Bis(1,1-di­methyl­biguanido)­nickel(II)

The title compound, [Ni(C₄H₁₀N₅)₂], was prepared from an aqueous KOH solution. The coordination geometry around the Ni atom is planar, with the central metal bonded to four ligand N atoms in two bidentate ligands. The deprotonation of the ligand causes an increase of the π-conjugation in the C—N—C system, reducing the bond angle at the N atom to 118.46 (16)°.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](N-C) = 0.003 Å
• R factor = 0.030
• wR factor = 0.072
• Data-to-parameter ratio = 14.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_420  Alert C D-H Without Acceptor       N(2)   -   H(12)             ?

PLAT_420  Alert C D-H Without Acceptor       N(5)   -   H(15B)            ?

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and _chemical_formula_moiety. This is
          usually due to the moiety formula being in the wrong format.
          Atom count from _chemical_formula_sum:   C8 H20 N10 Ni1
          Atom count from _chemical_formula_moiety:C4 H10 N5 Ni1


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

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Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: SHELXS97 (Sheldrick, 1997); program(s) used to solve structure: SHELXS97; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: SHELXL97.

Bis(1,1-dimethylbiguande)nickel(II)

Crystal data

[Ni(C4H10N5)2]	F(000) = 332
Mr = 315.05	Dx = 1.620 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1564 reflections
a = 6.412 (1) Å	θ = 2.9–27.5°
b = 9.032 (2) Å	µ = 1.51 mm^−1
c = 11.239 (2) Å	T = 173 K
β = 97.05 (3)°	Block, orange
V = 646.0 (2) Å^3	0.40 × 0.30 × 0.20 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID IP diffractometer	1494 independent reflections
Radiation source: fine-focus sealed tube	1159 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 100x100 microns pixels mm^-1	θmax = 27.5°, θmin = 2.9°
Oscillation scans	h = 0→8
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	k = 0→11
Tmin = 0.540, Tmax = 0.740	l = −14→14
1564 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: hydrogen atoms are generated by HFIX instructions
wR(F^2) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0409P)^2] where P = (Fo^2 + 2Fc^2)/3
1467 reflections	(Δ/σ)max = 0.001
102 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.55 e Å^−3

Special details

Experimental. ABSCOR BY T·Higashi 8 march,1995

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.0000	0.0000	0.01623 (12)
N1	0.4634 (2)	0.00804 (18)	0.16042 (15)	0.0199 (3)
N2	0.7070 (3)	0.14347 (19)	0.02827 (15)	0.0208 (4)
N3	0.9247 (3)	0.32489 (19)	0.12657 (14)	0.0226 (4)
N4	0.6763 (2)	0.21581 (18)	0.22815 (14)	0.0191 (4)
N5	0.4849 (3)	0.0950 (2)	0.35585 (16)	0.0274 (4)
C1	0.5382 (3)	0.1054 (2)	0.24156 (17)	0.0180 (4)
C2	0.7654 (3)	0.2216 (2)	0.12635 (17)	0.0183 (4)
C3	1.0568 (3)	0.3188 (3)	0.03008 (19)	0.0301 (5)
H3A	1.1246	0.2216	0.0300	0.045*
H3B	1.1645	0.3961	0.0423	0.045*
H3C	0.9701	0.3347	−0.0469	0.045*
C4	1.0354 (3)	0.3761 (2)	0.24075 (19)	0.0287 (5)
H4A	0.9343	0.3902	0.2985	0.043*
H4B	1.1058	0.4701	0.2285	0.043*
H4C	1.1400	0.3021	0.2717	0.043*
H11	0.399 (5)	−0.056 (4)	0.194 (3)	0.080*
H12	0.784 (5)	0.156 (3)	−0.023 (3)	0.080*
H15A	0.519 (5)	0.174 (4)	0.396 (3)	0.080*
H15B	0.378 (6)	0.047 (4)	0.363 (3)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01645 (17)	0.01617 (19)	0.01637 (19)	−0.00273 (14)	0.00321 (12)	−0.00093 (14)
N1	0.0190 (7)	0.0204 (8)	0.0208 (8)	−0.0047 (7)	0.0042 (6)	−0.0008 (7)
N2	0.0224 (8)	0.0228 (9)	0.0180 (8)	−0.0048 (7)	0.0056 (6)	−0.0019 (7)
N3	0.0223 (8)	0.0274 (9)	0.0188 (8)	−0.0091 (7)	0.0061 (6)	−0.0028 (7)
N4	0.0188 (8)	0.0185 (8)	0.0203 (9)	−0.0005 (6)	0.0041 (6)	−0.0025 (7)
N5	0.0318 (10)	0.0295 (10)	0.0230 (10)	−0.0092 (8)	0.0115 (8)	−0.0061 (8)
C1	0.0166 (9)	0.0191 (9)	0.0186 (9)	0.0031 (7)	0.0036 (7)	−0.0004 (8)
C2	0.0161 (9)	0.0150 (9)	0.0238 (10)	0.0006 (7)	0.0023 (7)	0.0020 (8)
C3	0.0290 (11)	0.0330 (12)	0.0303 (12)	−0.0123 (9)	0.0118 (9)	−0.0048 (10)
C4	0.0237 (10)	0.0364 (12)	0.0253 (11)	−0.0131 (9)	0.0006 (8)	−0.0033 (10)

