μ-Cyanido-1:2κ2N:C-tricyanido-2κ3C-(rac-5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane-1κ4N,N′,N′′,N′′′)dinickel(II) N,N-di­methyl­formamide monosolvate hemi­hydrate

Jiang, H.-M.; Ng, S.W.

doi:10.1107/S1600536810042625

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page m1467

https://doi.org/10.1107/S1600536810042625

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μ-Cyanido-1:2κ²N:C-tricyanido-2κ³C-(rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-1κ⁴N,N′,N′′,N′′′)dinickel(II) N,N-dimethylformamide monosolvate hemihydrate

Hai-Ming Jiang ^a and Seik Weng Ng ^b ^*

^aDepartment of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou Hunan 425100, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 18 October 2010; accepted 20 October 2010; online 30 October 2010)

The two Ni^II atoms in the title complex, [Ni₂(CN)₄(C₁₆H₃₆N₄)]·C₃H₇NO·0.5H₂O, are bridged by a cyanide ion. The macrocycle folds around one Ni^II atom, which is five-coordinated in an NiN₅ square-pyramidal geometry. The other Ni^II atom is surrounded by the cyanide ions in an NiN₄ square-planar geometry. The dimethylformamide solvent molecule is disordered over two positions in a 0.62 (1):0.38 (1) ratio and the water molecule is disordered about a center of inversion. The dinuclear molecule and solvent molecules are linked by N—H⋯O, N–H⋯N and O—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For two related structures, see: Jiang et al. (2005 , 2007 ).

Experimental

Crystal data

[Ni₂(CN)₄(C₁₆H₃₆N₄)]·C₃H₇NO·0.5H₂O
M_r = 588.09
Monoclinic, P 2₁ /n
a = 10.0122 (5) Å
b = 10.2109 (5) Å
c = 28.3246 (15) Å
β = 91.468 (1)°
V = 2894.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.33 mm⁻¹
T = 173 K
0.40 × 0.35 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.617, T_max = 0.825
14236 measured reflections
6181 independent reflections
4435 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.121
S = 1.03
6181 reflections
393 parameters
76 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H11⋯N7	0.84	2.01	2.825 (8)	163
N1—H1⋯N6ⁱ	0.88 (3)	2.49 (3)	2.854 (4)	105 (3)
N2—H2⋯O1	0.88 (3)	2.46 (2)	3.278 (7)	156 (3)
N2—H2⋯O1′	0.88 (3)	2.05 (2)	2.88 (1)	158 (3)
N3—H3⋯N5	0.87 (3)	2.48 (3)	2.843 (4)	106 (3)
N4—H4⋯O1	0.88 (3)	2.08 (2)	2.927 (8)	162 (3)
N4—H4⋯O1′	0.88 (3)	2.30 (2)	3.14 (1)	160 (3)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810042625/bt5382sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042625/bt5382Isup2.hkl

checkCIF report

Comment top

We have previously reported the adducts of 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane with nickel salts. The macrocycle in these adducts chelate to the metal atom in a tetradentate manner. With the counterion as a tetracyanidonickellate(II) dianion, a tetranuclear compound was isolated in which the two dianions each bridges two macrocycle-coordinated nickel atoms (Jiang et al., 2005). Another study reported a macrocycle-nickel–tetracyanidonickellate compound, which exists as a chain (Jiang et al., 2007). In dinuclear [Ni₂(C₁₆H₃₆N₄)]^.DMF^.0.5H₂O (Scheme I, Fig. 1) the two metal atoms are linked by only one cyanide bridge. The dinuclear molecule, DMF molecule and lattice water molecules are linked by N–H···O, N–H···N and O–H···O hydrogen bonds into a linear chain motif.

Related literature top

For two related structures, see: Jiang et al. (2005, 2007).

Experimental top

A DMF solution (20 ml) of dipotassium tetracyanonickellate dihydrate (0.139 g, 0.5 mmol) was layered with an acetonitrile solution (20 ml) of [Ni(rac-L)](ClO₄)₂(0.272 g, 0.5 mmol) (rac-L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in a glass tube. After about aone month, blue prismatic crystals formed along the walls.

Structure description top

For two related structures, see: Jiang et al. (2005, 2007).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of the title compound at the 70% probability level; hydrogen atoms are shown as spheres of arbitrary radius. The disorder is not shown.

