Diazido-bis(5,5'-dimethyl-2,2'-bipyridyl-κN,N')nickel(II) monohydrate.

In the crystal structure of the title compound, [Ni(N(3))(2)(C(12)H(12)N(2))(2)]·H(2)O, the Ni(II) atom is situated on a twofold axis and adopts a distorted octa-hedral geometry with the two 5,5'-dimethyl-2,2'-bipyridyl (dmbpy) and the two azide ligands in a cis arrangement. The water solvent mol-ecule is disordered over two positions in a 1:1 ratio.

Related literature

For general background to 2,2′-bipyridine and its derivatives, see: Blau (1888 ▶); Constable (1989 ▶); Constable & Steel (1989 ▶); Juris et al. (1988 ▶). For related dmbpy structures, see: n class="Disease">van Albada et al. (2004 ▶, 2005 ▶); Catalan et al. (1995 ▶); Kooijman et al. (2002 ▶). For Ni–N bond lengths in azido-containing mononuclear nickel(II) complexes, see: Urtiaga et al. (1995 ▶). For an NiII complex with 5,5′-dimethyl-2,2′-bipyridyl, see: Hou (2008 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[Ni(n class="Chemical">N3)2(C12H12N2)2]·H2O

M = 529.22

Orthorhombic,

a = 17.0770 (3) Å

b = 8.5350 (5) Å

c = 16.6700 (4) Å

V = 2429.69 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.84 mm−1

T = 293 K

0.53 × 0.45 × 0.40 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.630, T max = 0.712

7908 measured reflections

4209 independent reflections

2929 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.127

S = 1.03

4209 reflections

195 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.37 e Å−3

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: COLLECT and DEn class="Chemical">NZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809029407/rn2055sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029407/rn2055Isup2.hkl

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

[Ni(N3)2(C12H12N2)2]·H2O	F(000) = 1096
Mr = 529.22	Dx = 1.444 Mg m−3Dm = 1.440 Mg m−3Dm measured by flotation in aqueous KI
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 7908 reflections
a = 17.0770 (3) Å	θ = 2.7–27.5°
b = 8.5350 (5) Å	µ = 0.84 mm−1
c = 16.6700 (4) Å	T = 293 K
V = 2429.69 (16) Å3	Plate, green
Z = 4	0.53 × 0.45 × 0.40 mm

Nonius KappaCCD diffractometer	4209 independent reflections
Radiation source: fine-focus sealed tube	2929 reflections with I > 2σ(I)
graphite	Rint = 0.031
ω scans	θmax = 32.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→25
Tmin = 0.630, Tmax = 0.712	k = −12→12
7908 measured reflections	l = −24→24

