Dichlorido(dimethyl­formamide-κO)[1,4,7-tris­(2-cyano­ethyl)-1,4,7-triaza­cyclo­nonane-κ3N1,N4,N7]nickel(II)

Zhang, Z.; Wu, L.-Z.; Geng, Z.-R.; Wang, Z.-L.

doi:10.1107/S1600536808024422

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Pages m1114-m1115

doi:10.1107/S1600536808024422

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Dichlorido(dimethylformamide-κO)[1,4,7-tris(2-cyanoethyl)-1,4,7-triazacyclononane-κ³N¹,N⁴,N⁷]nickel(II)

Zhong Zhang,^a Li-Zhen Wu,^a Zhi-Rong Geng ^a and Zhi-Lin Wang ^a ^*

^aCoordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: zzkltl@yahoo.com.cn

(Received 9 July 2008; accepted 30 July 2008; online 6 August 2008)

The title complex, [NiCl₂(C₁₅H₂₄N₆)(C₃H₇NO)], is isomorphous with the Co^II analogue. Three N-atom donors from the facially coordinating triaza macrocyclic ligand, one O-atom donor from dimethylformamide and two Cl⁻ anions surround the Ni^II ion in a distorted octahedral coordination geometry. Intermolecular C—H⋯Cl and C—H⋯N hydrogen-bonding interactions link the complex molecules into a three-dimensional supramolecular architecture.

Related literature

For related literature, see: Graham et al. (2005 ); Li et al. (2005 ); Schlager et al. (1995 ); Tei et al. (1998 and 2003 ). For the isostructural Co complex, see: Zhang et al. (2008 ).

Experimental

Crystal data

[NiCl₂(C₁₅H₂₄N₆)(C₃H₇NO)]
M_r = 491.11
Monoclinic, P 2₁ /n
a = 9.7657 (10) Å
b = 19.698 (2) Å
c = 12.3504 (13) Å
β = 97.676 (2)°
V = 2354.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 298 (2) K
0.32 × 0.24 × 0.22 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.725, T_max = 0.798
12684 measured reflections
4616 independent reflections
3371 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.115
S = 1.00
4616 reflections
265 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cl1—Ni1	2.4315 (10)
Cl2—Ni1	2.4158 (10)
N1—Ni1	2.180 (3)
N2—Ni1	2.134 (3)
N3—Ni1	2.144 (3)
Ni1—O1	2.093 (2)

O1—Ni1—N2	88.31 (10)
O1—Ni1—N3	170.81 (11)
N2—Ni1—N3	83.12 (11)
O1—Ni1—N1	92.12 (10)
N2—Ni1—N1	83.15 (11)
N3—Ni1—N1	83.59 (11)
O1—Ni1—Cl2	89.34 (7)
N2—Ni1—Cl2	175.06 (8)
N3—Ni1—Cl2	98.94 (8)
N1—Ni1—Cl2	92.60 (8)
O1—Ni1—Cl1	90.90 (7)
N2—Ni1—Cl1	93.35 (8)
N3—Ni1—Cl1	92.91 (8)
N1—Ni1—Cl1	175.31 (8)
Cl2—Ni1—Cl1	91.02 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cl2ⁱ	0.97	2.76	3.667 (4)	156
C3—H3A⋯Cl2ⁱ	0.97	2.80	3.756 (4)	168
C11—H11A⋯Cl1ⁱ	0.97	2.66	3.565 (4)	155
C11—H11B⋯Cl2ⁱⁱ	0.97	2.65	3.497 (4)	146
C18—H18B⋯N5ⁱⁱⁱ	0.96	2.55	3.445 (7)	155
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) -x+1, -y+2, -z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808024422/bh2184sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024422/bh2184Isup2.hkl

checkCIF report

Comment top

1,4,7-Triazacyclononane ([9]aneN₃) derivatives with nitrile pendant arms have attracted much interest since these triazamacrocyclic ligands can promote the assembly of multi-dimensional polymeric compounds with Ag^I (Tei et al., 1998). However, these triazamacrocyclic ligands exhibit different coordination behaviors when coordinating to Cu^II and only mononuclear Cu^II complexes of these ligands can be obtained, where the nitrile pendant arms are not involved in the metal coordination (Tei et al., 2003). Herein, we report the synthesis and crystal structure of a monomeric Ni^II complex containing 1,4,7-tris(2-cyanoethyl)-1,4,7-triazacyclononane, (I), which is isostructural to its cobalt-containing analogue (Zhang et al., 2008).