µ-Cyanido-1:2κ²N:C-tricyanido-2κ³C-(rac- 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane- 1κ⁴N,N',N'',N''')dinickel(II) N,N-dimethylformamide monosolvate hemihydrate top

Crystal data top

[Ni₂(CN)₄(C₁₆H₃₆N₄)]·C₃H₇NO·0.5H₂O	F(000) = 1252
M_r = 588.09	D_x = 1.349 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5065 reflections
a = 10.0122 (5) Å	θ = 2.5–26.8°
b = 10.2109 (5) Å	µ = 1.33 mm⁻¹
c = 28.3246 (15) Å	T = 173 K
β = 91.468 (1)°	Prim, blue
V = 2894.8 (3) Å³	0.40 × 0.35 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	6181 independent reflections
Radiation source: fine-focus sealed tube	4435 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
φ and ω scans	θ_max = 27.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→11
T_min = 0.617, T_max = 0.825	k = −13→12
14236 measured reflections	l = −30→36

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0666P)² + 0.7079P] where P = (F_o² + 2F_c²)/3
6181 reflections	(Δ/σ)_max = 0.001
393 parameters	Δρ_max = 0.55 e Å⁻³
76 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Ni₂(CN)₄(C₁₆H₃₆N₄)]·C₃H₇NO·0.5H₂O	V = 2894.8 (3) Å³
M_r = 588.09	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.0122 (5) Å	µ = 1.33 mm⁻¹
b = 10.2109 (5) Å	T = 173 K
c = 28.3246 (15) Å	0.40 × 0.35 × 0.15 mm
β = 91.468 (1)°

