Hexakis(1H-imidazole-κN3)nickel(II) bis­(2,4-dibromo-6-formyl­phenolate) N,N-dimethyl­formamide disolvate

Ding, Y.; Li, C.

doi:10.1107/S1600536808018989

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m968

doi:10.1107/S1600536808018989

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Hexakis(1H-imidazole-κN³)nickel(II) bis(2,4-dibromo-6-formylphenolate) N,N-dimethylformamide disolvate

Yu Ding ^a ^* and Chunlian Li ^a

^aDepartment of Chemistry, Xiaogan University, Xiaogan, Hubei 432000, People's Republic of China
^*Correspondence e-mail: dy9802@126.com

(Received 15 April 2008; accepted 23 June 2008; online 28 June 2008)

In the cation of the title compound, [Ni(C₃H₄N₂)₆](C₇H₃Br₂O₂)₂·2C₃H₇NO, the Ni^II ion lies on an inversion center and is coordinated in a slightly distorted octahedral environment by six N atoms from six imidazole ligands. In the crystal structure, cations, anions and solvent molecules are linked by intermolecular N—H⋯O hydrogen bonds into one-dimensional chains along [010]. In addition, the crystal structure is stabilized by weak C—H⋯O and C—H⋯N hydrogen bonds.

Related literature

For related literature, see: Gelman et al. (2002 ).

Experimental

Crystal data

[Ni(C₃H₄N₂)₆](C₇H₃Br₂O₂)₂·2C₃H₇NO
M_r = 1171.22
Monoclinic, P 2₁ /c
a = 14.7271 (13) Å
b = 9.0221 (8) Å
c = 18.1143 (16) Å
β = 100.408 (2)°
V = 2367.2 (4) Å³
Z = 2
Mo Kα radiation
μ = 3.84 mm⁻¹
T = 292 (2) K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.308, T_max = 0.392 (expected range = 0.365–0.464)
13477 measured reflections
5147 independent reflections
3646 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.113
S = 1.01
5147 reflections
288 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ni1—N5	2.121 (2)
Ni1—N3	2.128 (2)
Ni1—N1	2.138 (2)

N5—Ni1—N5ⁱ	180
N5—Ni1—N3ⁱ	91.41 (9)
N5—Ni1—N3	88.59 (9)
N3ⁱ—Ni1—N3	180
N5—Ni1—N1ⁱ	89.86 (9)
N3—Ni1—N1ⁱ	91.48 (9)
N5—Ni1—N1	90.14 (9)
N3—Ni1—N1	88.52 (9)
N1ⁱ—Ni1—N1	180
Symmetry code: (i) -x+1, -y, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3ⁱⁱ	0.86	1.92	2.764 (5)	169
N4—H4A⋯O2ⁱⁱⁱ	0.86	1.85	2.703 (3)	170
N6—H6A⋯O2^iv	0.86	1.97	2.772 (3)	155
C7—H7⋯N1ⁱ	0.93	2.57	3.076 (4)	115
C8—H8⋯O1^v	0.93	2.59	3.264 (5)	130
C3—H3⋯N3	0.93	2.57	3.053 (4)	113
Symmetry codes: (i) -x+1, -y, -z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018989/lh2618sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018989/lh2618Isup2.hkl

checkCIF report

Comment top

Due to the weak coordination strength of dibromosalicylaldehydenate anions with transition metals, the dibromosalicylaldehydenate usually acts as the counterbalance of the charge. Herein, we report the crystal structure of such a compound, [Ni(Im)₆](DBSH)₂ 2DMF, (I), (Im = imidazole; H₂DBSH =3,5-dibromosalicylaldehyde; DMF =N,N-dimethylformamide). The molecular structure of (I) is shown in Fig.1. The Ni^II ion lying on an inversion center has a distorted octahedral geometry being coordinated by six N atoms from six imidazole ligands. Atoms N3, N3ⁱ, N5 & N5ⁱcomprise the equatorial plane, whereas the other two N atoms (N1 & N1ⁱ) occupy the axial positions (symmetry code as is Table 1). The Ni—N distances (Table 1), and the average Ni—N bond length of 2.12 Å, are longer than the Ni—N distances in [Ni(nap)(bip)](Cl)(nap = 1-naphthyl; bip =2,2^'-bipyridine-N,N^'; Ni—N 1.919 (8) Å) (Gelman et al., 2002). As shown in Fig.2, an organic cation layer is linked to an inorganic anionic layer through a series of N—H···O, C—H···O and C—H···N hydrogen bonds (Table 2), and adjacent 3,5-dibromosalicylaldehydenate anions are antiparallel. The hydrogen bonds stabilize the crystal structure.

