catena-Poly[tris(ethyl­enediamine-κ²N,N′)nickel(II) [cadmium(II)-di-μ-1,2-dicyano­ethyl­enedithiol­ato-κ³S,S′:S′] monohydrate]

The title compound, {[Ni(C₂H₈N₂)₃][Cd(C₄N₂S₂)₂]·H₂O}_n, contains chains of bis­(1,2-dicyano­ethyl­enedithiol­ato)­cadmate(II) complex anions, tri(ethyl­enediamine)nickel(II) cations and uncoordinated water mol­ecules. The Cd^II centre is in a very distorted CdS₆ octa­hedral environment. Three bidentate ethyl­enediamine ligands are coordinated to the Ni^II atom, resulting in somewhat distorted NiN₆ octa­hedra. The polymeric anionic chains, cations and water mol­ecules are linked by hydrogen bonds into a three-dimensional framework.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.013 Å
• R factor = 0.051
• wR factor = 0.083
• Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cd1    -   S3_a    ..      23.77 su

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   N5      ..       8.88 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   N7      ..       8.99 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   N8      ..       7.18 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   N9      ..       7.29 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   N10     ..       7.95 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Ni1
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         13
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C4     ...       1.46 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C5     -   C6     ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C7     -   C8     ...       1.44 Ang.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H1     ..  H1      ..       2.14 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N10    -   H10B   ...          ?
PLAT731_ALERT_1_C Bond    Calc     0.84(7), Rep     0.84(3) ......       2.33 su-Rat
              O1   -H2      1.555   1.555

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  17 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  13 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

Recently we have reported a number of d-block metal ion complexes with ethylenediamine (en) and 1,2-dicyanoethylenedithiolate (mnt) (Fu et al., 2004, 2004a,b; Wang, Fu & Wei, 2004; Wang, Fu & He, 2004), which display a plethora of interesting structures. We now report the crystal structure of the title compound, (I), which has a distinct crystal structure from those previously determined.

Compound (I) can be formulated as {[Ni (C₂H₈N₂)₃][Cd(C₄N₂S₂)₂]·H₂O}_n and consists of chains of bis(µ₂-1,2-dicyanoethylenedithiolato-κ³S,S':S')cadmium(II) complex anions, tri(ethylenediamine-κ²N,N')nickel(II) complex cations and uncoordinated water molecules (Fig. 1).

The central Ni^II atom of the cation is in an octahedral geometry, coordinated by three bidentate en ligands via six N atoms. The three trans angles for the octahedron are 169.1 (3), 168.4 (2) and 170.7 (3)°, and the other angles range from 81.1 (3)° to 96.7 (3)°, indicating a somewhat distorted octahedral geometry. The Ni—N distances (Table 1) are comparable to the values of 2.110 (3)–2.151 (2) Å observed in related complexes (Fu et al., 2004, 2004a,b; Wang, Fu & Wei, 2004; Wang, Fu & He, 2004).

Atom Cd1 of the anionic chain is coordinated by six S atoms, of which S1–S4 are from two chelating mnt ligands and constitute the basal plane of the coordination octahedron [mean Cd—S = 2.589 (2) Å]. The two longer Cd—S bonds [mean Cd—S = 3.032 (3) Å; Table 1], to atoms S3ⁱ and S2ⁱⁱ [symmetry codes: (i) 1 − x, −y, 2 − z; (ii) 2 − x, −y, 2 − z], are from additional mnt bridging ligands and occupy the apical positions of the octahedron. The CdS₄ basal plane of the octahedron is not completely planar and displays a puckered shape. Dihedral angles of 17.39 (19)° between the planar CdS₄ group and the N1/C1–C4/N2 (mnt²⁻) mean plane, and 26.78 (18)° between the planar CdS₄ group and the N3/C5–C8/N4 (mnt²⁻) mean plane, arise. The S—Cd—S bond angles within the basal plane are 84.01 (7) and 82.34 (7)°

Bridging atoms S3ⁱ and S2ⁱⁱ coordinate to two neighboring Cd atoms simultaneously, and these four atoms (as –S3—Cd1—S3ⁱ—Cd1ⁱ–) construct an essentially planar four-membered ring. In this way each mnt bivalent anion bridges two cadmium(II) ions to form a one-dimensional chain along the a axis, as shown in Fig. 2. The distances between neighbouring Cd atoms in the chain are 4.009 (9) and 4.139 (9) Å.