Data collection top

Bruker SMART APEX diffractometer	6181 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4435 reflections with I > 2σ(I)
T_min = 0.617, T_max = 0.825	R_int = 0.035
14236 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	76 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.55 e Å⁻³
6181 reflections	Δρ_min = −0.39 e Å⁻³
393 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.40876 (4)	0.41556 (4)	0.163713 (13)	0.02095 (12)
Ni2	0.41778 (4)	0.28354 (4)	0.332984 (14)	0.02452 (13)
O1W	0.5942 (8)	−0.0422 (7)	0.4816 (2)	0.076 (2)	0.50
H11	0.5490	0.0200	0.4702	0.115*	0.50
H12	0.5602	−0.0657	0.5071	0.115*	0.50
N1	0.2327 (3)	0.3662 (3)	0.12200 (10)	0.0284 (6)
H1	0.177 (3)	0.429 (3)	0.1287 (12)	0.034*
N2	0.4790 (3)	0.4921 (3)	0.09926 (10)	0.0282 (6)
H2	0.532 (3)	0.433 (3)	0.0872 (11)	0.034*
N3	0.6097 (3)	0.4408 (3)	0.19194 (9)	0.0261 (6)
H3	0.599 (3)	0.435 (3)	0.2224 (4)	0.031*
N4	0.4697 (3)	0.2182 (3)	0.15349 (11)	0.0285 (6)
H4	0.491 (4)	0.213 (4)	0.1236 (5)	0.034*
N5	0.3642 (3)	0.3681 (3)	0.23283 (10)	0.0310 (6)
N6	0.1889 (3)	0.0938 (3)	0.32576 (10)	0.0289 (6)
N7	0.4806 (4)	0.1648 (5)	0.42804 (14)	0.0729 (13)
N8	0.6614 (4)	0.4584 (4)	0.33648 (15)	0.0586 (10)
C1	0.2720 (4)	0.3856 (4)	0.07273 (12)	0.0358 (8)
H1A	0.1911	0.3951	0.0522	0.043*
H1B	0.3221	0.3080	0.0619	0.043*
C2	0.3578 (3)	0.5057 (4)	0.06859 (12)	0.0335 (8)
H2A	0.3839	0.5174	0.0354	0.040*
H2B	0.3067	0.5840	0.0781	0.040*
C3	0.5572 (4)	0.6160 (4)	0.10311 (13)	0.0360 (8)
H3A	0.5026	0.6822	0.1201	0.043*
C4	0.5928 (5)	0.6725 (5)	0.05472 (15)	0.0663 (15)
H4A	0.5106	0.6910	0.0364	0.100*
H4B	0.6468	0.6089	0.0377	0.100*
H4C	0.6437	0.7538	0.0592	0.100*
C5	0.6883 (4)	0.5960 (4)	0.13084 (12)	0.0341 (8)
H5A	0.7422	0.6765	0.1273	0.041*
H5B	0.7373	0.5242	0.1154	0.041*
C6	0.6846 (3)	0.5644 (3)	0.18365 (12)	0.0288 (7)
C7	0.6187 (4)	0.6735 (3)	0.21114 (13)	0.0370 (8)
H7A	0.5250	0.6817	0.2007	0.056*
H7B	0.6653	0.7562	0.2055	0.056*
H7C	0.6234	0.6530	0.2449	0.056*
C8	0.8294 (4)	0.5519 (4)	0.20212 (14)	0.0418 (9)
H8A	0.8302	0.5166	0.2343	0.063*
H8B	0.8718	0.6384	0.2023	0.063*
H8C	0.8785	0.4928	0.1816	0.063*
C9	0.6805 (3)	0.3219 (3)	0.17783 (14)	0.0347 (8)
H9A	0.7628	0.3116	0.1976	0.042*
H9B	0.7068	0.3298	0.1445	0.042*
C10	0.5924 (4)	0.2031 (3)	0.18337 (14)	0.0366 (9)
H10A	0.6413	0.1234	0.1739	0.044*
H10B	0.5682	0.1933	0.2169	0.044*
C11	0.3705 (4)	0.1138 (3)	0.16224 (14)	0.0356 (8)
H11A	0.3366	0.1257	0.1949	0.043*
C12	0.4307 (4)	−0.0238 (4)	0.15890 (18)	0.0563 (12)
H12A	0.5060	−0.0319	0.1815	0.084*
H12B	0.4622	−0.0385	0.1268	0.084*
H12C	0.3625	−0.0891	0.1662	0.084*
C13	0.2526 (4)	0.1236 (3)	0.12764 (13)	0.0359 (8)
H13A	0.1985	0.0431	0.1311	0.043*
H13B	0.2884	0.1224	0.0954	0.043*
C14	0.1569 (3)	0.2413 (3)	0.13060 (13)	0.0322 (8)
C15	0.0965 (4)	0.2505 (4)	0.17929 (14)	0.0407 (9)
H15A	0.0348	0.3249	0.1801	0.061*
H15B	0.1679	0.2629	0.2032	0.061*
H15C	0.0479	0.1695	0.1860	0.061*
C16	0.0434 (4)	0.2243 (4)	0.09397 (15)	0.0504 (11)
H16A	−0.0098	0.3048	0.0922	0.076*
H16B	−0.0137	0.1511	0.1032	0.076*
H16C	0.0809	0.2060	0.0630	0.076*
C17	0.3803 (3)	0.3420 (3)	0.27219 (12)	0.0266 (7)
C18	0.2738 (3)	0.1684 (3)	0.32772 (11)	0.0253 (7)
C19	0.4574 (4)	0.2135 (4)	0.39238 (14)	0.0441 (10)
C20	0.5677 (4)	0.3942 (4)	0.33603 (13)	0.0354 (8)
O1	0.5992 (7)	0.2131 (7)	0.0620 (3)	0.064 (2)	0.620 (6)
N9	0.7506 (6)	0.0709 (6)	0.0306 (2)	0.063 (2)	0.620 (6)
C21	0.6732 (6)	0.1167 (7)	0.0637 (2)	0.058 (2)	0.620 (6)
H21	0.6746	0.0693	0.0926	0.070*	0.620 (6)
C22	0.7521 (12)	0.1403 (11)	−0.0141 (3)	0.100 (4)	0.620 (6)
H22A	0.6744	0.1984	−0.0166	0.150*	0.620 (6)
H22B	0.7489	0.0770	−0.0401	0.150*	0.620 (6)
H22C	0.8341	0.1923	−0.0157	0.150*	0.620 (6)
C23	0.8352 (7)	−0.0424 (7)	0.0360 (3)	0.064 (2)	0.620 (6)