Related literature top

For related literature, see: Gelman et al. (2002).

Experimental top

The title compound was prepared by adding Ni(Ac)₂^.2H₂O (0.110 g, 0.5 mmol) to a solution of H₂(DBSH) 0.122 mg (0.5 mmol) in methanol (20 mL) and DMF (20 ml). After stirring the mixture for 2 h, the solution was filtered and kept for several days at ambient temperature to evaporate. Brown block-like crystals were obtained.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level [symmetry code: (i) -x+1, -y, -z]. H atoms have been omitted.
	Fig. 2. Part of the crystal structure showing hydrogen bonds as dashed lines.

Hexkis(1H-imidazole-κN³)nickel(II) bis(2,4-dibromo-6-formylphenolate) N,N-dimethylformamide disolvate top

Crystal data top

[Ni(C₃H₄N₂)₆](C₇H₃Br₂O₂)₂·2C₃H₇NO	F(000) = 1172
M_r = 1171.22	D_x = 1.643 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3743 reflections
a = 14.7271 (13) Å	θ = 2.3–25.2°
b = 9.0221 (8) Å	µ = 3.84 mm⁻¹
c = 18.1143 (16) Å	T = 292 K
β = 100.408 (2)°	Block, brown
V = 2367.2 (4) Å³	0.25 × 0.20 × 0.20 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	5147 independent reflections
Radiation source: fine-focus sealed tube	3646 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 27.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −18→10
T_min = 0.309, T_max = 0.392	k = −11→10
13477 measured reflections	l = −23→23

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0625P)²] where P = (F_o² + 2F_c²)/3
5147 reflections	(Δ/σ)_max = 0.001
288 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Ni(C₃H₄N₂)₆](C₇H₃Br₂O₂)₂·2C₃H₇NO	V = 2367.2 (4) Å³
M_r = 1171.22	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.7271 (13) Å	µ = 3.84 mm⁻¹
b = 9.0221 (8) Å	T = 292 K
c = 18.1143 (16) Å	0.25 × 0.20 × 0.20 mm
β = 100.408 (2)°

