4° |
b = 13.4881 (4) Å | µ = 5.10 mm−1 |
c = 15.9624 (7) Å | T = 200 K |
V = 3175.8 (2) Å3 | Prism, pale purple |
Z = 8 | 0.55 × 0.47 × 0.38 mm |
Data collection
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Oxford Diffraction Gemini R Mo diffractometer | 5271 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2835 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 10.5081 pixels mm-1 | θmax = 32.5°, θmin = 4.6° |
ω scans | h = −21→19 |
Absorption correction: multi-scan CrysAlis RED (Oxford Diffraction, 2009) | k = −10→19 |
Tmin = 0.337, Tmax = 1.000 | l = −24→16 |
19070 measured reflections |
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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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.043P)2] where P = (Fo2 + 2Fc2)/3 |
5271 reflections | (Δ/σ)max = 0.001 |
161 parameters | Δρmax = 1.65 e Å−3 |
36 restraints | Δρmin = −1.09 e Å−3 |
Crystal data
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[Ni(C2H8N2)3]I2 | V = 3175.8 (2) Å3 |
Mr = 492.82 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.7502 (6) Å | µ = 5.10 mm−1 |
b = 13.4881 (4) Å | T = 200 K |
c = 15.9624 (7) Å | 0.55 × 0.47 × 0.38 mm |
Data collection
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Oxford Diffraction Gemini R Mo diffractometer | 5271 independent reflections |
Absorption correction: multi-scan CrysAlis RED (Oxford Diffraction, 2009) | 2835 reflections with I > 2σ(I) |
Tmin = 0.337, Tmax = 1.000 | Rint = 0.042 |
19070 measured reflections |
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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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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-factorwR and goodness of fit S are based on F2, conventionalR-factors R are based on F, with F set to zero fornegative 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 largeas those based on F, and R- factors based on ALL data will beeven larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
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x | y | z | Uiso*/Ueq | Occ. (<1) | |
I1 | 0.611433 (17) | 0.132498 (19) | 0.122134 (16) | 0.03800 (7) | |
I2 | 0.362274 (19) | 0.435966 (17) | 0.131522 (15) | 0.03860 (7) | |
Ni | 0.42318 (3) | 0.25520 (3) | 0.37608 (3) | 0.02275 (10) | |
N31 | 0.4175 (2) | 0.20616 (19) | 0.25125 (19) | 0.0332 (7) | |
H31A | 0.3959 | 0.2561 | 0.2174 | 0.040* | |
H31B | 0.4746 | 0.1891 | 0.2331 | 0.040* | |
N32 | 0.3624 (2) | 0.11503 (19) | 0.39826 (18) | 0.0293 (7) | |