H23A	0.8188	−0.0843	0.0664	0.095*	0.620 (6)
H23B	0.9290	−0.0156	0.0348	0.095*	0.620 (6)
H23C	0.8152	−0.1046	0.0104	0.095*	0.620 (6)
O1'	0.5863 (12)	0.2654 (13)	0.0530 (4)	0.063 (4)	0.380 (6)
N9'	0.7086 (10)	0.1118 (10)	0.0163 (2)	0.053 (3)	0.380 (6)
C21'	0.6906 (10)	0.2298 (11)	0.0351 (3)	0.044 (3)	0.380 (6)
H21B	0.7628	0.2902	0.0346	0.053*	0.380 (6)
C22'	0.6064 (16)	0.0150 (16)	0.0151 (7)	0.120 (7)	0.380 (6)
H22D	0.5189	0.0578	0.0126	0.180*	0.380 (6)
H22E	0.6118	−0.0371	0.0442	0.180*	0.380 (6)
H22F	0.6182	−0.0423	−0.0122	0.180*	0.380 (6)
C23'	0.8349 (13)	0.0747 (18)	−0.0046 (5)	0.095 (6)	0.380 (6)
H23D	0.9048	0.1366	0.0055	0.142*	0.380 (6)
H23E	0.8250	0.0763	−0.0391	0.142*	0.380 (6)
H23F	0.8598	−0.0138	0.0058	0.142*	0.380 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0237 (2)	0.0160 (2)	0.0233 (2)	0.00309 (15)	0.00128 (15)	0.00060 (16)
Ni2	0.0249 (2)	0.0212 (2)	0.0276 (2)	−0.00409 (16)	0.00209 (17)	0.00290 (17)
O1W	0.118 (6)	0.062 (4)	0.048 (4)	0.007 (4)	−0.008 (4)	0.012 (3)
N1	0.0267 (15)	0.0263 (15)	0.0323 (15)	0.0035 (11)	−0.0017 (12)	−0.0028 (12)
N2	0.0302 (16)	0.0263 (15)	0.0281 (15)	0.0010 (12)	0.0012 (12)	0.0024 (12)
N3	0.0300 (15)	0.0219 (14)	0.0262 (14)	0.0001 (11)	−0.0007 (12)	0.0023 (12)
N4	0.0296 (15)	0.0164 (14)	0.0395 (16)	0.0021 (11)	0.0032 (13)	0.0003 (12)
N5	0.0344 (16)	0.0250 (15)	0.0338 (17)	−0.0053 (12)	0.0064 (13)	0.0025 (13)
N6	0.0306 (16)	0.0225 (15)	0.0336 (16)	−0.0002 (12)	0.0029 (12)	0.0012 (12)
N7	0.054 (3)	0.112 (4)	0.053 (2)	−0.006 (2)	−0.0085 (19)	0.040 (3)
N8	0.041 (2)	0.044 (2)	0.091 (3)	−0.0159 (17)	0.0035 (19)	0.000 (2)
C1	0.040 (2)	0.040 (2)	0.0273 (18)	−0.0005 (16)	−0.0068 (15)	−0.0015 (16)
C2	0.038 (2)	0.040 (2)	0.0219 (17)	0.0006 (16)	−0.0022 (15)	0.0066 (15)
C3	0.042 (2)	0.031 (2)	0.0351 (19)	−0.0068 (16)	0.0025 (16)	0.0113 (16)
C4	0.074 (3)	0.078 (4)	0.046 (3)	−0.032 (3)	−0.007 (2)	0.031 (3)
C5	0.036 (2)	0.0317 (19)	0.0353 (19)	−0.0061 (15)	0.0055 (15)	0.0002 (16)
C6	0.0314 (19)	0.0251 (18)	0.0297 (18)	−0.0053 (14)	−0.0007 (14)	0.0002 (14)
C7	0.041 (2)	0.0260 (18)	0.044 (2)	−0.0066 (16)	0.0026 (17)	−0.0060 (16)
C8	0.036 (2)	0.041 (2)	0.048 (2)	−0.0102 (17)	−0.0057 (17)	−0.0059 (18)
C9	0.0248 (18)	0.0279 (19)	0.051 (2)	0.0058 (14)	−0.0082 (16)	−0.0004 (16)
C10	0.038 (2)	0.0198 (18)	0.052 (2)	0.0080 (14)	−0.0071 (17)	0.0012 (16)
C11	0.035 (2)	0.0197 (17)	0.052 (2)	0.0012 (14)	0.0032 (17)	−0.0002 (16)
C12	0.050 (3)	0.0140 (19)	0.105 (4)	0.0030 (17)	0.004 (2)	0.003 (2)
C13	0.035 (2)	0.0240 (18)	0.049 (2)	−0.0072 (15)	0.0056 (17)	−0.0084 (16)
C14	0.0290 (19)	0.0250 (18)	0.042 (2)	−0.0057 (14)	0.0011 (15)	−0.0026 (15)
C15	0.0267 (19)	0.042 (2)	0.054 (2)	−0.0040 (16)	0.0095 (17)	−0.0040 (18)
C16	0.037 (2)	0.054 (3)	0.060 (3)	−0.0094 (19)	−0.0093 (19)	−0.009 (2)
C17	0.0288 (18)	0.0190 (16)	0.0322 (19)	−0.0051 (13)	0.0041 (14)	0.0025 (14)
C18	0.0289 (18)	0.0194 (16)	0.0277 (17)	−0.0032 (14)	0.0011 (14)	0.0053 (13)
C19	0.031 (2)	0.060 (3)	0.042 (2)	−0.0073 (18)	−0.0011 (17)	0.015 (2)
C20	0.034 (2)	0.0273 (19)	0.045 (2)	−0.0002 (15)	0.0024 (16)	0.0038 (16)
O1	0.060 (4)	0.084 (6)	0.049 (4)	0.033 (4)	0.013 (3)	−0.003 (4)
N9	0.060 (5)	0.079 (5)	0.050 (4)	0.013 (4)	0.011 (3)	−0.003 (4)
C21	0.057 (4)	0.080 (5)	0.038 (4)	0.008 (4)	0.008 (3)	−0.007 (4)
C22	0.123 (7)	0.097 (7)	0.080 (6)	0.030 (6)	0.010 (6)	0.015 (5)
C23	0.054 (4)	0.074 (5)	0.064 (5)	−0.004 (4)	0.023 (4)	−0.015 (4)
O1'	0.068 (6)	0.065 (7)	0.057 (6)	0.032 (5)	0.002 (5)	−0.017 (5)
N9'	0.052 (6)	0.053 (6)	0.056 (7)	0.000 (5)	0.018 (5)	−0.023 (5)
C21'	0.047 (6)	0.047 (6)	0.037 (5)	0.005 (5)	−0.002 (4)	−0.004 (5)
C22'	0.113 (10)	0.091 (9)	0.156 (11)	−0.002 (8)	0.022 (8)	−0.014 (8)
C23'	0.084 (8)	0.105 (9)	0.095 (9)	0.017 (7)	0.008 (7)	−0.036 (8)