As depicted in Fig. 1, the Ni^II ion in this complex is ligated by a [N₃OCl₂] donor set consisting of three N atoms from the [9]aneN₃ backbone, an O atom from a dimethylformamide molecule and two Cl^- anions. The twist angle is ca. 57.6° (Schlager et al. 1995), indicating that the coordination geometry around Ni^II is slightly distorted from regular octahedral. All bond lengths around Ni^II ion (Table 1) are comparable to those observed in related Ni^II complexes (Graham et al. 2005; Li et al. 2005). Pendant 2-cyanoethyl groups attached to the [9]aneN₃ framework are not involved in the coordination to the Ni^II center and point away from the macrocyclic cavity.

Two coordinated Cl^- anions participate in the formation of multiple C—H···Cl hydrogen bonds (Table 2), which serve to link the complexes into two-dimensional sheets parallel to (010). These sheets are further connected through C—H···N hydrogen bonds, generating a three-dimensional supramolecular network (Fig. 2).

Related literature top

For related literature, see: Graham et al. (2005); Li et al. (2005); Schlager et al. (1995); Tei et al. (1998 and 2003). For the isostructural Co complex, see: Zhang et al. (2008).

Experimental top

The triazamacrocyclic ligand 1,4,7-tris(2-cyanoethyl)-1,4,7-triazacyclononane was prepared following a literature procedure (Tei et al., 1998). A mixture of the triazamacrocyclic ligand (29 mg, 0.1 mmol) and NiCl₂.6H₂O (24 mg, 0.1 mmol) in MeOH (10 ml) was refluxed for 2 h. The precipitated green solid was filtered off and subsequently dissolved in dimethylformamide. Green single crystals of (I) suitable for X-ray diffraction analysis were obtained by slow diffusion of diethyl ether into the dimethylformamide solution. (yield: 31 mg, 63.2%). Analysis: found C 43.87, H 6.53, N 20.04%; calculated for C₁₈H₃₁Cl₂N₇NiO C 44.02, H 6.36, N 19.97%.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 30% probability level (arbitrary radii spheres for H atoms).
	Fig. 2. Packing diagram of the title compound, showing the three-dimensional network formed through intermolecular C—H···Cl and C—H···N hydrogen bonds (dashed lines). For clarity, H atoms not involved in hydrogen bonding have been omitted.

Dichlorido(dimethylformamide-κO)[1,4,7-tris(2-cyanoethyl)-1,4,7- triazacyclononane-κ³N¹,N⁴,N⁷]nickel(II) top

Crystal data top

[NiCl₂(C₁₅H₂₄N₆)(C₃H₇NO)]	F(000) = 1032
M_r = 491.11	D_x = 1.385 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2569 reflections
a = 9.7657 (10) Å	θ = 2.4–23.0°
b = 19.698 (2) Å	µ = 1.07 mm⁻¹
c = 12.3504 (13) Å	T = 298 K
β = 97.676 (2)°	Block, green
V = 2354.5 (4) Å³	0.32 × 0.24 × 0.22 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4616 independent reflections
Radiation source: sealed tube	3371 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω and ϕ scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→12
T_min = 0.725, T_max = 0.798	k = −24→19
12684 measured reflections	l = −14→15

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.05P)² + 1.55P] where P = (F_o² + 2F_c²)/3
4616 reflections	(Δ/σ)_max < 0.001
265 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³
0 constraints