Data collection top

Bruker SMART CCD diffractometer	5147 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3646 reflections with I > 2σ(I)
T_min = 0.309, T_max = 0.392	R_int = 0.031
13477 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.01	Δρ_max = 0.57 e Å⁻³
5147 reflections	Δρ_min = −0.32 e Å⁻³
288 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
Ni1	0.5000	0.0000	0.0000	0.03274 (14)
Br1	0.24272 (2)	0.17200 (5)	0.27116 (2)	0.06303 (15)
Br2	−0.11882 (4)	0.03677 (8)	0.12533 (3)	0.1107 (2)
N1	0.52342 (17)	−0.0719 (3)	0.11435 (13)	0.0402 (6)
N2	0.5794 (2)	−0.0782 (4)	0.23540 (15)	0.0586 (8)
H2A	0.6097	−0.0524	0.2786	0.070*
N3	0.56038 (16)	0.2073 (3)	0.03727 (13)	0.0393 (6)
N4	0.6664 (2)	0.3744 (3)	0.07883 (15)	0.0524 (7)
H4A	0.7192	0.4175	0.0890	0.063*
N5	0.36975 (16)	0.0871 (3)	0.01215 (13)	0.0379 (6)
N6	0.25325 (17)	0.2412 (3)	−0.00608 (16)	0.0487 (7)
H6A	0.2142	0.3053	−0.0279	0.058*
C16	−0.0057 (2)	−0.0903 (4)	0.41722 (18)	0.0451 (8)
H16	0.0403	−0.0923	0.4598	0.054*
N8	0.2044 (3)	0.7094 (4)	0.1345 (2)	0.0744 (9)
O1	−0.0693 (3)	−0.1323 (4)	0.42179 (16)	0.0882 (9)
O2	0.17355 (14)	0.0277 (2)	0.40408 (11)	0.0457 (5)
O3	0.3141 (2)	0.5358 (4)	0.13585 (18)	0.0927 (10)
C1	0.4906 (2)	−0.1939 (4)	0.1457 (2)	0.0545 (9)
H1	0.4506	−0.2635	0.1195	0.065*
C2	0.5247 (3)	−0.1991 (5)	0.2203 (2)	0.0647 (10)
H2	0.5130	−0.2710	0.2542	0.078*
C3	0.5773 (2)	−0.0056 (4)	0.17004 (18)	0.0498 (8)
H3	0.6100	0.0809	0.1651	0.060*
C4	0.6477 (2)	0.2437 (4)	0.04387 (17)	0.0465 (8)
H4	0.6916	0.1858	0.0264	0.056*
C5	0.5854 (3)	0.4248 (4)	0.0949 (2)	0.0609 (10)
H5	0.5761	0.5129	0.1192	0.073*
C6	0.5208 (2)	0.3220 (4)	0.06879 (19)	0.0517 (8)
H6	0.4586	0.3285	0.0719	0.062*
C7	0.3228 (2)	0.1833 (3)	−0.03379 (18)	0.0434 (7)
H7	0.3367	0.2082	−0.0803	0.052*
C8	0.2548 (2)	0.1816 (4)	0.0622 (2)	0.0590 (9)
H8	0.2149	0.2021	0.0952	0.071*
C9	0.3262 (2)	0.0860 (4)	0.07290 (19)	0.0522 (8)
H9	0.3435	0.0277	0.1154	0.063*
C10	0.1241 (2)	0.0919 (4)	0.27542 (18)	0.0461 (7)
C11	0.1103 (2)	0.0322 (3)	0.34538 (18)	0.0400 (7)
C12	0.0195 (2)	−0.0232 (3)	0.34397 (18)	0.0455 (8)
C13	−0.0480 (2)	−0.0201 (4)	0.2791 (2)	0.0546 (9)
H13	−0.1067	−0.0573	0.2801	0.066*
C14	−0.0282 (3)	0.0373 (4)	0.2142 (2)	0.0584 (9)
C15	0.0579 (2)	0.0958 (4)	0.21212 (18)	0.0565 (9)
H15	0.0707	0.1374	0.1681	0.068*
C19	0.2451 (3)	0.6031 (5)	0.1056 (2)	0.0727 (11)
H19	0.2195	0.5749	0.0569	0.087*
C17	0.2366 (4)	0.7550 (7)	0.2115 (3)	0.1150 (19)
H17A	0.1915	0.7283	0.2414	0.173*
H17B	0.2455	0.8604	0.2134	0.173*
H17C	0.2940	0.7065	0.2308	0.173*