H32A | 0.3902 | 0.0842 | 0.4428 | 0.035* | |
H32B | 0.3019 | 0.1228 | 0.4106 | 0.035* | |
C31 | 0.3571 (3) | 0.1199 (3) | 0.2463 (2) | 0.0391 (9) | |
H31C | 0.3696 | 0.0821 | 0.1944 | 0.047* | |
H31D | 0.2931 | 0.1419 | 0.2450 | 0.047* | |
C32 | 0.3731 (3) | 0.0550 (2) | 0.3218 (2) | 0.0358 (9) | |
H32C | 0.3291 | −0.0005 | 0.3222 | 0.043* | |
H32D | 0.4350 | 0.0267 | 0.3196 | 0.043* | |
N11A | 0.5571 (3) | 0.2044 (3) | 0.4045 (3) | 0.0245 (10) | 0.707(4) |
H11A | 0.5682 | 0.2102 | 0.4611 | 0.029* | 0.707(4) |
H11B | 0.5634 | 0.1389 | 0.3896 | 0.029* | 0.707(4) |
C11A | 0.6215 (5) | 0.2661 (5) | 0.3569 (5) | 0.0366 (12) | 0.707(4) |
H11C | 0.6215 | 0.2466 | 0.2972 | 0.044* | 0.707(4) |
H11D | 0.6836 | 0.2579 | 0.3793 | 0.044* | 0.707(4) |
C12A | 0.5913 (4) | 0.3713 (4) | 0.3662 (4) | 0.0398 (13) | 0.707(4) |
H12A | 0.5980 | 0.3921 | 0.4254 | 0.048* | 0.707(4) |
H12B | 0.6302 | 0.4147 | 0.3314 | 0.048* | 0.707(4) |
N12A | 0.4962 (4) | 0.3832 (5) | 0.3404 (6) | 0.0336 (8) | 0.707(4) |
H12C | 0.4930 | 0.3916 | 0.2832 | 0.040* | 0.707(4) |
H12D | 0.4716 | 0.4383 | 0.3656 | 0.040* | 0.707(4) |
N11B | 0.5522 (9) | 0.1873 (8) | 0.3751 (7) | 0.0245 (10) | 0.293(4) |
H11E | 0.5596 | 0.1490 | 0.4223 | 0.029* | 0.293(4) |
H11F | 0.5580 | 0.1471 | 0.3289 | 0.029* | 0.293(4) |
C11B | 0.6210 (11) | 0.2659 (11) | 0.3730 (12) | 0.0366 (12) | 0.293(4) |
H11G | 0.6800 | 0.2376 | 0.3555 | 0.044* | 0.293(4) |
H11H | 0.6283 | 0.2945 | 0.4297 | 0.044* | 0.293(4) |
C12B | 0.5934 (8) | 0.3463 (9) | 0.3126 (9) | 0.0398 (13) | 0.293(4) |
H12E | 0.6378 | 0.4013 | 0.3144 | 0.048* | 0.293(4) |
H12F | 0.5919 | 0.3197 | 0.2548 | 0.048* | 0.293(4) |
N12B | 0.5030 (10) | 0.3828 (13) | 0.3364 (15) | 0.0336 (8) | 0.293(4) |
H12G | 0.4757 | 0.4135 | 0.2915 | 0.040* | 0.293(4) |
H12H | 0.5077 | 0.4279 | 0.3794 | 0.040* | 0.293(4) |
N21A | 0.4089 (4) | 0.2980 (6) | 0.5029 (5) | 0.0373 (9) | 0.707(4) |
H21A | 0.3906 | 0.2446 | 0.5347 | 0.045* | 0.707(4) |
H21B | 0.4635 | 0.3202 | 0.5235 | 0.045* | 0.707(4) |
C21A | 0.3404 (4) | 0.3778 (4) | 0.5075 (4) | 0.0418 (13) | 0.707(4) |
H21C | 0.3179 | 0.3841 | 0.5657 | 0.050* | 0.707(4) |
H21D | 0.3683 | 0.4417 | 0.4912 | 0.050* | 0.707(4) |
C22A | 0.2648 (4) | 0.3553 (4) | 0.4514 (3) | 0.0352 (13) | 0.707(4) |
H22A | 0.2226 | 0.4123 | 0.4493 | 0.042* | 0.707(4) |
H22B | 0.2311 | 0.2969 | 0.4725 | 0.042* | 0.707(4) |
N22A | 0.3007 (5) | 0.3345 (5) | 0.3666 (3) | 0.0279 (10) | 0.707(4) |
H22C | 0.3105 | 0.3931 | 0.3385 | 0.033* | 0.707(4) |
H22D | 0.2591 | 0.2979 | 0.3367 | 0.033* | 0.707(4) |