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.127	w = 1/[σ2(Fo2) + (0.0689P)2 + 0.3234P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
4209 reflections	Δρmax = 0.35 e Å−3
195 parameters	Δρmin = −0.37 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.023 (3)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	1.0000	0.25758 (3)	0.2500	0.03045 (11)
C1	0.85037 (9)	0.1839 (2)	0.15504 (10)	0.0394 (4)
C2	0.77052 (9)	0.1813 (2)	0.13931 (10)	0.0430 (4)
C3	0.72270 (11)	0.2632 (2)	0.19237 (13)	0.0485 (5)
C4	0.75485 (10)	0.3478 (3)	0.25456 (10)	0.0444 (4)
C5	0.83592 (9)	0.3501 (2)	0.26388 (9)	0.0351 (3)
C6	0.87691 (8)	0.44736 (19)	0.32433 (9)	0.0346 (3)
C7	0.83951 (10)	0.5554 (2)	0.37348 (11)	0.0455 (4)
C8	0.88410 (10)	0.6520 (2)	0.42157 (11)	0.0474 (4)
C9	0.96489 (10)	0.6414 (2)	0.42151 (9)	0.0404 (4)
C10	0.99748 (9)	0.5262 (2)	0.37327 (10)	0.0378 (3)
C11	0.73848 (11)	0.0947 (3)	0.06809 (12)	0.0571 (5)
C12	1.01596 (15)	0.7508 (2)	0.46878 (14)	0.0526 (5)
N1	0.88262 (7)	0.26572 (15)	0.21515 (8)	0.0341 (3)
N2	0.95560 (7)	0.43102 (16)	0.32590 (7)	0.0339 (3)
N3	1.02626 (9)	0.08562 (18)	0.16354 (8)	0.0434 (3)
N4	1.08684 (8)	0.07905 (18)	0.12842 (8)	0.0402 (3)
N5	1.14499 (9)	0.0716 (3)	0.09306 (11)	0.0655 (5)
O19	0.9708 (3)	0.7988 (4)	0.2398 (3)	0.0853 (15)	0.50
H1	0.8876 (10)	0.120 (2)	0.1214 (11)	0.044 (5)*
H3	0.6660 (14)	0.261 (2)	0.1832 (13)	0.053 (6)*
H4	0.7209 (11)	0.404 (2)	0.2906 (12)	0.053 (6)*
H7	0.7824 (12)	0.563 (2)	0.3731 (11)	0.049 (5)*
H8	0.8591 (13)	0.735 (2)	0.4557 (14)	0.054 (6)*
H10	1.0548 (12)	0.509 (2)	0.3715 (11)	0.045 (5)*
H11A	0.7797	0.0357	0.0432	0.086*
H11B	0.7175	0.1683	0.0302	0.086*
H11C	0.6978	0.0247	0.0853	0.086*
H12A	1.0385	0.8272	0.4334	0.079*
H12B	1.0570	0.6922	0.4944	0.079*
H12C	0.9850	0.8028	0.5088	0.079*

	U11	U22	U33	U12	U13	U23
Ni1	0.02557 (16)	0.03435 (17)	0.03144 (16)	0.000	0.00161 (9)	0.000
C1	0.0336 (7)	0.0443 (9)	0.0403 (8)	−0.0033 (7)	−0.0006 (6)	−0.0012 (7)
C2	0.0361 (8)	0.0476 (10)	0.0455 (8)	−0.0063 (7)	−0.0043 (6)	0.0019 (8)
C3	0.0302 (8)	0.0605 (12)	0.0549 (10)	−0.0022 (7)	−0.0036 (7)	0.0015 (8)
C4	0.0294 (7)	0.0546 (11)	0.0492 (9)	0.0034 (7)	0.0021 (6)	−0.0002 (8)
C5	0.0292 (7)	0.0377 (8)	0.0384 (7)	−0.0002 (6)	0.0018 (5)	0.0033 (6)
C6	0.0304 (7)	0.0378 (8)	0.0354 (7)	0.0030 (6)	0.0020 (5)	0.0024 (6)
C7	0.0369 (8)	0.0533 (11)	0.0462 (9)	0.0066 (7)	0.0046 (7)	−0.0081 (8)
C8	0.0483 (9)	0.0506 (11)	0.0433 (9)	0.0086 (8)	0.0059 (7)	−0.0100 (8)
C9	0.0477 (9)	0.0399 (9)	0.0336 (7)	−0.0002 (7)	−0.0016 (6)	−0.0010 (7)
C10	0.0342 (7)	0.0411 (8)	0.0381 (8)	−0.0004 (6)	−0.0013 (5)	−0.0009 (7)
C11	0.0462 (10)	0.0693 (14)	0.0556 (11)	−0.0115 (9)	−0.0091 (8)	−0.0088 (10)
C12	0.0645 (12)	0.0489 (11)	0.0444 (10)	−0.0032 (8)	−0.0044 (9)	−0.0116 (8)
N1	0.0281 (6)	0.0384 (7)	0.0360 (7)	−0.0014 (5)	0.0007 (5)	0.0000 (5)
N2	0.0313 (6)	0.0357 (7)	0.0347 (6)	0.0013 (5)	0.0017 (4)	−0.0005 (5)
N3	0.0424 (7)	0.0447 (8)	0.0431 (7)	−0.0017 (6)	0.0084 (6)	−0.0076 (6)
N4	0.0373 (7)	0.0448 (8)	0.0383 (7)	0.0076 (6)	−0.0032 (5)	−0.0040 (6)
N5	0.0386 (8)	0.0938 (15)	0.0640 (10)	0.0137 (9)	0.0085 (7)	−0.0099 (10)
O19	0.132 (5)	0.0521 (16)	0.072 (3)	−0.021 (2)	0.026 (3)	−0.0070 (18)