C18	0.1235 (4)	0.7834 (6)	0.0939 (3)	0.1070 (17)
H18A	0.1126	0.7516	0.0425	0.161*
H18B	0.1332	0.8886	0.0961	0.161*
H18C	0.0710	0.7590	0.1162	0.161*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0284 (3)	0.0338 (3)	0.0357 (3)	0.0004 (2)	0.0047 (2)	−0.0001 (2)
Br1	0.0482 (2)	0.0825 (3)	0.0575 (2)	−0.01576 (18)	0.00701 (17)	0.00634 (18)
Br2	0.0836 (4)	0.1536 (5)	0.0743 (3)	−0.0336 (3)	−0.0404 (3)	0.0199 (3)
N1	0.0382 (14)	0.0433 (15)	0.0396 (14)	0.0043 (12)	0.0087 (11)	0.0020 (12)
N2	0.067 (2)	0.071 (2)	0.0378 (15)	0.0125 (17)	0.0083 (14)	0.0040 (15)
N3	0.0374 (14)	0.0380 (14)	0.0418 (14)	−0.0036 (11)	0.0047 (11)	−0.0010 (11)
N4	0.0472 (17)	0.0496 (17)	0.0562 (17)	−0.0136 (13)	−0.0017 (13)	−0.0045 (14)
N5	0.0311 (13)	0.0386 (14)	0.0442 (14)	0.0012 (10)	0.0070 (11)	−0.0019 (11)
N6	0.0337 (14)	0.0465 (16)	0.0626 (17)	0.0100 (12)	0.0001 (12)	−0.0058 (14)
C16	0.0262 (15)	0.059 (2)	0.0451 (18)	−0.0011 (15)	−0.0081 (13)	−0.0160 (16)
N8	0.088 (3)	0.061 (2)	0.069 (2)	−0.0127 (19)	0.0011 (19)	−0.0037 (18)
O1	0.111 (3)	0.091 (2)	0.0664 (18)	−0.015 (2)	0.0265 (18)	0.0002 (16)
O2	0.0361 (12)	0.0528 (14)	0.0436 (12)	0.0005 (9)	−0.0051 (10)	−0.0011 (10)
O3	0.099 (3)	0.093 (2)	0.079 (2)	0.002 (2)	−0.0024 (19)	0.0033 (18)
C1	0.050 (2)	0.056 (2)	0.058 (2)	0.0017 (16)	0.0107 (16)	0.0111 (17)
C2	0.070 (3)	0.075 (3)	0.053 (2)	0.004 (2)	0.0205 (19)	0.019 (2)
C3	0.054 (2)	0.055 (2)	0.0405 (17)	0.0034 (16)	0.0089 (15)	−0.0004 (16)
C4	0.0444 (19)	0.047 (2)	0.0474 (18)	−0.0039 (15)	0.0072 (14)	−0.0012 (16)
C5	0.061 (2)	0.042 (2)	0.077 (3)	−0.0013 (17)	0.005 (2)	−0.0146 (19)
C6	0.0444 (19)	0.0440 (19)	0.066 (2)	0.0017 (15)	0.0070 (16)	−0.0112 (16)
C7	0.0353 (16)	0.0476 (19)	0.0443 (17)	0.0019 (14)	−0.0006 (13)	−0.0022 (15)
C8	0.050 (2)	0.067 (2)	0.066 (2)	0.0175 (18)	0.0270 (18)	0.0084 (19)
C9	0.050 (2)	0.055 (2)	0.055 (2)	0.0130 (16)	0.0214 (16)	0.0123 (16)
C10	0.0384 (17)	0.0481 (19)	0.0507 (18)	−0.0033 (14)	0.0051 (14)	0.0018 (15)
C11	0.0319 (16)	0.0354 (17)	0.0498 (18)	0.0041 (12)	−0.0002 (13)	−0.0057 (13)
C12	0.0368 (17)	0.048 (2)	0.0504 (19)	0.0013 (14)	0.0029 (14)	−0.0005 (15)
C13	0.0382 (19)	0.057 (2)	0.064 (2)	−0.0085 (15)	−0.0036 (16)	−0.0035 (17)
C14	0.052 (2)	0.065 (2)	0.050 (2)	−0.0074 (17)	−0.0156 (16)	0.0011 (17)
C15	0.059 (2)	0.061 (2)	0.0443 (18)	−0.0076 (18)	−0.0037 (16)	0.0047 (17)
C19	0.088 (3)	0.068 (3)	0.058 (2)	−0.020 (2)	0.004 (2)	0.002 (2)
C17	0.147 (5)	0.104 (4)	0.090 (4)	−0.009 (4)	0.010 (3)	−0.022 (3)
C18	0.108 (4)	0.073 (3)	0.126 (4)	0.000 (3)	−0.015 (3)	0.004 (3)