N21B | 0.3959 (10) | 0.3014 (15) | 0.5003 (12) | 0.0373 (9) | 0.293(4) |
H21E | 0.4126 | 0.2528 | 0.5376 | 0.045* | 0.293(4) |
H21F | 0.4281 | 0.3581 | 0.5125 | 0.045* | 0.293(4) |
C21B | 0.2973 (9) | 0.3207 (9) | 0.5064 (8) | 0.0418 (13) | 0.293(4) |
H21G | 0.2635 | 0.2573 | 0.5066 | 0.050* | 0.293(4) |
H21H | 0.2835 | 0.3566 | 0.5590 | 0.050* | 0.293(4) |
C22B | 0.2706 (12) | 0.3802 (11) | 0.4348 (8) | 0.0352 (13) | 0.293(4) |
H22E | 0.3050 | 0.4431 | 0.4343 | 0.042* | 0.293(4) |
H22F | 0.2052 | 0.3961 | 0.4382 | 0.042* | 0.293(4) |
N22B | 0.2895 (13) | 0.3231 (14) | 0.3576 (9) | 0.0279 (10) | 0.293(4) |
H22G | 0.2901 | 0.3644 | 0.3117 | 0.033* | 0.293(4) |
H22H | 0.2461 | 0.2752 | 0.3495 | 0.033* | 0.293(4) |
Atomic displacement parameters (Å2)
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U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.02763 (13) | 0.04501 (14) | 0.04135 (15) | −0.00301 (10) | 0.00464 (11) | −0.00509 (12) |
I2 | 0.05250 (17) | 0.02837 (11) | 0.03493 (14) | −0.00384 (10) | −0.00855 (12) | −0.00025 (11) |
Ni | 0.0228 (2) | 0.01934 (17) | 0.0261 (2) | 0.00048 (15) | −0.00030 (19) | 0.00281 (17) |
N31 | 0.0388 (18) | 0.0298 (14) | 0.0311 (16) | 0.0024 (13) | 0.0089 (14) | −0.0018 (14) |
N32 | 0.0307 (16) | 0.0246 (13) | 0.0327 (16) | −0.0070 (12) | −0.0054 (13) | 0.0054 (13) |
C31 | 0.047 (2) | 0.045 (2) | 0.0248 (18) | −0.0084 (18) | 0.0037 (18) | −0.0089 (18) |
C32 | 0.051 (2) | 0.0238 (16) | 0.033 (2) | −0.0079 (16) | 0.0012 (18) | −0.0016 (16) |
N11A | 0.0270 (18) | 0.0242 (19) | 0.022 (3) | −0.0039 (15) | −0.007 (2) | −0.0052 (18) |
C11A | 0.035 (2) | 0.0383 (17) | 0.036 (3) | 0.0028 (14) | 0.0021 (18) | −0.0046 (18) |
C12A | 0.031 (3) | 0.051 (3) | 0.037 (3) | −0.020 (2) | 0.010 (3) | 0.001 (3) |
N12A | 0.0333 (19) | 0.0277 (15) | 0.0398 (19) | −0.0044 (13) | 0.0086 (16) | 0.0071 (15) |
N11B | 0.0270 (18) | 0.0242 (19) | 0.022 (3) | −0.0039 (15) | −0.007 (2) | −0.0052 (18) |
C11B | 0.035 (2) | 0.0383 (17) | 0.036 (3) | 0.0028 (14) | 0.0021 (18) | −0.0046 (18) |
C12B | 0.031 (3) | 0.051 (3) | 0.037 (3) | −0.020 (2) | 0.010 (3) | 0.001 (3) |
N12B | 0.0333 (19) | 0.0277 (15) | 0.0398 (19) | −0.0044 (13) | 0.0086 (16) | 0.0071 (15) |
N21A | 0.052 (2) | 0.0343 (17) | 0.0254 (17) | −0.0082 (18) | −0.0119 (18) | 0.0056 (15) |
C21A | 0.055 (4) | 0.033 (3) | 0.037 (3) | −0.003 (2) | −0.001 (3) | −0.002 (3) |
C22A | 0.039 (2) | 0.036 (3) | 0.031 (2) | 0.0025 (19) | 0.0101 (19) | −0.003 (2) |
N22A | 0.027 (2) | 0.0278 (19) | 0.0286 (19) | 0.0027 (16) | −0.0043 (16) | 0.0020 (16) |