The water H atoms and the NH groups of the en ligands serve as hydrogen-bond donors (Table 2). The acceptor species include water O and mnt N and S atoms. Some of these bonds connect adjacent inversion-related chains, forming a three-dimensional network (Table 2 and Fig. 3).

S2. Experimental

H₂mnt (1.00 mmol) and NaOH (2.00 mmol) were dissolved in ethanol (20 ml). To this solution, en (1.50 mmol) and an ethanol mixture (30 ml) of CdSO₄ (1.00 mmol) and NiSO₄ (0.50 mmol) were added dropwise at 313 K. The mixture was stirred for 6 h and part of the solvent was evaporated in a rotary vacuum evaporator. The resulting solution was filtered and left in air for about 20 days. Large green block-like crystals of (I) suitable for X-ray analysis were obtained. Analysis found: C 25.75, H 3.96, N 21.38, S 19.58%; calculated for C₁₄H₂₆CdN₁₀NiOS₄: C 25.88, H 4.03, N 21.55, S 19.74%.

S3. Refinement

The water H atoms were found in difference maps. The O—H distances were restrained to 0.90 (1) Å and the U_iso(H) values were allowed to refine. Please check s.u. values in Table 2; they do not correspond to those in CIF. All other H atoms were placed in idealized positions (C—H = 0.97 Å and N—H = 0.90 Å) and refined as riding on their carrier atoms with U_iso(H) = 1.2U_eq(carrier).

Computing details

Data collection: SMART (Bruker,1997); cell refinement: SAINT (Bruker,1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of the asymmetric atoms of (I), showing 30% probability displacement ellipsoids (arbitrary spheres for the H atoms).
	Fig. 2. The chain-like structure for the complex anion of (I).
	Fig. 3. Packing diagram for (I), viewed down a, with hydrogen-bonded interactions indicated by dashed lines.

catena-Poly[bis(ethylenediamine-κ²N,N')copper(II) (2,3-dimercaptobutenedinitrile-κ²S,S')(2,3-dimercaptobutenedinitrile- κ⁴S,S',N,N')cuprate(II)]

Crystal data

[Ni(C2H8N2)3][Cd(C4N2S2)2]·H2O	F(000) = 1312
Mr = 649.80	Dx = 1.749 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1561 reflections
a = 7.5796 (15) Å	θ = 2.4–19.6°
b = 19.255 (4) Å	µ = 1.99 mm^−1
c = 17.201 (4) Å	T = 293 K
β = 100.509 (4)°	Block, green
V = 2468.3 (9) Å^3	0.30 × 0.15 × 0.12 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	4346 independent reflections
Radiation source: fine-focus sealed tube	2220 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.069
ϕ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→8
Tmin = 0.587, Tmax = 0.796	k = −22→16
12887 measured reflections	l = −20→20