Ni1—N1i	2.0882 (13)	C6—C7	1.389 (2)
Ni1—N1	2.0882 (13)	C7—C8	1.379 (3)
Ni1—N2i	2.0897 (13)	C7—H7	0.978 (19)
Ni1—N2	2.0897 (13)	C8—C9	1.383 (2)
Ni1—N3	2.1053 (14)	C8—H8	1.00 (2)
Ni1—N3i	2.1053 (14)	C9—C10	1.387 (2)
C1—N1	1.340 (2)	C9—C12	1.501 (3)
C1—C2	1.389 (2)	C10—N2	1.340 (2)
C1—H1	1.008 (19)	C10—H10	0.99 (2)
C2—C3	1.392 (3)	C11—H11A	0.9600
C2—C11	1.502 (3)	C11—H11B	0.9600
C3—C4	1.377 (3)	C11—H11C	0.9600
C3—H3	0.98 (2)	C12—H12A	0.9600
C4—C5	1.393 (2)	C12—H12B	0.9600
C4—H4	0.96 (2)	C12—H12C	0.9600
C5—N1	1.347 (2)	N3—N4	1.1901 (19)
C5—C6	1.481 (2)	N4—N5	1.157 (2)
C6—N2	1.3512 (18)	O19—O19i	1.053 (9)
N1i—Ni1—N1	176.19 (7)	C8—C7—C6	119.07 (15)
N1i—Ni1—N2i	78.26 (5)	C8—C7—H7	121.0 (12)
N1—Ni1—N2i	98.99 (5)	C6—C7—H7	119.9 (12)
N1i—Ni1—N2	98.99 (5)	C7—C8—C9	120.74 (16)
N1—Ni1—N2	78.26 (5)	C7—C8—H8	121.0 (13)
N2i—Ni1—N2	89.80 (7)	C9—C8—H8	118.2 (13)
N1i—Ni1—N3	90.53 (5)	C8—C9—C10	116.59 (16)
N1—Ni1—N3	92.13 (5)	C8—C9—C12	122.57 (17)
N2i—Ni1—N3	90.12 (6)	C10—C9—C12	120.81 (17)
N2—Ni1—N3	170.26 (5)	N2—C10—C9	123.88 (15)
N1i—Ni1—N3i	92.13 (5)	N2—C10—H10	114.9 (11)
N1—Ni1—N3i	90.53 (5)	C9—C10—H10	121.2 (11)
N2i—Ni1—N3i	170.26 (5)	C2—C11—H11A	109.5
N2—Ni1—N3i	90.12 (6)	C2—C11—H11B	109.5
N3—Ni1—N3i	91.61 (8)	H11A—C11—H11B	109.5
N1—C1—C2	123.57 (16)	C2—C11—H11C	109.5
N1—C1—H1	116.1 (10)	H11A—C11—H11C	109.5
C2—C1—H1	120.3 (10)	H11B—C11—H11C	109.5
C1—C2—C3	116.64 (16)	C9—C12—H12A	109.5
C1—C2—C11	120.97 (17)	C9—C12—H12B	109.5
C3—C2—C11	122.39 (16)	H12A—C12—H12B	109.5
C4—C3—C2	120.49 (16)	C9—C12—H12C	109.5
C4—C3—H3	121.3 (12)	H12A—C12—H12C	109.5
C2—C3—H3	118.2 (12)	H12B—C12—H12C	109.5
C3—C4—C5	119.18 (17)	C1—N1—C5	119.11 (14)