Crystal data top

[NiCl₂(C₁₅H₂₄N₆)(C₃H₇NO)]	V = 2354.5 (4) Å³
M_r = 491.11	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.7657 (10) Å	µ = 1.07 mm⁻¹
b = 19.698 (2) Å	T = 298 K
c = 12.3504 (13) Å	0.32 × 0.24 × 0.22 mm
β = 97.676 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4616 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3371 reflections with I > 2σ(I)
T_min = 0.725, T_max = 0.798	R_int = 0.050
12684 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.01	Δρ_max = 0.32 e Å⁻³
4616 reflections	Δρ_min = −0.48 e Å⁻³
265 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.2245 (3)	0.82135 (19)	0.3865 (3)	0.0332 (8)
H1A	0.2389	0.7806	0.4307	0.040*
H1B	0.2251	0.8599	0.4355	0.040*
C2	0.3401 (4)	0.8287 (2)	0.3188 (3)	0.0362 (8)
H2B	0.4277	0.8238	0.3654	0.043*
H2A	0.3371	0.8738	0.2870	0.043*
C3	0.3526 (4)	0.70715 (18)	0.2734 (3)	0.0349 (8)
H3A	0.3479	0.7078	0.3514	0.042*
H3B	0.4437	0.6912	0.2624	0.042*
C4	0.2440 (4)	0.65873 (18)	0.2181 (3)	0.0366 (8)
H4A	0.2621	0.6501	0.1440	0.044*
H4B	0.2503	0.6158	0.2571	0.044*
C5	0.0623 (4)	0.69268 (18)	0.3255 (3)	0.0366 (8)
H5A	0.1427	0.6852	0.3792	0.044*
H5B	−0.0044	0.6574	0.3349	0.044*
C6	0.0012 (4)	0.75946 (19)	0.3469 (3)	0.0343 (8)
H6B	−0.0091	0.7626	0.4238	0.041*
H6A	−0.0901	0.7628	0.3053	0.041*
C7	0.0122 (4)	0.88213 (18)	0.3182 (3)	0.0342 (8)
H7A	−0.0541	0.8841	0.2524	0.041*
H7B	0.0780	0.9185	0.3136	0.041*
C8	−0.0650 (4)	0.8969 (2)	0.4150 (3)	0.0414 (9)
H8A	−0.1106	0.9405	0.4029	0.050*
H8B	−0.1364	0.8628	0.4164	0.050*
C9	0.0205 (5)	0.8984 (2)	0.5247 (4)	0.0558 (12)
C10	0.4296 (4)	0.7914 (2)	0.1522 (3)	0.0368 (8)
H10A	0.3966	0.8310	0.1097	0.044*
H10B	0.4280	0.7535	0.1019	0.044*
C11	0.5811 (4)	0.8044 (2)	0.2007 (3)	0.0421 (9)
H11A	0.6035	0.7764	0.2651	0.051*
H11B	0.6408	0.7907	0.1478	0.051*
C12	0.6089 (4)	0.8739 (2)	0.2298 (4)	0.0464 (10)
C13	0.0002 (4)	0.64777 (18)	0.1412 (3)	0.0399 (9)
H13A	0.0219	0.6536	0.0674	0.048*
H13B	−0.0894	0.6685	0.1440	0.048*
C14	−0.0142 (5)	0.5712 (2)	0.1616 (4)	0.0497 (10)
H14A	−0.0132	0.5635	0.2393	0.060*
H14B	−0.1026	0.5558	0.1247	0.060*
C15	0.0981 (5)	0.5304 (2)	0.1224 (4)	0.0562 (12)
C16	0.1301 (4)	0.90640 (19)	0.0180 (3)	0.0386 (9)
H16	0.0691	0.8790	−0.0269	0.046*
C17	0.2656 (6)	1.0076 (3)	0.0392 (4)	0.0698 (16)
H17A	0.2512	1.0069	0.1145	0.105*
H17B	0.2524	1.0529	0.0111	0.105*
H17C	0.3580	0.9929	0.0330	0.105*
C18	0.1201 (6)	0.9843 (3)	−0.1349 (4)	0.0695 (15)
H18A	0.0661	0.9484	−0.1718	0.104*
H18B	0.1977	0.9938	−0.1726	0.104*
H18C	0.0641	1.0243	−0.1339	0.104*
Cl1	0.17488 (9)	0.74622 (4)	−0.02223 (7)	0.0322 (2)
Cl2	−0.11545 (8)	0.80646 (4)	0.07904 (7)	0.0317 (2)