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)] = 0.051	Hydrogen site location: difmap and geom
wR(F^2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0141P)^2] where P = (Fo^2 + 2Fc^2)/3
4346 reflections	(Δ/σ)max = 0.001
286 parameters	Δρmax = 0.88 e Å^−3
4 restraints	Δρmin = −0.77 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.74918 (10)	0.03798 (4)	1.00912 (4)	0.0590 (3)
Ni1	0.11839 (14)	0.29140 (5)	0.96600 (5)	0.0294 (3)
N1	1.1518 (12)	0.1300 (5)	1.3106 (5)	0.093 (3)
N2	1.1703 (12)	−0.0685 (5)	1.3014 (5)	0.088 (3)
N3	0.3509 (12)	−0.0100 (5)	0.6924 (5)	0.089 (3)
N4	0.4554 (16)	0.1840 (5)	0.7199 (5)	0.122 (4)
N5	0.2319 (9)	0.1972 (3)	1.0178 (4)	0.050 (2)
H5A	0.1444	0.1687	1.0277	0.060*
H5B	0.2922	0.1754	0.9844	0.060*
N6	0.3339 (9)	0.3348 (4)	1.0519 (4)	0.059 (2)
H6A	0.3923	0.3678	1.0296	0.071*
H6B	0.2908	0.3537	1.0925	0.071*
N7	−0.0792 (9)	0.2953 (3)	1.0410 (4)	0.056 (2)
H7A	−0.1500	0.2575	1.0324	0.067*
H7B	−0.0240	0.2949	1.0919	0.067*
N8	0.0089 (10)	0.3936 (3)	0.9380 (4)	0.059 (2)
H8A	0.0970	0.4235	0.9323	0.071*
H8B	−0.0713	0.3925	0.8925	0.071*
N9	−0.0619 (9)	0.2407 (4)	0.8724 (4)	0.059 (2)
H9A	−0.0971	0.1996	0.8892	0.070*
H9B	−0.1600	0.2672	0.8569	0.070*
N10	0.2792 (9)	0.2982 (3)	0.8752 (4)	0.062 (2)
H10A	0.3330	0.3400	0.8766	0.074*
H10B	0.3644	0.2651	0.8821	0.074*
O1	0.4310 (11)	0.4543 (5)	0.9367 (5)	0.106 (3)
S1	0.9130 (3)	0.12532 (12)	1.10874 (14)	0.0522 (7)
S2	0.9539 (3)	−0.05198 (11)	1.09359 (12)	0.0465 (7)
S3	0.5457 (3)	−0.03029 (12)	0.90052 (12)	0.0478 (7)
S4	0.5892 (3)	0.14580 (12)	0.92933 (13)	0.0473 (7)
C1	1.0891 (12)	0.1025 (5)	1.2544 (6)	0.055 (3)
C2	1.0132 (11)	0.0692 (5)	1.1819 (5)	0.041 (2)
C3	1.0272 (10)	0.0002 (5)	1.1759 (4)	0.038 (2)
C4	1.1077 (12)	−0.0390 (5)	1.2463 (5)	0.057 (3)
C5	0.4170 (13)	0.0101 (5)	0.7528 (6)	0.060 (3)
C6	0.4939 (10)	0.0350 (5)	0.8301 (4)	0.044 (2)
C7	0.5163 (11)	0.1045 (5)	0.8403 (5)	0.044 (2)
C8	0.4785 (16)	0.1491 (5)	0.7722 (6)	0.078 (4)
C9	0.3558 (12)	0.2142 (5)	1.0927 (5)	0.056 (3)
H9C	0.2884	0.2219	1.1347	0.067*
H9D	0.4388	0.1762	1.1080	0.067*
C10	0.4539 (13)	0.2770 (5)	1.0794 (5)	0.060 (3)
H10C	0.5284	0.2674	1.0404	0.072*
H10D	0.5323	0.2901	1.1282	0.072*
C11	−0.1887 (12)	0.3577 (4)	1.0255 (5)	0.057 (3)
H11A	−0.2355	0.3704	1.0724	0.069*
H11B	−0.2895	0.3489	0.9831	0.069*
C12	−0.0780 (12)	0.4157 (5)	1.0028 (6)	0.064 (3)
H12A	−0.1537	0.4557	0.9865	0.077*
H12B	0.0121	0.4291	1.0478	0.077*