C3—C4—H4	119.4 (12)	C1—N1—Ni1	125.82 (11)
C5—C4—H4	121.4 (12)	C5—N1—Ni1	114.73 (10)
N1—C5—C4	120.87 (15)	C10—N2—C6	118.67 (13)
N1—C5—C6	115.47 (13)	C10—N2—Ni1	126.35 (10)
C4—C5—C6	123.61 (15)	C6—N2—Ni1	114.97 (10)
N2—C6—C7	120.95 (15)	N4—N3—Ni1	123.70 (12)
N2—C6—C5	115.17 (13)	N5—N4—N3	178.73 (18)
C7—C6—C5	123.77 (14)
N1—C1—C2—C3	−3.3 (3)	N2—Ni1—N1—C1	176.04 (14)
N1—C1—C2—C11	176.43 (18)	N3—Ni1—N1—C1	−2.32 (14)
C1—C2—C3—C4	3.1 (3)	N3i—Ni1—N1—C1	−93.95 (14)
C11—C2—C3—C4	−176.62 (19)	N2i—Ni1—N1—C5	−98.70 (11)
C2—C3—C4—C5	−0.2 (3)	N2—Ni1—N1—C5	−10.79 (11)
C3—C4—C5—N1	−2.9 (3)	N3—Ni1—N1—C5	170.84 (11)
C3—C4—C5—C6	174.78 (17)	N3i—Ni1—N1—C5	79.22 (12)
N1—C5—C6—N2	−4.0 (2)	C9—C10—N2—C6	0.2 (2)
C4—C5—C6—N2	178.28 (16)	C9—C10—N2—Ni1	178.82 (12)
N1—C5—C6—C7	172.35 (16)	C7—C6—N2—C10	−3.0 (2)
C4—C5—C6—C7	−5.4 (3)	C5—C6—N2—C10	173.45 (14)
N2—C6—C7—C8	3.1 (3)	C7—C6—N2—Ni1	178.23 (13)
C5—C6—C7—C8	−173.01 (16)	C5—C6—N2—Ni1	−5.34 (17)
C6—C7—C8—C9	−0.4 (3)	N1i—Ni1—N2—C10	7.22 (14)
C7—C8—C9—C10	−2.2 (3)	N1—Ni1—N2—C10	−170.09 (14)
C7—C8—C9—C12	175.99 (19)	N2i—Ni1—N2—C10	−70.86 (13)
C8—C9—C10—N2	2.4 (3)	N3i—Ni1—N2—C10	99.40 (14)
C12—C9—C10—N2	−175.83 (16)	N1i—Ni1—N2—C6	−174.10 (10)
C2—C1—N1—C5	0.4 (3)	N1—Ni1—N2—C6	8.59 (10)
C2—C1—N1—Ni1	173.26 (13)	N2i—Ni1—N2—C6	107.82 (11)
C4—C5—N1—C1	2.8 (2)	N3i—Ni1—N2—C6	−81.92 (11)
C6—C5—N1—C1	−175.05 (14)	N1i—Ni1—N3—N4	−32.56 (15)
C4—C5—N1—Ni1	−170.89 (13)	N1—Ni1—N3—N4	144.70 (14)
C6—C5—N1—Ni1	11.29 (17)	N2i—Ni1—N3—N4	45.70 (14)
N2i—Ni1—N1—C1	88.14 (14)	N3i—Ni1—N3—N4	−124.71 (16)

Table 1

Selected geometric parameters (Å, °)

Ni1—N1	2.0882 (13)
Ni1—N2	2.0897 (13)
Ni1—N3	2.1053 (14)

Symmetry code: (i) .