N1	0.0873 (3)	0.81727 (13)	0.3173 (2)	0.0270 (6)
N2	0.3315 (3)	0.77684 (15)	0.2292 (2)	0.0330 (7)
N3	0.1036 (3)	0.68642 (15)	0.2155 (2)	0.0329 (6)
N4	0.0800 (4)	0.8977 (2)	0.6093 (3)	0.0572 (10)
N5	0.6267 (4)	0.9299 (2)	0.2485 (3)	0.0616 (11)
N6	0.1815 (4)	0.4987 (2)	0.0903 (3)	0.0617 (11)
N7	0.1697 (4)	0.96334 (18)	−0.0217 (3)	0.0538 (10)
Ni1	0.12289 (5)	0.78712 (2)	0.15350 (4)	0.03039 (14)
O1	0.1693 (3)	0.88679 (12)	0.11226 (19)	0.0358 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0328 (19)	0.042 (2)	0.0252 (18)	0.0027 (15)	0.0034 (14)	−0.0026 (15)
C2	0.0270 (17)	0.048 (2)	0.032 (2)	0.0031 (15)	−0.0006 (14)	−0.0051 (16)
C3	0.0298 (18)	0.042 (2)	0.0324 (19)	0.0158 (15)	0.0016 (14)	0.0045 (16)
C4	0.054 (2)	0.0288 (18)	0.0279 (19)	0.0061 (16)	0.0081 (16)	0.0058 (15)
C5	0.048 (2)	0.0265 (18)	0.037 (2)	−0.0006 (15)	0.0106 (17)	0.0025 (15)
C6	0.0291 (18)	0.040 (2)	0.034 (2)	−0.0007 (15)	0.0077 (15)	0.0037 (16)
C7	0.043 (2)	0.0294 (19)	0.0311 (19)	0.0040 (15)	0.0103 (16)	−0.0047 (15)
C8	0.045 (2)	0.043 (2)	0.038 (2)	0.0070 (17)	0.0135 (17)	−0.0058 (17)
C9	0.068 (3)	0.063 (3)	0.042 (3)	−0.014 (2)	0.027 (2)	−0.018 (2)
C10	0.0333 (19)	0.050 (2)	0.0278 (19)	−0.0001 (16)	0.0079 (15)	−0.0020 (16)
C11	0.0308 (19)	0.066 (3)	0.032 (2)	0.0045 (18)	0.0121 (16)	0.0035 (18)
C12	0.031 (2)	0.049 (3)	0.061 (3)	−0.0012 (18)	0.0136 (18)	0.002 (2)
C13	0.041 (2)	0.029 (2)	0.048 (2)	−0.0078 (16)	0.0020 (17)	0.0043 (16)
C14	0.057 (3)	0.040 (2)	0.054 (3)	−0.0087 (19)	0.013 (2)	−0.0047 (19)
C15	0.049 (3)	0.042 (2)	0.075 (3)	0.004 (2)	−0.003 (2)	−0.021 (2)
C16	0.043 (2)	0.039 (2)	0.035 (2)	−0.0012 (16)	0.0080 (17)	0.0145 (16)
C17	0.079 (4)	0.061 (3)	0.061 (3)	−0.036 (3)	−0.020 (3)	0.020 (2)
C18	0.074 (3)	0.068 (3)	0.062 (3)	−0.012 (3)	−0.006 (3)	0.035 (3)
Cl1	0.0318 (4)	0.0364 (5)	0.0285 (4)	0.0003 (3)	0.0045 (3)	−0.0005 (3)
Cl2	0.0306 (4)	0.0356 (4)	0.0287 (4)	0.0001 (3)	0.0038 (3)	−0.0004 (3)
N1	0.0264 (14)	0.0266 (14)	0.0287 (15)	0.0040 (11)	0.0064 (11)	0.0023 (11)
N2	0.0238 (15)	0.0357 (17)	0.0401 (18)	−0.0016 (12)	0.0066 (12)	−0.0054 (13)
N3	0.0339 (15)	0.0323 (16)	0.0330 (16)	−0.0026 (12)	0.0057 (12)	0.0018 (13)
N4	0.059 (2)	0.074 (3)	0.041 (2)	−0.003 (2)	0.0162 (18)	−0.0245 (19)
N5	0.058 (2)	0.063 (3)	0.071 (3)	−0.016 (2)	0.034 (2)	−0.020 (2)
N6	0.070 (3)	0.055 (2)	0.060 (3)	0.010 (2)	0.009 (2)	−0.0248 (19)
N7	0.070 (2)	0.045 (2)	0.045 (2)	−0.0092 (18)	0.0022 (18)	0.0168 (17)
Ni1	0.0296 (2)	0.0339 (3)	0.0277 (2)	−0.00010 (18)	0.00394 (17)	0.00023 (19)
O1	0.0419 (14)	0.0377 (14)	0.0267 (13)	−0.0016 (11)	0.0002 (11)	0.0069 (11)