Geometric parameters (Å, º) top

Ni1—N5	2.076 (3)	C8—H8A	0.9800
Ni1—N6ⁱ	2.091 (3)	C8—H8B	0.9800
Ni1—N2	2.122 (3)	C8—H8C	0.9800
Ni1—N4	2.127 (3)	C9—C10	1.510 (5)
Ni1—N1	2.156 (3)	C9—H9A	0.9900
Ni1—N3	2.161 (3)	C9—H9B	0.9900
Ni2—C17	1.852 (3)	C10—H10A	0.9900
Ni2—C19	1.861 (4)	C10—H10B	0.9900
Ni2—C18	1.863 (3)	C11—C13	1.519 (5)
Ni2—C20	1.879 (4)	C11—C12	1.533 (5)
O1W—H11	0.84	C11—H11A	1.0000
O1W—H12	0.84	C12—H12A	0.9800
N1—C1	1.473 (4)	C12—H12B	0.9800
N1—C14	1.507 (4)	C12—H12C	0.9800
N1—H1	0.88 (3)	C13—C14	1.540 (5)
N2—C2	1.481 (4)	C13—H13A	0.9900
N2—C3	1.490 (4)	C13—H13B	0.9900
N2—H2	0.88 (3)	C14—C15	1.523 (5)
N3—C9	1.467 (4)	C14—C16	1.529 (5)
N3—C6	1.489 (4)	C15—H15A	0.9800
N3—H3	0.87 (3)	C15—H15B	0.9800
N4—C10	1.482 (4)	C15—H15C	0.9800
N4—C11	1.483 (4)	C16—H16A	0.9800
N4—H4	0.88 (3)	C16—H16B	0.9800
N5—C17	1.154 (4)	C16—H16C	0.9800
N6—C18	1.142 (4)	O1—C21	1.233 (7)
N6—Ni1ⁱⁱ	2.091 (3)	N9—C21	1.318 (7)
N7—C19	1.144 (5)	N9—C23	1.440 (7)
N8—C20	1.144 (5)	N9—C22	1.450 (8)
C1—C2	1.504 (5)	C21—H21	0.9500
C1—H1A	0.9900	C22—H22A	0.9800
C1—H1B	0.9900	C22—H22B	0.9800
C2—H2A	0.9900	C22—H22C	0.9800
C2—H2B	0.9900	C23—H23A	0.9800
C3—C5	1.526 (5)	C23—H23B	0.9800
C3—C4	1.537 (5)	C23—H23C	0.9800
C3—H3A	1.0000	O1'—C21'	1.228 (9)
C4—H4A	0.9800	N9'—C21'	1.331 (14)
C4—H4B	0.9800	N9'—C22'	1.422 (9)
C4—H4C	0.9800	N9'—C23'	1.461 (9)
C5—C6	1.532 (5)	C21'—H21B	0.9500
C5—H5A	0.9900	C22'—H22D	0.9800
C5—H5B	0.9900	C22'—H22E	0.9800
C6—C7	1.519 (5)	C22'—H22F	0.9800
C6—C8	1.534 (5)	C23'—H23D	0.9800
C7—H7A	0.9800	C23'—H23E	0.9800
C7—H7B	0.9800	C23'—H23F	0.9800
C7—H7C	0.9800

