Dichlorido(dimethyl-formamide-κO)[1,4,7-tris-(2-cyano-ethyl)-1,4,7-triaza-cyclo-nonane-κN,N,N]nickel(II).

The title complex, [NiCl(2)(C(15)H(24)N(6))(C(3)H(7)NO)], is isomorphous with the Co(II) analogue. Three N-atom donors from the facially coordinating triaza macrocyclic ligand, one O-atom donor from dimethyl-formamide and two Cl(-) anions surround the Ni(II) ion in a distorted octa-hedral coordination geometry. Inter-molecular C-H⋯Cl and C-H⋯N hydrogen-bonding inter-actions link the complex mol-ecules into a three-dimensional supra-molecular 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 = 491.11

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.115

S = 1.00

4616 reflections

265 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.48 e Å−3

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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[NiCl2(C15H24N6)(C3H7NO)]	F000 = 1032
Mr = 491.11	Dx = 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 = 2.4–23.0º
b = 19.698 (2) Å	µ = 1.07 mm−1
c = 12.3504 (13) Å	T = 298 (2) K
β = 97.676 (2)º	Cell measurement pressure: 101(2) kPa
V = 2354.5 (4) Å3	Block, green
Z = 4	0.32 × 0.24 × 0.22 mm

Bruker SMART APEX CCD area-detector diffractometer	4616 independent reflections
Radiation source: sealed tube	3371 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.050
T = 298(2) K	θmax = 26.0º
ω and φ scans	θmin = 2.0º
Absorption correction: multi-scan(SADABS; Bruker, 2000)	h = −12→12
Tmin = 0.725, Tmax = 0.798	k = −24→19
12684 measured reflections	l = −14→15

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053	H-atom parameters constrained
wR(F2) = 0.115	w = 1/[σ2(Fo2) + (0.05P)2 + 1.55P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
4616 reflections	Δρmax = 0.32 e Å−3
265 parameters	Δρmin = −0.48 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

	x	y	z	Uiso*/Ueq
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)

	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)

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

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

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) ; (ii) ; (iii) .