Geometric parameters (Å, º) top

C1—N1	1.492 (4)	C10—H10A	0.9700
C1—C2	1.499 (5)	C10—H10B	0.9700
C1—H1A	0.9700	C11—C12	1.433 (6)
C1—H1B	0.9700	C11—H11A	0.9700
C2—N2	1.500 (5)	C11—H11B	0.9700
C2—H2B	0.9700	C12—N5	1.134 (6)
C2—H2A	0.9700	C13—N3	1.480 (5)
C3—N2	1.482 (5)	C13—C14	1.538 (5)
C3—C4	1.518 (5)	C13—H13A	0.9700
C3—H3A	0.9700	C13—H13B	0.9700
C3—H3B	0.9700	C14—C15	1.491 (6)
C4—N3	1.473 (5)	C14—H14A	0.9700
C4—H4A	0.9700	C14—H14B	0.9700
C4—H4B	0.9700	C15—N6	1.139 (6)
C5—N3	1.473 (5)	C16—O1	1.238 (4)
C5—C6	1.483 (5)	C16—N7	1.304 (5)
C5—H5A	0.9700	C16—H16	0.9300
C5—H5B	0.9700	C17—N7	1.419 (6)
C6—N1	1.490 (4)	C17—H17A	0.9600
C6—H6B	0.9700	C17—H17B	0.9600
C6—H6A	0.9700	C17—H17C	0.9600
C7—N1	1.474 (4)	C18—N7	1.476 (6)
C7—C8	1.524 (5)	C18—H18A	0.9600
C7—H7A	0.9700	C18—H18B	0.9600
C7—H7B	0.9700	C18—H18C	0.9600
C8—C9	1.493 (6)	Cl1—Ni1	2.4315 (10)
C8—H8A	0.9700	Cl2—Ni1	2.4158 (10)
C8—H8B	0.9700	N1—Ni1	2.180 (3)
C9—N4	1.126 (6)	N2—Ni1	2.134 (3)
C10—N2	1.466 (4)	N3—Ni1	2.144 (3)
C10—C11	1.541 (5)	Ni1—O1	2.093 (2)