N21B | 0.052 (2) | 0.0343 (17) | 0.0254 (17) | −0.0082 (18) | −0.0119 (18) | 0.0056 (15) |
C21B | 0.055 (4) | 0.033 (3) | 0.037 (3) | −0.003 (2) | −0.001 (3) | −0.002 (3) |
C22B | 0.039 (2) | 0.036 (3) | 0.031 (2) | 0.0025 (19) | 0.0101 (19) | −0.003 (2) |
N22B | 0.027 (2) | 0.0278 (19) | 0.0286 (19) | 0.0027 (16) | −0.0043 (16) | 0.0020 (16) |
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Ni—N31 | 2.101 (3) | N11B—H11E | 0.9200 |
Ni—N22A | 2.105 (7) | N11B—H11F | 0.9200 |
Ni—N11B | 2.113 (13) | C11B—C12B | 1.507 (14) |
Ni—N12A | 2.113 (7) | C11B—H11G | 0.9900 |
Ni—N21A | 2.116 (7) | C11B—H11H | 0.9900 |
Ni—N21B | 2.117 (19) | C12B—N12B | 1.472 (14) |
Ni—N32 | 2.122 (3) | C12B—H12E | 0.9900 |
Ni—N11A | 2.140 (5) | C12B—H12F | 0.9900 |
Ni—N12B | 2.180 (18) | N12B—H12G | 0.9200 |
Ni—N22B | 2.194 (18) | N12B—H12H | 0.9200 |
N31—C31 | 1.467 (4) | N21A—C21A | 1.478 (8) |
N31—H31A | 0.9200 | N21A—H21A | 0.9200 |
N31—H31B | 0.9200 | N21A—H21B | 0.9200 |
N32—C32 | 1.473 (4) | C21A—C22A | 1.462 (8) |
N32—H32A | 0.9200 | C21A—H21C | 0.9900 |
N32—H32B | 0.9200 | C21A—H21D | 0.9900 |
C31—C32 | 1.508 (5) | C22A—N22A | 1.482 (6) |
C31—H31C | 0.9900 | C22A—H22A | 0.9900 |
C31—H31D | 0.9900 | C22A—H22B | 0.9900 |
C32—H32C | 0.9900 | N22A—H22C | 0.9200 |
C32—H32D | 0.9900 | N22A—H22D | 0.9200 |
N11A—C11A | 1.473 (7) | N21B—C21B | 1.481 (14) |
N11A—H11A | 0.9200 | N21B—H21E | 0.9200 |
N11A—H11B | 0.9200 | N21B—H21F | 0.9200 |
C11A—C12A | 1.495 (8) | C21B—C22B | 1.450 (14) |
C11A—H11C | 0.9900 | C21B—H21G | 0.9900 |
C11A—H11D | 0.9900 | C21B—H21H | 0.9900 |
C12A—N12A | 1.470 (8) | C22B—N22B | 1.480 (14) |
C12A—H12A | 0.9900 | C22B—H22E | 0.9900 |
C12A—H12B | 0.9900 | C22B—H22F | 0.9900 |
N12A—H12C | 0.9200 | N22B—H22G | 0.9200 |
N12A—H12D | 0.9200 | N22B—H22H | 0.9200 |
N11B—C11B | 1.467 (14) | ||
N31—Ni—N22A | 93.25 (16) | C11A—C12A—H12A | 109.4 |
N31—Ni—N11B | 83.9 (3) | N12A—C12A—H12B | 109.4 |
N22A—Ni—N11B | 173.3 (4) | C11A—C12A—H12B | 109.4 |
N31—Ni—N12A | 91.3 (3) | H12A—C12A—H12B | 108.0 |
N22A—Ni—N12A | 90.2 (2) | C12A—N12A—Ni | 108.7 (4) |
N11B—Ni—N12A | 83.8 (3) | C12A—N12A—H12C | 109.9 |
N31—Ni—N21A | 171.6 (2) | Ni—N12A—H12C | 109.9 |
N22A—Ni—N21A | 81.1 (2) | C12A—N12A—H12D | 109.9 |
N11B—Ni—N21A | 102.4 (4) | Ni—N12A—H12D | 109.9 |
N12A—Ni—N21A | 94.9 (3) | H12C—N12A—H12D | 108.3 |
N31—Ni—N21B | 166.7 (4) | C11B—N11B—Ni | 108.0 (9) |
N22A—Ni—N21B | 75.8 (4) | C11B—N11B—H11E | 110.1 |
N11B—Ni—N21B | 107.8 (5) | Ni—N11B—H11E | 110.1 |
N12A—Ni—N21B | 96.2 (6) | C11B—N11B—H11F | 110.1 |
N21A—Ni—N21B | 5.4 (5) | Ni—N11B—H11F | 110.1 |
N31—Ni—N32 | 81.99 (11) | H11E—N11B—H11F | 108.4 |