N5—Ni1—N6ⁱ	87.47 (11)	H7A—C7—H7B	109.5
N5—Ni1—N2	168.80 (11)	C6—C7—H7C	109.5
N6ⁱ—Ni1—N2	88.20 (11)	H7A—C7—H7C	109.5
N5—Ni1—N4	88.68 (11)	H7B—C7—H7C	109.5
N6ⁱ—Ni1—N4	168.73 (11)	C6—C8—H8A	109.5
N2—Ni1—N4	97.42 (11)	C6—C8—H8B	109.5
N5—Ni1—N1	105.64 (11)	H8A—C8—H8B	109.5
N6ⁱ—Ni1—N1	84.45 (11)	C6—C8—H8C	109.5
N2—Ni1—N1	84.20 (11)	H8A—C8—H8C	109.5
N4—Ni1—N1	86.41 (11)	H8B—C8—H8C	109.5
N5—Ni1—N3	84.24 (11)	N3—C9—C10	110.4 (3)
N6ⁱ—Ni1—N3	106.11 (11)	N3—C9—H9A	109.6
N2—Ni1—N3	87.05 (11)	C10—C9—H9A	109.6
N4—Ni1—N3	84.01 (11)	N3—C9—H9B	109.6
N1—Ni1—N3	166.08 (10)	C10—C9—H9B	109.6
C17—Ni2—C19	176.11 (17)	H9A—C9—H9B	108.1
C17—Ni2—C18	89.49 (14)	N4—C10—C9	109.5 (3)
C19—Ni2—C18	88.66 (15)	N4—C10—H10A	109.8
C17—Ni2—C20	89.51 (15)	C9—C10—H10A	109.8
C19—Ni2—C20	92.17 (16)	N4—C10—H10B	109.8
C18—Ni2—C20	177.02 (15)	C9—C10—H10B	109.8
H11—O1W—H12	108.8	H10A—C10—H10B	108.2
C1—N1—C14	114.5 (3)	N4—C11—C13	111.0 (3)
C1—N1—Ni1	104.7 (2)	N4—C11—C12	112.5 (3)
C14—N1—Ni1	121.1 (2)	C13—C11—C12	108.7 (3)
C1—N1—H1	107 (2)	N4—C11—H11A	108.2
C14—N1—H1	105 (2)	C13—C11—H11A	108.2
Ni1—N1—H1	103 (2)	C12—C11—H11A	108.2
C2—N2—C3	112.6 (3)	C11—C12—H12A	109.5
C2—N2—Ni1	104.8 (2)	C11—C12—H12B	109.5
C3—N2—Ni1	115.8 (2)	H12A—C12—H12B	109.5
C2—N2—H2	109 (2)	C11—C12—H12C	109.5
C3—N2—H2	107 (2)	H12A—C12—H12C	109.5
Ni1—N2—H2	107 (2)	H12B—C12—H12C	109.5
C9—N3—C6	114.2 (3)	C11—C13—C14	119.4 (3)
C9—N3—Ni1	104.6 (2)	C11—C13—H13A	107.5
C6—N3—Ni1	120.7 (2)	C14—C13—H13A	107.5
C9—N3—H3	106 (2)	C11—C13—H13B	107.5
C6—N3—H3	107 (2)	C14—C13—H13B	107.5
Ni1—N3—H3	103 (2)	H13A—C13—H13B	107.0
C10—N4—C11	112.3 (3)	N1—C14—C15	107.9 (3)
C10—N4—Ni1	104.9 (2)	N1—C14—C16	110.8 (3)
C11—N4—Ni1	117.6 (2)	C15—C14—C16	108.4 (3)
C10—N4—H4	109 (2)	N1—C14—C13	109.6 (3)
C11—N4—H4	107 (2)	C15—C14—C13	111.1 (3)
Ni1—N4—H4	105 (2)	C16—C14—C13	109.1 (3)
C17—N5—Ni1	159.5 (3)	C14—C15—H15A	109.5
C18—N6—Ni1ⁱⁱ	157.5 (3)	C14—C15—H15B	109.5
N1—C1—C2	110.5 (3)	H15A—C15—H15B	109.5
N1—C1—H1A	109.5	C14—C15—H15C	109.5
C2—C1—H1A	109.5	H15A—C15—H15C	109.5
N1—C1—H1B	109.5	H15B—C15—H15C	109.5
C2—C1—H1B	109.5	C14—C16—H16A	109.5
H1A—C1—H1B	108.1	C14—C16—H16B	109.5
N2—C2—C1	109.8 (3)	H16A—C16—H16B	109.5
N2—C2—H2A	109.7	C14—C16—H16C	109.5
C1—C2—H2A	109.7	H16A—C16—H16C	109.5
N2—C2—H2B	109.7	H16B—C16—H16C	109.5
C1—C2—H2B	109.7	N5—C17—Ni2	173.3 (3)
H2A—C2—H2B	108.2	N6—C18—Ni2	176.8 (3)
N2—C3—C5	111.6 (3)	N7—C19—Ni2	176.8 (4)
N2—C3—C4	112.8 (3)	N8—C20—Ni2	177.1 (4)
C5—C3—C4	107.0 (3)	C21—N9—C23	124.4 (7)
N2—C3—H3A	108.5	C21—N9—C22	117.8 (7)
C5—C3—H3A	108.5	C23—N9—C22	117.8 (7)
C4—C3—H3A	108.5	O1—C21—N9	128.3 (7)
C3—C4—H4A	109.5	O1—C21—H21	115.8
C3—C4—H4B	109.5	N9—C21—H21	115.8
H4A—C4—H4B	109.5	C21'—N9'—C22'	122.3 (11)
C3—C4—H4C	109.5	C21'—N9'—C23'	121.6 (11)
H4A—C4—H4C	109.5	C22'—N9'—C23'	116.1 (13)
H4B—C4—H4C	109.5	O1'—C21'—N9'	123.9 (12)
C3—C5—C6	119.3 (3)	O1'—C21'—H21B	118.0
C3—C5—H5A	107.5	N9'—C21'—H21B	118.0
C6—C5—H5A	107.5	N9'—C22'—H22D	109.5
C3—C5—H5B	107.5	N9'—C22'—H22E	109.5
C6—C5—H5B	107.5	H22D—C22'—H22E	109.5
H5A—C5—H5B	107.0	N9'—C22'—H22F	109.5
N3—C6—C7	108.3 (3)	H22D—C22'—H22F	109.5
N3—C6—C5	110.9 (3)	H22E—C22'—H22F	109.5
C7—C6—C5	111.6 (3)	N9'—C23'—H23D	109.5
N3—C6—C8	110.6 (3)	N9'—C23'—H23E	109.5
C7—C6—C8	107.8 (3)	H23D—C23'—H23E	109.5
C5—C6—C8	107.7 (3)	N9'—C23'—H23F	109.5
C6—C7—H7A	109.5	H23D—C23'—H23F	109.5
C6—C7—H7B	109.5	H23E—C23'—H23F	109.5