Geometric parameters (Å, º) top

Ni1—N5	2.121 (2)	O2—C11	1.282 (4)
Ni1—N5ⁱ	2.121 (2)	O3—C19	1.224 (5)
Ni1—N3ⁱ	2.128 (2)	C1—C2	1.355 (5)
Ni1—N3	2.128 (2)	C1—H1	0.9300
Ni1—N1ⁱ	2.138 (2)	C2—H2	0.9300
Ni1—N1	2.138 (2)	C3—H3	0.9300
Br1—C10	1.905 (3)	C4—H4	0.9300
Br1—H8	3.1509	C5—C6	1.351 (5)
Br2—C14	1.896 (3)	C5—H5	0.9300
N1—C3	1.309 (4)	C6—H6	0.9300
N1—C1	1.366 (4)	C7—H7	0.9300
N2—C3	1.348 (4)	C8—C9	1.346 (5)
N2—C2	1.354 (5)	C8—H8	0.9300
N2—H2A	0.8600	C9—H9	0.9300
N3—C4	1.312 (4)	C10—C15	1.365 (4)
N3—C6	1.362 (4)	C10—C11	1.425 (4)
N4—C4	1.343 (4)	C11—C12	1.424 (4)
N4—C5	1.357 (4)	C12—C13	1.396 (5)
N4—H4A	0.8600	C13—C14	1.364 (5)
N5—C7	1.310 (4)	C13—H13	0.9300
N5—C9	1.370 (4)	C14—C15	1.381 (5)
N6—C7	1.327 (4)	C15—H15	0.9300
N6—C8	1.345 (4)	C19—H19	0.9300
N6—H6A	0.8600	C17—H17A	0.9600
C16—O1	1.028 (4)	C17—H17B	0.9600
C16—C12	1.563 (5)	C17—H17C	0.9600
C16—H16	0.9300	C18—H18A	0.9600
N8—C19	1.290 (6)	C18—H18B	0.9600
N8—C18	1.446 (6)	C18—H18C	0.9600
N8—C17	1.450 (6)

N5—Ni1—N5ⁱ	180	N3—C4—H4	124.0
N5—Ni1—N3ⁱ	91.41 (9)	N4—C4—H4	124.0
N5ⁱ—Ni1—N3ⁱ	88.59 (9)	C6—C5—N4	106.5 (3)
N5—Ni1—N3	88.59 (9)	C6—C5—H5	126.7
N5ⁱ—Ni1—N3	91.41 (9)	N4—C5—H5	126.7
N3ⁱ—Ni1—N3	180	C5—C6—N3	110.0 (3)
N5—Ni1—N1ⁱ	89.86 (9)	C5—C6—H6	125.0
N5ⁱ—Ni1—N1ⁱ	90.14 (9)	N3—C6—H6	125.0
N3ⁱ—Ni1—N1ⁱ	88.52 (9)	N5—C7—N6	112.0 (3)
N3—Ni1—N1ⁱ	91.48 (9)	N5—C7—H7	124.0
N5—Ni1—N1	90.14 (9)	N6—C7—H7	124.0
N5ⁱ—Ni1—N1	89.86 (9)	N6—C8—C9	105.8 (3)
N3ⁱ—Ni1—N1	91.48 (9)	N6—C8—H8	127.1
N3—Ni1—N1	88.52 (9)	C9—C8—H8	127.1
N1ⁱ—Ni1—N1	180	C8—C9—N5	110.3 (3)
C10—Br1—H8	96.9	C8—C9—H9	124.9
C3—N1—C1	105.0 (3)	N5—C9—H9	124.9
C3—N1—Ni1	125.3 (2)	C15—C10—C11	124.2 (3)
C1—N1—Ni1	129.8 (2)	C15—C10—Br1	118.5 (3)
C3—N2—C2	107.2 (3)	C11—C10—Br1	117.3 (2)
C3—N2—H2A	126.4	O2—C11—C12	122.9 (3)
C2—N2—H2A	126.4	O2—C11—C10	123.4 (3)
C4—N3—C6	105.0 (3)	C12—C11—C10	113.7 (3)
C4—N3—Ni1	126.5 (2)	C13—C12—C11	122.1 (3)
C6—N3—Ni1	127.9 (2)	C13—C12—C16	118.7 (3)
C4—N4—C5	106.5 (3)	C11—C12—C16	119.2 (3)
C4—N4—H4A	126.8	C14—C13—C12	120.2 (3)
C5—N4—H4A	126.8	C14—C13—H13	119.9
C7—N5—C9	104.2 (3)	C12—C13—H13	119.9
C7—N5—Ni1	124.2 (2)	C13—C14—C15	120.6 (3)
C9—N5—Ni1	130.1 (2)	C13—C14—Br2	120.2 (3)
C7—N6—C8	107.7 (3)	C15—C14—Br2	119.1 (3)
C7—N6—H6A	126.1	C10—C15—C14	119.2 (3)
C8—N6—H6A	126.1	C10—C15—H15	120.4
O1—C16—C12	124.8 (3)	C14—C15—H15	120.4
O1—C16—H16	117.6	O3—C19—N8	126.5 (4)
C12—C16—H16	117.6	O3—C19—H19	116.7
C19—N8—C18	122.5 (4)	N8—C19—H19	116.7
C19—N8—C17	120.4 (4)	N8—C17—H17A	109.5
C18—N8—C17	117.0 (4)	N8—C17—H17B	109.5
C2—C1—N1	110.3 (3)	H17A—C17—H17B	109.5
C2—C1—H1	124.8	N8—C17—H17C	109.5
N1—C1—H1	124.8	H17A—C17—H17C	109.5
N2—C2—C1	105.9 (3)	H17B—C17—H17C	109.5
N2—C2—H2	127.1	N8—C18—H18A	109.5
C1—C2—H2	127.1	N8—C18—H18B	109.5
N1—C3—N2	111.7 (3)	H18A—C18—H18B	109.5
N1—C3—H3	124.2	N8—C18—H18C	109.5
N2—C3—H3	124.2	H18A—C18—H18C	109.5
N3—C4—N4	112.1 (3)	H18B—C18—H18C	109.5

