Tris(ethane-1,2-diamine-κ2N,N′)nickel(II) diiodide

Brewer, G.; Butcher, R.J.; Jasinski, J.P.

doi:10.1107/S1600536809054580

Tris(ethane-1,2-diamine-κ²N,N′)nickel(II) diiodide

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—H

I 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 Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809054580/pb2013Isup2.hkl Contains datablock I

CCDC reference: 766702

checkCIF report

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 found



Alert level B
PLAT910_ALERT_3_B Missing # of FCF Reflections Below Th(Min) .....         17
PLAT923_ALERT_1_B S    values in the CIF and FCF Differ by .......       0.03

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C11A   --  C12A    ..       6.64 su
PLAT420_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         12
PLAT480_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        433
PLAT922_ALERT_1_C wR2 * 100.0 in the CIF and FCF Differ by .......       0.26

Alert level G
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................      35.00 Perc.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         36
PLAT710_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   1.555
PLAT710_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   1.555
PLAT710_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   1.555
PLAT710_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   1.555
PLAT710_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   1.555
PLAT710_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   1.555
PLAT710_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   1.555
PLAT710_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   1.555
PLAT710_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   1.555
PLAT710_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   1.555
PLAT811_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 of tris(2-aminoethyl)amine(tren) with imidazole-2-carboxaldehyde form double salts with metal (K⁺, Rb⁺, Cs⁺ and NH₄⁺) perchlorates (Brewer et al., 2007) and metal (M = Na⁺, K⁺, Rb⁺, Cs⁺ and NH₄⁺) tetrafluoroborates (Alvarado et al., 2009). Thus this system shows size selectivity for alkali metal cations. Structural studies of the 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 these structures also reveal a linear polymeric anion, [(MX₃)^2-]_n (X=ClO₄^- or BF₄–), similar to that observed above suggesting that anions of this type are stable in certain settings and may be used in other reactions. The anions in all of the above complexes are tethered to the cations through hydogen bonds involving either amine, –NH₂ or the bidentate hydrogen bonding donor, -N=C_imine(H)—C_imidazole—N_imidazole(H). In an effort to determine the nature of the interactions between the amine, –NH₂ (in the cation building unit used in the formation of double salts) and the anion in stabilizing these salts we report the crystal structure of the title compound, C₆H₂₄N₆NiI₂, (I).

C₆H₂₄N₆NiI₂, (I), crystallizes with a [Ni(en)₃²⁺] cation and two I^_ ions in the asymmetric unit (Fig. 1). In the cation, two of the 1,2-ethanediamine-N,N' rings surrrounding the Ni²⁺ ion contain disordered carbon and nitrogen atoms while the third exhibits extensive weak N—H···I interactions with the two iodide ions (Table 1) that extend throughout the crystalline lattice producing an infinite network along the (011) plane of the unit cell (Fig. 2). The major components of the two disordered 5-membered Ni²⁺-1,2-ethanediamine-N,N' rings adopt sightly distorted half-chair conformations (Cremer & Pople, 1975) with puckering 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 for ring 31 (Ni/N31/C31/C32/N32) are 0.438 (4)Å and 270.967 (6)°. For an ideal half-chair, Phi(2) = k x 36° + 18° or 180° + Phi(2). The dihedral angle between the mean planes of the normal ring (31) and the major components of the disordered rings (11 & 21) measures 85.6 (8)° and 83.5 (0)°, while between rings 11 and 21 themselves is 87.2 (7)°. Bond distances within the cation are normal (Allen et al., 2002) and comparable to those in similar structures (Dvorkin et al., 1989, 1991; Farago et al., 1967; Cramer et al. 1976; Cramer & Huneke, 1978).

The presence of I1 and I2 in the crystal lattice allows for the formation of a collection of weak intermolecular N–H···I interactions which thereby 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 excess ethylenediamine was added to the green solution. The resulting violet/purple solution was allowed to go to dryness. The crude [Ni(en)₃]Cl₂ was redissolved in water saturated with potassium iodide. The dark blockish crystals suitable for x-ray studies, in space group Pbca, were collected by filtration on standing.

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, showing the [Ni(en)₃²⁺] cation and two I^_ ions in the asymmetric unit, the atom labeling scheme and 50% probability displacement ellipsoids. Only the major components 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 indicate weak N—H···I hydrogen bond interactions.

Fig. 2. Packing diagram of the title compound, (I), viewed down the a axis. Dashed lines indicate weak intermolecular N—H···I interactions which produces a infinite weak bonding network arranged along the (011) plane of the unit cell.

Tris(ethane-1,2-diamine-κ²N,N')nickel(II) diiodide top

Crystal data top

[Ni(C₂H₈N₂)₃]I₂	F(000) = 1888
M_r = 492.82	D_x = 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 top

Oxford Diffraction Gemini R Mo diffractometer	5271 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2835 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 10.5081 pixels mm^-1	θ_max = 32.5°, θ_min = 4.6°
ω scans	h = −21→19
Absorption correction: multi-scan CrysAlis RED (Oxford Diffraction, 2009)	k = −10→19
T_min = 0.337, T_max = 1.000	l = −24→16
19070 measured reflections

Refinement top

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(F_o²) + (0.043P)²] where P = (F_o² + 2F_c²)/3
5271 reflections	(Δ/σ)_max = 0.001
161 parameters	Δρ_max = 1.65 e Å⁻³
36 restraints	Δρ_min = −1.09 e Å⁻³

Crystal data top

[Ni(C₂H₈N₂)₃]I₂	V = 3175.8 (2) Å³
M_r = 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 top

Oxford Diffraction Gemini R Mo diffractometer	5271 independent reflections
Absorption correction: multi-scan CrysAlis RED (Oxford Diffraction, 2009)	2835 reflections with I > 2σ(I)
T_min = 0.337, T_max = 1.000	R_int = 0.042
19070 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	36 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 0.96	Δρ_max = 1.65 e Å⁻³
5271 reflections	Δρ_min = −1.09 e Å⁻³
161 parameters

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	U_iso*/U_eq	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) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···I1^iv	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
M_r	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)
T_min, T_max	0.337, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	19070, 5271, 2835
R_int	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
Δρ_max, Δρ_min (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) top

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)

Hydrogen-bond geometry (Å, º) top

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···I1^iv	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.

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