N5—Ni1—N1—C1	−173.4 (2)	C14—N1—C1—C2	−174.7 (3)
N6ⁱ—Ni1—N1—C1	100.8 (2)	Ni1—N1—C1—C2	−39.7 (3)
N2—Ni1—N1—C1	12.0 (2)	C3—N2—C2—C1	−170.5 (3)
N4—Ni1—N1—C1	−85.8 (2)	Ni1—N2—C2—C1	−43.8 (3)
N3—Ni1—N1—C1	−39.3 (5)	N1—C1—C2—N2	59.1 (4)
N5—Ni1—N1—C14	−42.2 (3)	C2—N2—C3—C5	−174.4 (3)
N6ⁱ—Ni1—N1—C14	−128.0 (2)	Ni1—N2—C3—C5	65.1 (3)
N2—Ni1—N1—C14	143.3 (2)	C2—N2—C3—C4	−53.9 (4)
N4—Ni1—N1—C14	45.4 (2)	Ni1—N2—C3—C4	−174.4 (3)
N3—Ni1—N1—C14	92.0 (5)	N2—C3—C5—C6	−67.3 (4)
N5—Ni1—N2—C2	−134.8 (5)	C4—C3—C5—C6	168.9 (3)
N6ⁱ—Ni1—N2—C2	−67.6 (2)	C9—N3—C6—C7	−165.2 (3)
N4—Ni1—N2—C2	102.6 (2)	Ni1—N3—C6—C7	68.8 (3)
N1—Ni1—N2—C2	17.0 (2)	C9—N3—C6—C5	72.1 (4)
N3—Ni1—N2—C2	−173.8 (2)	Ni1—N3—C6—C5	−53.9 (3)
N5—Ni1—N2—C3	−10.2 (7)	C9—N3—C6—C8	−47.3 (4)
N6ⁱ—Ni1—N2—C3	57.1 (2)	Ni1—N3—C6—C8	−173.4 (2)
N4—Ni1—N2—C3	−132.7 (2)	C3—C5—C6—N3	59.8 (4)
N1—Ni1—N2—C3	141.7 (2)	C3—C5—C6—C7	−61.0 (4)
N3—Ni1—N2—C3	−49.1 (2)	C3—C5—C6—C8	−179.1 (3)
N5—Ni1—N3—C9	102.4 (2)	C6—N3—C9—C10	−174.9 (3)
N6ⁱ—Ni1—N3—C9	−171.9 (2)	Ni1—N3—C9—C10	−40.9 (3)
N2—Ni1—N3—C9	−84.7 (2)	C11—N4—C10—C9	−172.1 (3)
N4—Ni1—N3—C9	13.1 (2)	Ni1—N4—C10—C9	−43.3 (3)
N1—Ni1—N3—C9	−33.6 (5)	N3—C9—C10—N4	59.6 (4)
N5—Ni1—N3—C6	−127.3 (2)	C10—N4—C11—C13	−174.0 (3)
N6ⁱ—Ni1—N3—C6	−41.6 (2)	Ni1—N4—C11—C13	64.1 (3)
N2—Ni1—N3—C6	45.6 (2)	C10—N4—C11—C12	−52.0 (4)
N4—Ni1—N3—C6	143.4 (2)	Ni1—N4—C11—C12	−173.8 (3)
N1—Ni1—N3—C6	96.7 (5)	N4—C11—C13—C14	−67.8 (4)
N5—Ni1—N4—C10	−68.0 (2)	C12—C11—C13—C14	168.0 (3)
N6ⁱ—Ni1—N4—C10	−138.0 (5)	C1—N1—C14—C15	−167.1 (3)
N2—Ni1—N4—C10	102.6 (2)	Ni1—N1—C14—C15	66.0 (3)
N1—Ni1—N4—C10	−173.8 (2)	C1—N1—C14—C16	−48.6 (4)
N3—Ni1—N4—C10	16.3 (2)	Ni1—N1—C14—C16	−175.5 (2)
N5—Ni1—N4—C11	57.5 (3)	C1—N1—C14—C13	71.8 (4)
N6ⁱ—Ni1—N4—C11	−12.5 (7)	Ni1—N1—C14—C13	−55.1 (3)
N2—Ni1—N4—C11	−131.9 (3)	C11—C13—C14—N1	61.6 (4)
N1—Ni1—N4—C11	−48.2 (3)	C11—C13—C14—C15	−57.6 (4)
N3—Ni1—N4—C11	141.9 (3)	C11—C13—C14—C16	−177.0 (3)
N6ⁱ—Ni1—N5—C17	−117.1 (8)	C23—N9—C21—O1	179.4 (4)
N2—Ni1—N5—C17	−49.8 (11)	C22—N9—C21—O1	0.2 (4)
N4—Ni1—N5—C17	73.5 (8)	C22'—N9'—C21'—O1'	0.4 (4)
N1—Ni1—N5—C17	159.3 (8)	C23'—N9'—C21'—O1'	180.0 (3)
N3—Ni1—N5—C17	−10.7 (8)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···N7	0.84	2.01	2.825 (8)	163
N1—H1···N6ⁱ	0.88 (3)	2.49 (3)	2.854 (4)	105 (3)
N2—H2···O1	0.88 (3)	2.46 (2)	3.278 (7)	156 (3)
N2—H2···O1′	0.88 (3)	2.05 (2)	2.88 (1)	158 (3)
N3—H3···N5	0.87 (3)	2.48 (3)	2.843 (4)	106 (3)
N4—H4···O1	0.88 (3)	2.08 (2)	2.927 (8)	162 (3)
N4—H4···O1′	0.88 (3)	2.30 (2)	3.14 (1)	160 (3)