C13	0.0323 (14)	0.2301 (5)	0.8062 (5)	0.072 (3)
H13A	−0.0550	0.2251	0.7577	0.086*
H13B	0.1014	0.1875	0.8146	0.086*
C14	0.1531 (14)	0.2882 (5)	0.7976 (5)	0.076 (3)
H14A	0.0841	0.3302	0.7834	0.091*
H14B	0.2206	0.2781	0.7562	0.091*
H1	0.534 (5)	0.460 (4)	0.962 (4)	0.080*
H2	0.370 (11)	0.476 (4)	0.899 (4)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0687 (5)	0.0490 (5)	0.0497 (5)	−0.0014 (4)	−0.0145 (4)	0.0023 (4)
Ni1	0.0350 (6)	0.0320 (6)	0.0224 (6)	−0.0019 (6)	0.0088 (5)	−0.0017 (5)
N1	0.092 (8)	0.116 (8)	0.060 (6)	−0.010 (6)	−0.011 (6)	−0.034 (6)
N2	0.099 (8)	0.111 (8)	0.048 (6)	0.008 (6)	−0.003 (6)	0.024 (5)
N3	0.099 (8)	0.118 (8)	0.048 (6)	−0.001 (6)	0.005 (6)	−0.025 (6)
N4	0.232 (13)	0.089 (8)	0.050 (6)	0.047 (8)	0.035 (8)	0.027 (6)
N5	0.054 (5)	0.055 (5)	0.049 (5)	−0.021 (4)	0.027 (4)	−0.014 (4)
N6	0.075 (6)	0.059 (6)	0.044 (5)	−0.013 (5)	0.013 (4)	0.005 (4)
N7	0.070 (6)	0.036 (5)	0.059 (5)	0.003 (5)	0.005 (4)	0.011 (4)
N8	0.074 (6)	0.063 (6)	0.048 (5)	−0.014 (5)	0.031 (5)	0.000 (4)
N9	0.062 (6)	0.067 (6)	0.050 (5)	−0.001 (4)	0.021 (4)	0.011 (4)
N10	0.070 (6)	0.039 (5)	0.078 (6)	0.001 (5)	0.019 (5)	−0.003 (5)
O1	0.102 (7)	0.097 (7)	0.102 (7)	0.002 (6)	−0.031 (5)	0.010 (5)
S1	0.0634 (19)	0.0404 (16)	0.0494 (16)	−0.0092 (13)	0.0009 (14)	0.0005 (12)
S2	0.0556 (17)	0.0438 (16)	0.0374 (14)	0.0044 (13)	0.0009 (12)	0.0014 (12)
S3	0.0546 (17)	0.0475 (16)	0.0399 (14)	−0.0072 (14)	0.0046 (12)	0.0017 (13)
S4	0.0567 (17)	0.0421 (15)	0.0428 (15)	0.0057 (13)	0.0085 (13)	0.0007 (12)
C1	0.054 (7)	0.062 (8)	0.047 (7)	−0.008 (6)	0.002 (6)	−0.003 (6)
C2	0.042 (6)	0.047 (6)	0.036 (6)	−0.009 (5)	0.008 (5)	−0.009 (5)
C3	0.035 (6)	0.052 (6)	0.029 (5)	0.004 (5)	0.012 (4)	−0.001 (5)
C4	0.054 (7)	0.076 (8)	0.040 (6)	−0.002 (6)	0.011 (5)	0.008 (6)
C5	0.065 (8)	0.067 (8)	0.047 (7)	0.012 (6)	0.006 (6)	0.001 (6)
C6	0.040 (6)	0.061 (7)	0.031 (5)	0.004 (5)	0.003 (4)	−0.005 (5)
C7	0.051 (6)	0.048 (6)	0.037 (6)	0.013 (5)	0.018 (5)	0.003 (5)
C8	0.134 (11)	0.065 (8)	0.038 (7)	0.038 (8)	0.019 (7)	0.003 (6)
C9	0.065 (7)	0.050 (7)	0.052 (6)	−0.002 (6)	0.009 (5)	0.001 (6)
C10	0.080 (8)	0.048 (7)	0.054 (7)	−0.015 (6)	0.018 (6)	−0.008 (5)
C11	0.066 (8)	0.048 (7)	0.059 (7)	0.005 (6)	0.017 (6)	0.011 (5)
C12	0.065 (8)	0.052 (7)	0.080 (8)	0.004 (6)	0.023 (6)	−0.003 (6)
C13	0.104 (9)	0.062 (8)	0.047 (7)	−0.038 (7)	0.005 (6)	−0.013 (6)
C14	0.097 (9)	0.089 (9)	0.048 (7)	−0.003 (8)	0.028 (6)	0.000 (7)