N5—Ni1—N1—C3	−102.9 (3)	C4—N4—C5—C6	−0.1 (4)
N5ⁱ—Ni1—N1—C3	77.1 (3)	N4—C5—C6—N3	0.6 (4)
N3ⁱ—Ni1—N1—C3	165.7 (3)	C4—N3—C6—C5	−0.9 (4)
N3—Ni1—N1—C3	−14.3 (3)	Ni1—N3—C6—C5	170.9 (2)
N5—Ni1—N1—C1	79.5 (3)	C9—N5—C7—N6	−0.4 (3)
N5ⁱ—Ni1—N1—C1	−100.5 (3)	Ni1—N5—C7—N6	−167.72 (19)
N3ⁱ—Ni1—N1—C1	−11.9 (3)	C8—N6—C7—N5	0.8 (4)
N3—Ni1—N1—C1	168.1 (3)	C7—N6—C8—C9	−0.9 (4)
N5—Ni1—N3—C4	−178.5 (3)	N6—C8—C9—N5	0.7 (4)
N5ⁱ—Ni1—N3—C4	1.5 (3)	C7—N5—C9—C8	−0.2 (4)
N1ⁱ—Ni1—N3—C4	−88.6 (3)	Ni1—N5—C9—C8	166.1 (2)
N1—Ni1—N3—C4	91.4 (3)	H8—Br1—C10—C15	−12.2
N5—Ni1—N3—C6	11.4 (3)	H8—Br1—C10—C11	168.2
N5ⁱ—Ni1—N3—C6	−168.6 (3)	C15—C10—C11—O2	179.1 (3)
N1ⁱ—Ni1—N3—C6	101.2 (3)	Br1—C10—C11—O2	−1.3 (4)
N1—Ni1—N3—C6	−78.8 (3)	C15—C10—C11—C12	−0.5 (5)
N3ⁱ—Ni1—N5—C7	−105.8 (2)	Br1—C10—C11—C12	179.1 (2)
N3—Ni1—N5—C7	74.2 (2)	O2—C11—C12—C13	−178.7 (3)
N1ⁱ—Ni1—N5—C7	−17.3 (2)	C10—C11—C12—C13	0.9 (4)
N1—Ni1—N5—C7	162.7 (2)	O2—C11—C12—C16	1.2 (4)
N3ⁱ—Ni1—N5—C9	90.3 (3)	C10—C11—C12—C16	−179.3 (3)
N3—Ni1—N5—C9	−89.7 (3)	O1—C16—C12—C13	−0.6 (6)
N1ⁱ—Ni1—N5—C9	178.8 (3)	O1—C16—C12—C11	179.6 (4)
N1—Ni1—N5—C9	−1.2 (3)	C11—C12—C13—C14	0.0 (5)
C3—N1—C1—C2	0.5 (4)	C16—C12—C13—C14	−179.8 (3)
Ni1—N1—C1—C2	178.4 (2)	C12—C13—C14—C15	−1.4 (6)
C3—N2—C2—C1	−0.6 (4)	C12—C13—C14—Br2	178.3 (3)
N1—C1—C2—N2	0.1 (4)	C11—C10—C15—C14	−0.8 (5)
C1—N1—C3—N2	−0.9 (4)	Br1—C10—C15—C14	179.6 (3)
Ni1—N1—C3—N2	−179.0 (2)	C13—C14—C15—C10	1.8 (6)
C2—N2—C3—N1	1.0 (4)	Br2—C14—C15—C10	−177.9 (3)
C6—N3—C4—N4	0.9 (4)	C18—N8—C19—O3	179.4 (5)
Ni1—N3—C4—N4	−171.08 (19)	C17—N8—C19—O3	−3.5 (7)
C5—N4—C4—N3	−0.5 (4)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱⁱ	0.86	1.92	2.764 (5)	169
N4—H4A···O2ⁱⁱⁱ	0.86	1.85	2.703 (3)	170
N6—H6A···O2^iv	0.86	1.97	2.772 (3)	155
C7—H7···N1ⁱ	0.93	2.57	3.076 (4)	115
C8—H8···O1^v	0.93	2.59	3.264 (5)	130
C3—H3···N3	0.93	2.57	3.053 (4)	113