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Ni₂(CN)₄(C₁₆H₃₆N₄)]·C₃H₇NO·0.5H₂O
M_r	588.09
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	10.0122 (5), 10.2109 (5), 28.3246 (15)
β (°)	91.468 (1)
V (Å³)	2894.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.33
Crystal size (mm)	0.40 × 0.35 × 0.15

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.617, 0.825
No. of measured, independent and observed [I > 2σ(I)] reflections	14236, 6181, 4435
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.121, 1.03
No. of reflections	6181
No. of parameters	393
No. of restraints	76
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.39

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···N7	0.84	2.01	2.825 (8)	163
N1—H1···N6ⁱ	0.88 (3)	2.49 (3)	2.854 (4)	105 (3)
N2—H2···O1	0.88 (3)	2.46 (2)	3.278 (7)	156 (3)
N2—H2···O1'	0.88 (3)	2.05 (2)	2.88 (1)	158 (3)
N3—H3···N5	0.87 (3)	2.48 (3)	2.843 (4)	106 (3)
N4—H4···O1	0.88 (3)	2.08 (2)	2.927 (8)	162 (3)
N4—H4···O1'	0.88 (3)	2.30 (2)	3.14 (1)	160 (3)

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

Acknowledgements

We thank the Scientific Research Fund of Hunan Provincial Education Department (10 C0730) and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2003). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jiang, L., Feng, X.-L., Su, C.-Y., Chen, X.-M. & Lu, T.-B. (2007). Inorg. Chem. 46, 2637–2644. Web of Science CSD CrossRef PubMed CAS Google Scholar
Jiang, L., Lu, T.-B. & Feng, X.-L. (2005). Inorg. Chem. 44, 7056–7062. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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