N22A—Ni—N32 | 95.9 (2) | N11B—C11B—C12B | 110.4 (12) |
N11B—Ni—N32 | 89.7 (3) | N11B—C11B—H11G | 109.6 |
N12A—Ni—N32 | 171.2 (2) | C12B—C11B—H11G | 109.6 |
N21A—Ni—N32 | 92.4 (2) | N11B—C11B—H11H | 109.6 |
N21B—Ni—N32 | 91.5 (6) | C12B—C11B—H11H | 109.6 |
N31—Ni—N11A | 97.93 (14) | H11G—C11B—H11H | 108.1 |
N22A—Ni—N11A | 166.02 (19) | N12B—C12B—C11B | 108.7 (12) |
N11B—Ni—N11A | 14.3 (3) | N12B—C12B—H12E | 110.0 |
N12A—Ni—N11A | 81.26 (19) | C11B—C12B—H12E | 110.0 |
N21A—Ni—N11A | 88.6 (2) | N12B—C12B—H12F | 110.0 |
N21B—Ni—N11A | 94.0 (4) | C11B—C12B—H12F | 110.0 |
N32—Ni—N11A | 93.98 (14) | H12E—C12B—H12F | 108.3 |
N31—Ni—N12B | 89.7 (6) | C12B—N12B—Ni | 107.5 (10) |
N22A—Ni—N12B | 92.4 (4) | C12B—N12B—H12G | 110.2 |
N11B—Ni—N12B | 81.6 (4) | Ni—N12B—H12G | 110.2 |
N12A—Ni—N12B | 2.6 (6) | C12B—N12B—H12H | 110.2 |
N21A—Ni—N12B | 96.7 (7) | Ni—N12B—H12H | 110.2 |
N21B—Ni—N12B | 98.2 (8) | H12G—N12B—H12H | 108.5 |
N32—Ni—N12B | 168.6 (5) | C21A—N21A—Ni | 108.3 (4) |
N11A—Ni—N12B | 79.4 (4) | C21A—N21A—H21A | 110.0 |
N31—Ni—N22B | 88.1 (4) | Ni—N21A—H21A | 110.0 |
N22A—Ni—N22B | 6.7 (5) | C21A—N21A—H21B | 110.0 |
N11B—Ni—N22B | 171.8 (5) | Ni—N21A—H21B | 110.0 |
N12A—Ni—N22B | 94.6 (5) | H21A—N21A—H21B | 108.4 |
N21A—Ni—N22B | 85.7 (4) | C22A—C21A—N21A | 109.8 (5) |
N21B—Ni—N22B | 80.4 (5) | C22A—C21A—H21C | 109.7 |
N32—Ni—N22B | 90.9 (5) | N21A—C21A—H21C | 109.7 |
N11A—Ni—N22B | 172.7 (4) | C22A—C21A—H21D | 109.7 |
N12B—Ni—N22B | 96.7 (6) | N21A—C21A—H21D | 109.7 |
C31—N31—Ni | 109.0 (2) | H21C—C21A—H21D | 108.2 |
C31—N31—H31A | 109.9 | C21A—C22A—N22A | 109.1 (5) |
Ni—N31—H31A | 109.9 | C21A—C22A—H22A | 109.9 |
C31—N31—H31B | 109.9 | N22A—C22A—H22A | 109.9 |
Ni—N31—H31B | 109.9 | C21A—C22A—H22B | 109.9 |
H31A—N31—H31B | 108.3 | N22A—C22A—H22B | 109.9 |
C32—N32—Ni | 107.9 (2) | H22A—C22A—H22B | 108.3 |
C32—N32—H32A | 110.1 | C22A—N22A—Ni | 109.7 (4) |
Ni—N32—H32A | 110.1 | C22A—N22A—H22C | 109.7 |
C32—N32—H32B | 110.1 | Ni—N22A—H22C | 109.7 |
Ni—N32—H32B | 110.1 | C22A—N22A—H22D | 109.7 |
H32A—N32—H32B | 108.4 | Ni—N22A—H22D | 109.7 |
N31—C31—C32 | 108.8 (3) | H22C—N22A—H22D | 108.2 |
N31—C31—H31C | 109.9 | C21B—N21B—Ni | 107.4 (10) |
C32—C31—H31C | 109.9 | C21B—N21B—H21E | 110.2 |
N31—C31—H31D | 109.9 | Ni—N21B—H21E | 110.2 |
C32—C31—H31D | 109.9 | C21B—N21B—H21F | 110.2 |
H31C—C31—H31D | 108.3 | Ni—N21B—H21F | 110.2 |
N32—C32—C31 | 109.0 (3) | H21E—N21B—H21F | 108.5 |
N32—C32—H32C | 109.9 | C22B—C21B—N21B | 108.2 (12) |
C31—C32—H32C | 109.9 | C22B—C21B—H21G | 110.1 |
N32—C32—H32D | 109.9 | N21B—C21B—H21G | 110.1 |