N1—C1—C2	111.8 (3)	C14—C13—H13A	107.8
N1—C1—H1A	109.3	N3—C13—H13B	107.8
C2—C1—H1A	109.3	C14—C13—H13B	107.8
N1—C1—H1B	109.3	H13A—C13—H13B	107.1
C2—C1—H1B	109.3	C15—C14—C13	112.9 (4)
H1A—C1—H1B	107.9	C15—C14—H14A	109.0
C1—C2—N2	111.9 (3)	C13—C14—H14A	109.0
C1—C2—H2B	109.2	C15—C14—H14B	109.0
N2—C2—H2B	109.2	C13—C14—H14B	109.0
C1—C2—H2A	109.2	H14A—C14—H14B	107.8
N2—C2—H2A	109.2	N6—C15—C14	178.3 (5)
H2B—C2—H2A	107.9	O1—C16—N7	123.5 (4)
N2—C3—C4	111.2 (3)	O1—C16—H16	118.2
N2—C3—H3A	109.4	N7—C16—H16	118.2
C4—C3—H3A	109.4	N7—C17—H17A	109.5
N2—C3—H3B	109.4	N7—C17—H17B	109.5
C4—C3—H3B	109.4	H17A—C17—H17B	109.5
H3A—C3—H3B	108.0	N7—C17—H17C	109.5
N3—C4—C3	111.7 (3)	H17A—C17—H17C	109.5
N3—C4—H4A	109.3	H17B—C17—H17C	109.5
C3—C4—H4A	109.3	N7—C18—H18A	109.5
N3—C4—H4B	109.3	N7—C18—H18B	109.5
C3—C4—H4B	109.3	H18A—C18—H18B	109.5
H4A—C4—H4B	107.9	N7—C18—H18C	109.5
N3—C5—C6	113.9 (3)	H18A—C18—H18C	109.5
N3—C5—H5A	108.8	H18B—C18—H18C	109.5
C6—C5—H5A	108.8	C7—N1—C6	111.3 (3)
N3—C5—H5B	108.8	C7—N1—C1	111.0 (3)
C6—C5—H5B	108.8	C6—N1—C1	113.2 (3)
H5A—C5—H5B	107.7	C7—N1—Ni1	112.6 (2)
C5—C6—N1	112.3 (3)	C6—N1—Ni1	100.7 (2)
C5—C6—H6B	109.1	C1—N1—Ni1	107.69 (19)
N1—C6—H6B	109.1	C10—N2—C3	110.5 (3)
C5—C6—H6A	109.1	C10—N2—C2	111.6 (3)
N1—C6—H6A	109.1	C3—N2—C2	111.5 (3)
H6B—C6—H6A	107.9	C10—N2—Ni1	111.5 (2)
N1—C7—C8	118.1 (3)	C3—N2—Ni1	109.1 (2)
N1—C7—H7A	107.8	C2—N2—Ni1	102.4 (2)
C8—C7—H7A	107.8	C4—N3—C5	112.3 (3)
N1—C7—H7B	107.8	C4—N3—C13	112.3 (3)
C8—C7—H7B	107.8	C5—N3—C13	111.5 (3)
H7A—C7—H7B	107.1	C4—N3—Ni1	103.0 (2)
C9—C8—C7	116.1 (3)	C5—N3—Ni1	107.4 (2)
C9—C8—H8A	108.3	C13—N3—Ni1	109.9 (2)
C7—C8—H8A	108.3	C16—N7—C17	122.5 (4)
C9—C8—H8B	108.3	C16—N7—C18	121.4 (4)
C7—C8—H8B	108.3	C17—N7—C18	116.1 (4)
H8A—C8—H8B	107.4	O1—Ni1—N2	88.31 (10)
N4—C9—C8	176.6 (5)	O1—Ni1—N3	170.81 (11)
N2—C10—C11	117.2 (3)	N2—Ni1—N3	83.12 (11)
N2—C10—H10A	108.0	O1—Ni1—N1	92.12 (10)
C11—C10—H10A	108.0	N2—Ni1—N1	83.15 (11)
N2—C10—H10B	108.0	N3—Ni1—N1	83.59 (11)
C11—C10—H10B	108.0	O1—Ni1—Cl2	89.34 (7)
H10A—C10—H10B	107.2	N2—Ni1—Cl2	175.06 (8)
C12—C11—C10	113.4 (3)	N3—Ni1—Cl2	98.94 (8)
C12—C11—H11A	108.9	N1—Ni1—Cl2	92.60 (8)
C10—C11—H11A	108.9	O1—Ni1—Cl1	90.90 (7)
C12—C11—H11B	108.9	N2—Ni1—Cl1	93.35 (8)
C10—C11—H11B	108.9	N3—Ni1—Cl1	92.91 (8)
H11A—C11—H11B	107.7	N1—Ni1—Cl1	175.31 (8)
N5—C12—C11	176.7 (5)	Cl2—Ni1—Cl1	91.02 (3)
N3—C13—C14	118.2 (3)	C16—O1—Ni1	118.2 (2)
N3—C13—H13A	107.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl2ⁱ	0.97	2.76	3.667 (4)	156
C2—H2A···O1	0.97	2.54	3.076 (5)	115
C3—H3A···Cl2ⁱ	0.97	2.80	3.756 (4)	168
C7—H7A···Cl2	0.97	2.63	3.394 (4)	135
C10—H10A···O1	0.97	2.48	3.147 (5)	126
C10—H10B···Cl1	0.97	2.73	3.192 (4)	110
C11—H11A···Cl1ⁱ	0.97	2.66	3.565 (4)	155
C11—H11B···Cl2ⁱⁱ	0.97	2.65	3.497 (4)	146
C13—H13A···Cl1	0.97	2.69	3.415 (4)	132
C16—H16···Cl1	0.93	2.81	3.233 (4)	109
C16—H16···Cl2	0.93	2.76	3.268 (4)	115
C18—H18B···N5ⁱⁱⁱ	0.96	2.55	3.445 (7)	155