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

Experimental details

Crystal data
Chemical formula	[Ni(C₃H₄N₂)₆](C₇H₃Br₂O₂)₂·2C₃H₇NO
M_r	1171.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	14.7271 (13), 9.0221 (8), 18.1143 (16)
β (°)	100.408 (2)
V (Å³)	2367.2 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.84
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.309, 0.392
No. of measured, independent and observed [I > 2σ(I)] reflections	13477, 5147, 3646
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.113, 1.01
No. of reflections	5147
No. of parameters	288
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.32

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Ni1—N5	2.121 (2)	Ni1—N1	2.138 (2)
Ni1—N3	2.128 (2)

N5—Ni1—N5ⁱ	180	N3—Ni1—N1ⁱ	91.48 (9)
N5—Ni1—N3ⁱ	91.41 (9)	N5—Ni1—N1	90.14 (9)
N5—Ni1—N3	88.59 (9)	N3—Ni1—N1	88.52 (9)
N3ⁱ—Ni1—N3	180	N1ⁱ—Ni1—N1	180
N5—Ni1—N1ⁱ	89.86 (9)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱⁱ	0.86	1.92	2.764 (5)	168.8
N4—H4A···O2ⁱⁱⁱ	0.86	1.85	2.703 (3)	170.3
N6—H6A···O2^iv	0.86	1.97	2.772 (3)	154.7
C7—H7···N1ⁱ	0.93	2.57	3.076 (4)	114.8
C8—H8···O1^v	0.93	2.59	3.264 (5)	130.2
C3—H3···N3	0.93	2.57	3.053 (4)	113.0

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

Acknowledgements

This work was supported by the Natural Science Foundation of Hubei Province (No. Q20082601) and the Foundation of Xiaogan University (Z2008012).

References

Bruker (2001). SAINT, SMART and SADABS. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Gelman, D., Dechert, S., Schumann, H. & Blum, J. (2002). Inorg. Chim. Acta, 334, 149–158. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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