Geometric parameters (Å, º)

Cd1—S1	2.555 (2)	N10—C14	1.506 (9)
Cd1—S3	2.558 (2)	N10—H10A	0.9000
Cd1—S2	2.588 (2)	N10—H10B	0.9000
Cd1—S4	2.657 (2)	O1—H1	0.83 (3)
Cd1—S3^i	2.949 (3)	O1—H2	0.84 (3)
Cd1—S2^ii	3.116 (3)	S1—C2	1.725 (9)
Ni1—N5	2.133 (6)	S2—C3	1.742 (8)
Ni1—N9	2.147 (7)	S3—C6	1.739 (8)
Ni1—N7	2.149 (7)	S3—Cd1^i	2.949 (2)
Ni1—N10	2.153 (7)	S4—C7	1.725 (8)
Ni1—N8	2.156 (7)	C1—C2	1.427 (11)
Ni1—N6	2.161 (6)	C2—C3	1.339 (10)
N1—C1	1.128 (10)	C3—C4	1.462 (11)
N2—C4	1.133 (10)	C5—C6	1.434 (11)
N3—C5	1.136 (10)	C6—C7	1.357 (11)
N4—C8	1.111 (11)	C7—C8	1.438 (12)
N5—C9	1.485 (9)	C9—C10	1.459 (10)
N5—H5A	0.9000	C9—H9C	0.9700
N5—H5B	0.9000	C9—H9D	0.9700
N6—C10	1.460 (9)	C10—H10C	0.9700
N6—H6A	0.9000	C10—H10D	0.9700
N6—H6B	0.9000	C11—C12	1.492 (11)
N7—C11	1.457 (9)	C11—H11A	0.9700
N7—H7A	0.9000	C11—H11B	0.9700
N7—H7B	0.9000	C12—H12A	0.9700
N8—C12	1.457 (10)	C12—H12B	0.9700
N8—H8A	0.9000	C13—C14	1.470 (11)
N8—H8B	0.9000	C13—H13A	0.9700
N9—C13	1.464 (10)	C13—H13B	0.9700
N9—H9A	0.9000	C14—H14A	0.9700
N9—H9B	0.9000	C14—H14B	0.9700
S1—Cd1—S3	169.19 (8)	C14—N10—H10B	110.4
S1—Cd1—S2	84.01 (7)	Ni1—N10—H10B	110.4
S3—Cd1—S2	106.61 (7)	H10A—N10—H10B	108.6
S1—Cd1—S4	87.27 (8)	H1—O1—H2	132 (10)
S3—Cd1—S4	82.34 (7)	C2—S1—Cd1	99.9 (3)
S2—Cd1—S4	169.62 (8)	C3—S2—Cd1	98.0 (3)
S1—Cd1—S3^i	90.12 (8)	C6—S3—Cd1	99.6 (3)
S3—Cd1—S3^i	86.85 (7)	C6—S3—Cd1^i	107.9 (3)
S2—Cd1—S3^i	96.03 (8)	Cd1—S3—Cd1^i	93.15 (7)
S4—Cd1—S3^i	89.60 (7)	C7—S4—Cd1	98.1 (3)
S1—Cd1—S2^ii	90.60 (8)	N1—C1—C2	178.0 (12)
S3—Cd1—S2^ii	91.83 (7)	C3—C2—C1	119.2 (8)
S2—Cd1—S2^ii	87.42 (7)	C3—C2—S1	126.6 (7)
S4—Cd1—S2^ii	87.04 (7)	C1—C2—S1	114.2 (7)
S3^i—Cd1—S2^ii	176.53 (6)	C2—C3—C4	118.4 (8)
N5—Ni1—N9	94.6 (3)	C2—C3—S2	128.1 (7)
N5—Ni1—N7	92.9 (2)	C4—C3—S2	113.5 (7)
N9—Ni1—N7	92.8 (3)	N2—C4—C3	179.1 (11)
N5—Ni1—N10	96.7 (3)	N3—C5—C6	177.8 (12)
N9—Ni1—N10	81.4 (3)	C7—C6—C5	118.0 (8)
N7—Ni1—N10	169.1 (3)	C7—C6—S3	128.0 (7)
N5—Ni1—N8	168.4 (2)	C5—C6—S3	114.0 (7)
N9—Ni1—N8	94.6 (3)	C6—C7—C8	118.9 (8)
N7—Ni1—N8	79.6 (3)	C6—C7—S4	125.6 (7)
N10—Ni1—N8	91.6 (3)	C8—C7—S4	115.6 (7)
N5—Ni1—N6	81.1 (3)	N4—C8—C7	177.6 (15)
N9—Ni1—N6	170.7 (3)	C10—C9—N5	107.9 (7)
N7—Ni1—N6	95.7 (3)	C10—C9—H9C	110.1
N10—Ni1—N6	90.9 (3)	N5—C9—H9C	110.1
N8—Ni1—N6	90.7 (3)	C10—C9—H9D	110.1
C9—N5—Ni1	108.5 (5)	N5—C9—H9D	110.1
C9—N5—H5A	110.0	H9C—C9—H9D	108.4
Ni1—N5—H5A	110.0	C9—C10—N6	112.1 (8)
C9—N5—H5B	110.0	C9—C10—H10C	109.2
Ni1—N5—H5B	110.0	N6—C10—H10C	109.2
H5A—N5—H5B	108.4	C9—C10—H10D	109.2
C10—N6—Ni1	106.0 (5)	N6—C10—H10D	109.2
C10—N6—H6A	110.5	H10C—C10—H10D	107.9
Ni1—N6—H6A	110.5	N7—C11—C12	109.7 (8)
C10—N6—H6B	110.5	N7—C11—H11A	109.7
Ni1—N6—H6B	110.5	C12—C11—H11A	109.7
H6A—N6—H6B	108.7	N7—C11—H11B	109.7
C11—N7—Ni1	110.8 (5)	C12—C11—H11B	109.7
C11—N7—H7A	109.5	H11A—C11—H11B	108.2
Ni1—N7—H7A	109.5	N8—C12—C11	109.6 (8)
C11—N7—H7B	109.5	N8—C12—H12A	109.7
Ni1—N7—H7B	109.5	C11—C12—H12A	109.7
H7A—N7—H7B	108.1	N8—C12—H12B	109.7
C12—N8—Ni1	107.7 (5)	C11—C12—H12B	109.7
C12—N8—H8A	110.2	H12A—C12—H12B	108.2
Ni1—N8—H8A	110.2	N9—C13—C14	111.9 (8)
C12—N8—H8B	110.2	N9—C13—H13A	109.2
Ni1—N8—H8B	110.2	C14—C13—H13A	109.2
H8A—N8—H8B	108.5	N9—C13—H13B	109.2
C13—N9—Ni1	108.2 (5)	C14—C13—H13B	109.2
C13—N9—H9A	110.1	H13A—C13—H13B	107.9
Ni1—N9—H9A	110.1	C13—C14—N10	108.3 (8)
C13—N9—H9B	110.1	C13—C14—H14A	110.0
Ni1—N9—H9B	110.1	N10—C14—H14A	110.0
H9A—N9—H9B	108.4	C13—C14—H14B	110.0
C14—N10—Ni1	106.5 (5)	N10—C14—H14B	110.0
C14—N10—H10A	110.4	H14A—C14—H14B	108.4
Ni1—N10—H10A	110.4