C31—C32—H32D | 109.9 | C22B—C21B—H21H | 110.1 |
H32C—C32—H32D | 108.3 | N21B—C21B—H21H | 110.1 |
C11A—N11A—Ni | 107.8 (3) | H21G—C21B—H21H | 108.4 |
C11A—N11A—H11A | 110.2 | C21B—C22B—N22B | 108.5 (12) |
Ni—N11A—H11A | 110.2 | C21B—C22B—H22E | 110.0 |
C11A—N11A—H11B | 110.2 | N22B—C22B—H22E | 110.0 |
Ni—N11A—H11B | 110.2 | C21B—C22B—H22F | 110.0 |
H11A—N11A—H11B | 108.5 | N22B—C22B—H22F | 110.0 |
N11A—C11A—C12A | 107.0 (5) | H22E—C22B—H22F | 108.4 |
N11A—C11A—H11C | 110.3 | C22B—N22B—Ni | 105.9 (10) |
C12A—C11A—H11C | 110.3 | C22B—N22B—H22G | 110.5 |
N11A—C11A—H11D | 110.3 | Ni—N22B—H22G | 110.5 |
C12A—C11A—H11D | 110.3 | C22B—N22B—H22H | 110.5 |
H11C—C11A—H11D | 108.6 | Ni—N22B—H22H | 110.5 |
N12A—C12A—C11A | 111.1 (5) | H22G—N22B—H22H | 108.7 |
N12A—C12A—H12A | 109.4 | ||
N22A—Ni—N31—C31 | −81.5 (3) | C11B—C12B—N12B—Ni | −38.7 (17) |
N11B—Ni—N31—C31 | 104.6 (4) | N31—Ni—N12B—C12B | −70.9 (13) |
N12A—Ni—N31—C31 | −171.7 (3) | N22A—Ni—N12B—C12B | −164.2 (13) |
N21A—Ni—N31—C31 | −34.1 (14) | N11B—Ni—N12B—C12B | 12.9 (13) |
N21B—Ni—N31—C31 | −47 (2) | N12A—Ni—N12B—C12B | 162 (18) |
N32—Ni—N31—C31 | 14.0 (2) | N21A—Ni—N12B—C12B | 114.5 (13) |
N11A—Ni—N31—C31 | 106.9 (3) | N21B—Ni—N12B—C12B | 119.8 (13) |
N12B—Ni—N31—C31 | −173.8 (4) | N32—Ni—N12B—C12B | −28 (4) |
N22B—Ni—N31—C31 | −77.1 (6) | N11A—Ni—N12B—C12B | 27.2 (12) |
N31—Ni—N32—C32 | 14.7 (2) | N22B—Ni—N12B—C12B | −159.0 (13) |
N22A—Ni—N32—C32 | 107.2 (3) | N31—Ni—N21A—C21A | −63.5 (16) |
N11B—Ni—N32—C32 | −69.1 (4) | N22A—Ni—N21A—C21A | −15.4 (5) |
N12A—Ni—N32—C32 | −25.7 (15) | N11B—Ni—N21A—C21A | 158.8 (5) |
N21A—Ni—N32—C32 | −171.5 (3) | N12A—Ni—N21A—C21A | 74.0 (5) |
N21B—Ni—N32—C32 | −176.9 (4) | N21B—Ni—N21A—C21A | −30 (8) |
N11A—Ni—N32—C32 | −82.7 (3) | N32—Ni—N21A—C21A | −111.0 (5) |
N12B—Ni—N32—C32 | −29 (3) | N11A—Ni—N21A—C21A | 155.1 (5) |
N22B—Ni—N32—C32 | 102.7 (4) | N12B—Ni—N21A—C21A | 75.9 (6) |
Ni—N31—C31—C32 | −39.9 (3) | N22B—Ni—N21A—C21A | −20.3 (7) |
Ni—N32—C32—C31 | −40.5 (3) | Ni—N21A—C21A—C22A | 41.1 (6) |
N31—C31—C32—N32 | 54.4 (4) | N21A—C21A—C22A—N22A | −52.7 (7) |
N31—Ni—N11A—C11A | 69.7 (4) | C21A—C22A—N22A—Ni | 37.8 (6) |
N22A—Ni—N11A—C11A | −73.1 (10) | N31—Ni—N22A—C22A | 161.9 (4) |
N11B—Ni—N11A—C11A | 79.1 (15) | N11B—Ni—N22A—C22A | −134 (3) |
N12A—Ni—N11A—C11A | −20.4 (4) | N12A—Ni—N22A—C22A | −106.9 (5) |
N21A—Ni—N11A—C11A | −115.6 (4) | N21A—Ni—N22A—C22A | −11.9 (5) |
N21B—Ni—N11A—C11A | −116.1 (7) | N21B—Ni—N22A—C22A | −10.5 (7) |
N32—Ni—N11A—C11A | 152.1 (4) | N32—Ni—N22A—C22A | 79.6 (4) |