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x+1, y, z; (iii) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[NiCl₂(C₁₅H₂₄N₆)(C₃H₇NO)]
M_r	491.11
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.7657 (10), 19.698 (2), 12.3504 (13)
β (°)	97.676 (2)
V (Å³)	2354.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.07
Crystal size (mm)	0.32 × 0.24 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.725, 0.798
No. of measured, independent and observed [I > 2σ(I)] reflections	12684, 4616, 3371
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.115, 1.01
No. of reflections	4616
No. of parameters	265
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.48

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997).

Selected geometric parameters (Å, º) top

Cl1—Ni1	2.4315 (10)	N2—Ni1	2.134 (3)
Cl2—Ni1	2.4158 (10)	N3—Ni1	2.144 (3)
N1—Ni1	2.180 (3)	Ni1—O1	2.093 (2)

O1—Ni1—N2	88.31 (10)	N3—Ni1—Cl2	98.94 (8)
O1—Ni1—N3	170.81 (11)	N1—Ni1—Cl2	92.60 (8)
N2—Ni1—N3	83.12 (11)	O1—Ni1—Cl1	90.90 (7)
O1—Ni1—N1	92.12 (10)	N2—Ni1—Cl1	93.35 (8)
N2—Ni1—N1	83.15 (11)	N3—Ni1—Cl1	92.91 (8)
N3—Ni1—N1	83.59 (11)	N1—Ni1—Cl1	175.31 (8)
O1—Ni1—Cl2	89.34 (7)	Cl2—Ni1—Cl1	91.02 (3)
N2—Ni1—Cl2	175.06 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl2ⁱ	0.97	2.76	3.667 (4)	156
C3—H3A···Cl2ⁱ	0.97	2.80	3.756 (4)	168
C11—H11A···Cl1ⁱ	0.97	2.66	3.565 (4)	155
C11—H11B···Cl2ⁱⁱ	0.97	2.65	3.497 (4)	146
C18—H18B···N5ⁱⁱⁱ	0.96	2.55	3.445 (7)	155

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x+1, y, z; (iii) −x+1, −y+2, −z.

Acknowledgements

This project was supported by the National Natural Science Foundation of China (grant No. 20475026).

References

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