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1^iii	0.83 (5)	2.38 (7)	2.847 (13)	116 (5)
O1—H2···N3^iv	0.84 (7)	2.10 (8)	2.870 (12)	154 (8)
N5—H5A···S1^v	0.90	2.57	3.404 (7)	154
N5—H5B···S4	0.90	2.66	3.483 (7)	153
N6—H6A···O1	0.90	2.36	3.209 (12)	157
N6—H6B···N2^vi	0.90	2.34	3.141 (11)	149
N7—H7A···S1^v	0.90	2.86	3.478 (6)	127
N7—H7B···N4^vii	0.90	2.27	3.066 (11)	147
N8—H8A···O1	0.90	2.59	3.410 (11)	152
N8—H8A···N3^iv	0.90	2.59	3.237 (11)	129
N8—H8B···N1^viii	0.90	2.34	3.189 (11)	156
N9—H9A···S4^v	0.90	2.79	3.498 (8)	136
N9—H9B···N1^viii	0.90	2.48	3.346 (12)	160
N10—H10A···O1	0.90	2.49	3.322 (11)	154

Symmetry codes: (iii) −x+1, −y+1, −z+2; (iv) −x+1/2, y+1/2, −z+3/2; (v) x−1, y, z; (vi) −x+3/2, y+1/2, −z+5/2; (vii) x−1/2, −y+1/2, z+1/2; (viii) x−3/2, −y+1/2, z−1/2.