N12B—Ni—N11A—C11A | −18.5 (7) | N11A—Ni—N22A—C22A | −55.0 (11) |
N22B—Ni—N11A—C11A | −76 (4) | N12B—Ni—N22A—C22A | −108.3 (8) |
Ni—N11A—C11A—C12A | 44.7 (6) | N22B—Ni—N22A—C22A | 121 (5) |
N11A—C11A—C12A—N12A | −54.8 (7) | N31—Ni—N21B—C21B | −13 (3) |
C11A—C12A—N12A—Ni | 36.2 (7) | N22A—Ni—N21B—C21B | 22.5 (10) |
N31—Ni—N12A—C12A | −106.1 (5) | N11B—Ni—N21B—C21B | −163.3 (10) |
N22A—Ni—N12A—C12A | 160.6 (5) | N12A—Ni—N21B—C21B | 111.1 (11) |
N11B—Ni—N12A—C12A | −22.4 (6) | N21A—Ni—N21B—C21B | −172 (9) |
N21A—Ni—N12A—C12A | 79.5 (5) | N32—Ni—N21B—C21B | −73.1 (12) |
N21B—Ni—N12A—C12A | 84.8 (6) | N11A—Ni—N21B—C21B | −167.2 (11) |
N32—Ni—N12A—C12A | −66.1 (18) | N12B—Ni—N21B—C21B | 112.9 (12) |
N11A—Ni—N12A—C12A | −8.3 (5) | N22B—Ni—N21B—C21B | 17.5 (12) |
N12B—Ni—N12A—C12A | −53 (17) | Ni—N21B—C21B—C22B | −47.1 (15) |
N22B—Ni—N12A—C12A | 165.6 (6) | N21B—C21B—C22B—N22B | 61.4 (18) |
N31—Ni—N11B—C11B | 106.4 (10) | C21B—C22B—N22B—Ni | −42.9 (16) |
N22A—Ni—N11B—C11B | 41 (3) | N31—Ni—N22B—C22B | −173.6 (11) |
N12A—Ni—N11B—C11B | 14.4 (10) | N22A—Ni—N22B—C22B | −34 (4) |
N21A—Ni—N11B—C11B | −79.3 (11) | N11B—Ni—N22B—C22B | −161 (3) |
N21B—Ni—N11B—C11B | −80.2 (12) | N12A—Ni—N22B—C22B | −82.5 (12) |
N32—Ni—N11B—C11B | −171.7 (10) | N21A—Ni—N22B—C22B | 12.2 (11) |
N11A—Ni—N11B—C11B | −64.3 (15) | N21B—Ni—N22B—C22B | 13.1 (12) |
N12B—Ni—N11B—C11B | 15.8 (12) | N32—Ni—N22B—C22B | 104.5 (11) |
N22B—Ni—N11B—C11B | 94 (4) | N11A—Ni—N22B—C22B | −27 (5) |
Ni—N11B—C11B—C12B | −42.4 (16) | N12B—Ni—N22B—C22B | −84.1 (13) |
N11B—C11B—C12B—N12B | 55.6 (19) |
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D—H···A | D—H | H···A | D···A | D—H···A |
N31—H31A···I2 | 0.92 | 2.83 | 3.731 (3) | 167 |
N31—H31B···I1 | 0.92 | 2.79 | 3.663 (3) | 158 |
N32—H32A···I2i | 0.92 | 3.05 | 3.786 (3) | 138 |
N32—H32B···I1ii | 0.92 | 2.86 | 3.724 (3) | 157 |
N11A—H11B···I2iii | 0.92 | 2.97 | 3.854 (4) | 162 |
N12A—H12C···I2 | 0.92 | 3.15 | 3.940 (8) | 145 |
N11B—H11F···I2iii | 0.92 | 3.15 | 3.619 (12) | 114 |
N12B—H12G···I2 | 0.92 | 3.07 | 3.94 (2) | 159 |
N12B—H12H···I1iv | 0.92 | 3.27 | 3.824 (16) | 121 |
N21A—H21A···I2i | 0.92 | 2.92 | 3.826 (8) | 171 |
N21A—H21B···I1i | 0.92 | 2.77 | 3.665 (7) | 166 |
N22A—H22D···I1ii | 0.92 | 3.19 | 3.905 (7) | 136 |
N21B—H21E···I2i | 0.92 | 3.05 | 3.86 (2) | 148 |
N21B—H21F···I1i | 0.92 | 3.22 | 3.832 (16) | 125 |
N22B—H22G···I2 | 0.92 | 3.21 | 4.061 (16) | 154 |
N22B—H22H···I1ii | 0.92 | 2.80 | 3.69 (2) | 163 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x−1/2, y, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2.