Geometric parameters (Å, º)

Ni1—N1	1.8480 (17)	N4—C2	1.341 (2)
Ni1—N1^i	1.8480 (17)	N4—C1	1.354 (2)
Ni1—N2^i	1.8543 (16)	N5—C1	1.372 (2)
Ni1—N2	1.8543 (16)	N5—H15A	0.86 (3)
N1—C1	1.314 (2)	N5—H15B	0.83 (4)
N1—H11	0.83 (3)	C3—H3A	0.9800
N2—C2	1.324 (2)	C3—H3B	0.9800
N2—H12	0.81 (3)	C3—H3C	0.9800
N3—C2	1.383 (2)	C4—H4A	0.9800
N3—C3	1.457 (2)	C4—H4B	0.9800
N3—C4	1.463 (3)	C4—H4C	0.9800
N1^i—Ni1—N1	180.0	N1—C1—N4	127.12 (17)
N1^i—Ni1—N2	91.18 (7)	N1—C1—N5	119.47 (18)
N1—Ni1—N2	88.82 (7)	N4—C1—N5	113.32 (17)
N1^i—Ni1—N2^i	88.82 (7)	N2—C2—N4	125.66 (17)
N1—Ni1—N2^i	91.18 (7)	N2—C2—N3	119.64 (17)
N2—Ni1—N2^i	180.0	N4—C2—N3	114.63 (17)
C1—N1—Ni1	128.60 (13)	N3—C3—H3A	109.5
C1—N1—H11	108 (2)	N3—C3—H3B	109.5
Ni1—N1—H11	124 (2)	H3A—C3—H3B	109.5
C2—N2—Ni1	129.70 (14)	N3—C3—H3C	109.5
C2—N2—H12	112 (2)	H3A—C3—H3C	109.5
Ni1—N2—H12	118 (2)	H3B—C3—H3C	109.5
C2—N3—C3	118.05 (17)	N3—C4—H4A	109.5
C2—N3—C4	119.55 (16)	N3—C4—H4B	109.5
C3—N3—C4	113.65 (17)	H4A—C4—H4B	109.5
C2—N4—C1	118.46 (16)	N3—C4—H4C	109.5
C1—N5—H15A	111 (2)	H4A—C4—H4C	109.5
C1—N5—H15B	116 (3)	H4B—C4—H4C	109.5
H15A—N5—H15B	123 (3)
N2^i—Ni1—N1—C1	−168.71 (17)	Ni1—N2—C2—N4	−2.8 (3)
N2—Ni1—N1—C1	11.29 (17)	Ni1—N2—C2—N3	−179.43 (14)
N1^i—Ni1—N2—C2	172.91 (18)	C1—N4—C2—N2	11.5 (3)
N1—Ni1—N2—C2	−7.09 (18)	C1—N4—C2—N3	−171.65 (16)
N1^i—Ni1—N2—C2	172.91 (18)	C3—N3—C2—N2	−14.8 (3)
Ni1—N1—C1—N4	−6.5 (3)	C4—N3—C2—N2	−160.38 (18)
Ni1—N1—C1—N5	177.29 (14)	C3—N3—C2—N4	168.15 (18)
C2—N4—C1—N1	−7.0 (3)	C4—N3—C2—N4	22.6 (3)
C2—N4—C1—N5	169.45 (17)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H15A···N2^ii	0.86 (3)	2.43 (3)	3.269 (3)	164 (3)
N1—H11···N4^iii	0.83 (3)	2.31 (4)	3.100 (2)	159 (3)

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