Experimental details
Crystal data | |
Chemical formula | [Ni(C2H8N2)3]I2 |
Mr | 492.82 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 200 |
a, b, c (Å) | 14.7502 (6), 13.4881 (4), 15.9624 (7) |
V (Å3) | 3175.8 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 5.10 |
Crystal size (mm) | 0.55 × 0.47 × 0.38 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini R Mo diffractometer |
Absorption correction | Multi-scan CrysAlis RED (Oxford Diffraction, 2009) |
Tmin, Tmax | 0.337, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19070, 5271, 2835 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.756 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.091, 0.96 |
No. of reflections | 5271 |
No. of parameters | 161 |
No. of restraints | 36 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.65, −1.09 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Selected geometric parameters (Å, º)
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Ni—N31 | 2.101 (3) | Ni—N21A | 2.116 (7) |
Ni—N22A | 2.105 (7) | Ni—N32 | 2.122 (3) |
Ni—N12A | 2.113 (7) | Ni—N11A | 2.140 (5) |
N31—Ni—N22A | 93.25 (16) | N12A—Ni—N32 | 171.2 (2) |
N31—Ni—N12A | 91.3 (3) | N21A—Ni—N32 | 92.4 (2) |
N22A—Ni—N12A | 90.2 (2) | N31—Ni—N11A | 97.93 (14) |
N31—Ni—N21A | 171.6 (2) | N22A—Ni—N11A | 166.02 (19) |
N22A—Ni—N21A | 81.1 (2) | N12A—Ni—N11A | 81.26 (19) |
N12A—Ni—N21A | 94.9 (3) | N21A—Ni—N11A | 88.6 (2) |
N31—Ni—N32 | 81.99 (11) | N32—Ni—N11A | 93.98 (14) |
N22A—Ni—N32 | 95.9 (2) |
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D—H···A | D—H | H···A | D···A | D—H···A |
N31—H31A···I2 | 0.92 | 2.83 | 3.731(3) | 166.6 |
N31—H31B···I1 | 0.92 | 2.79 | 3.663(3) | 158.4 |
N32—H32A···I2i | 0.92 | 3.05 | 3.786(3) | 138.0 |
N32—H32B···I1ii | 0.92 | 2.86 | 3.724(3) | 156.7 |
N11A—H11B···I2iii | 0.92 | 2.97 | 3.854(4) | 162.2 |
N12A—H12C···I2 | 0.92 | 3.15 | 3.940(8) | 144.7 |
N11B—H11F···I2iii | 0.92 | 3.15 | 3.619(12) | 114.0 |
N12B—H12G···I2 | 0.92 | 3.07 | 3.94(2) | 158.6 |
N12B—H12H···I1iv | 0.92 | 3.27 | 3.824(16) | 120.8 |
N21A—H21A···I2i | 0.92 | 2.92 | 3.826(8) | 170.8 |
N21A—H21B···I1i | 0.92 | 2.77 | 3.665(7) | 165.7 |
N22A—H22D···I1ii | 0.92 | 3.19 | 3.905(7) | 136.3 |
N21B—H21E···I2i | 0.92 | 3.05 | 3.86(2) | 148.2 |
N21B—H21F···I1i | 0.92 | 3.22 | 3.832(16) | 125.4 |
N22B—H22G···I2 | 0.92 | 3.21 | 4.061(16) | 153.8 |
N22B—H22H···I1ii | 0.92 | 2.80 | 3.69(2) | 162.6 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x−1/2, y, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2.