Diaqua­bis(N-ethyl-N′,N′-dimethyl­ethylenediamine-κ2N,N′)nickel(II) dichloride

Liang, Y.-N.; Chen, Z.-L.; Zhang, Y.-Z.; Ng, S.W.

doi:10.1107/S1600536807031467

Diaquabis(N-ethyl-N′,N′-dimethylethylenediamine-κ²N,N′)nickel(II) dichloride

Y.-N. Liang, Z.-L. Chen, Y.-Z. Zhang and S. W. Ng

In the title compound, [Ni(C₆H₁₆N₂)₂(H₂O)₂]Cl₂, the Ni^II cation (site symmetry $\overline{1}$ ) is coordinated by two N,N-bidentate ligands and two water molecules, resulting in a slightly distorted trans-NiO₂N₄ octahedron. The complex cations and chloride anions are linked by N—H

Cl and O—H

Cl hydrogen bonds into a chain.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031467/hb2461sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031467/hb2461Isup2.hkl Contains datablock I

CCDC reference: 657518

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.003 Å
R factor = 0.030
wR factor = 0.078
Data-to-parameter ratio = 20.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.82
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        100 Ang.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          4
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   O1W     ..       5.48 su
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         21
            N2  -NI1 -N2  -C5     11.00  0.00   3.666   1.555   1.555   1.555
PLAT715_ALERT_1_C D-H     Unknown or Inconsistent Label ..........    O1<I>W<
PLAT715_ALERT_1_C D-H     Unknown or Inconsistent Label ..........    O1<I>W<
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........    H1<I>N<
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.824
            Tmax scaled      0.824 Tmin scaled      0.706
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

A number of nickel dichloride complexes of substituted ethylenediamines have been characterized by X-ray diffraction; these have the nickel atom chelated by two ligands. The octahedral geometry is completed by two water molecules. Such aquanickel salts are exemplified by the N,N-dimethylethylenediamine and N,N-diethylethylenediamine complexes (Ide & Norman, 2007; Ihara et al., 1991). The title compound, (I), shows a similar metal geometry (Fig. 1, Table 1). and the bite angle of the ligand is also similar to those found in such compounds. The components interact by way of N—H···Cl and O—H···Cl hydrogen bonds (Table 2).

Related literature top

For other nickel dichloride complexes of substituted ethylenediamines, see Ide & Norman (2007) and Ihara et al. (1991).

Experimental top

To an ethanol solution (5 ml) of nickel chloride hexahydrate (0.119 g, 0.5 mmol) was added an ethanol solution (5 ml) of N,N-dimethyl-N'-ethyl-ethylenediamine (1.6 ml, 1 mmol). The solution was filtered. Ether was diffused into the filtrate; light blue crystals of (I) were isolated after a week.

Structure description top

For other nickel dichloride complexes of substituted ethylenediamines, see Ide & Norman (2007) and Ihara et al. (1991).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top

Fig. 1. View of part of a chain in (I) showing 50% displacement ellipsoids for the non-hydrogen atoms.

Diaquabis[N,N-dimethyl-N'-ethylethylenediamine-κ²N,N']nickel(II) dichloride top

Crystal data top

[Ni(C₆H₁₆N₂)₂(H₂O)₂]Cl₂	F(000) = 428
M_r = 398.06	D_x = 1.366 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2782 reflections
a = 7.802 (1) Å	θ = 2.6–27.5°
b = 12.550 (1) Å	µ = 1.29 mm⁻¹
c = 9.935 (1) Å	T = 295 K
β = 95.750 (1)°	Block, light blue
V = 967.9 (2) Å³	0.20 × 0.20 × 0.15 mm
Z = 2

Data collection top

Bruker APEX CCD diffractometer	2203 independent reflections
Radiation source: fine-focus sealed tube	1843 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
φ and ω scans	θ_max = 27.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.856, T_max = 1.000	k = −12→16
5912 measured reflections	l = −12→12

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0399P)² + 0.2921P] where P = (F_o² + 2F_c²)/3
2203 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 0.47 e Å⁻³
3 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Ni(C₆H₁₆N₂)₂(H₂O)₂]Cl₂	V = 967.9 (2) Å³
M_r = 398.06	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.802 (1) Å	µ = 1.29 mm⁻¹
b = 12.550 (1) Å	T = 295 K
c = 9.935 (1) Å	0.20 × 0.20 × 0.15 mm
β = 95.750 (1)°

Data collection top

Bruker APEX CCD diffractometer	2203 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1843 reflections with I > 2σ(I)
T_min = 0.856, T_max = 1.000	R_int = 0.019
5912 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	3 restraints
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.47 e Å⁻³
2203 reflections	Δρ_min = −0.36 e Å⁻³
109 parameters

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

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.5000	0.5000	0.02374 (11)
Cl1	0.02304 (6)	0.31615 (4)	0.44701 (7)	0.05183 (18)
O1W	0.23497 (17)	0.52469 (12)	0.44802 (15)	0.0353 (3)
N1	0.4525 (2)	0.33584 (12)	0.46081 (17)	0.0303 (3)
N2	0.5432 (2)	0.50319 (12)	0.28146 (16)	0.0340 (4)
C1	0.4882 (3)	0.14532 (19)	0.5352 (3)	0.0565 (6)
H1A	0.5675	0.0980	0.5854	0.085*
H1B	0.4670	0.1206	0.4436	0.085*
H1C	0.3818	0.1470	0.5760	0.085*
C2	0.5644 (3)	0.25613 (15)	0.5361 (2)	0.0415 (5)
H2A	0.5879	0.2796	0.6291	0.050*
H2B	0.6734	0.2531	0.4971	0.050*
C3	0.4438 (3)	0.32060 (16)	0.3122 (2)	0.0431 (5)
H3A	0.3294	0.3387	0.2712	0.052*
H3B	0.4655	0.2464	0.2922	0.052*
C4	0.5748 (3)	0.38971 (18)	0.2536 (2)	0.0441 (5)
H4A	0.6894	0.3701	0.2927	0.053*
H4B	0.5689	0.3785	0.1567	0.053*
C5	0.6964 (3)	0.5649 (2)	0.2497 (2)	0.0560 (6)
H5A	0.7056	0.5622	0.1541	0.084*
H5B	0.7981	0.5347	0.2973	0.084*
H5C	0.6846	0.6376	0.2771	0.084*
C6	0.3960 (3)	0.5413 (2)	0.1889 (2)	0.0508 (6)
H6A	0.4261	0.5397	0.0976	0.076*
H6B	0.3681	0.6130	0.2125	0.076*
H6C	0.2983	0.4960	0.1966	0.076*
H1W1	0.170 (3)	0.4708 (13)	0.448 (3)	0.055 (8)*
H1W2	0.177 (3)	0.5738 (14)	0.478 (2)	0.056 (8)*
H1N	0.3539 (16)	0.3279 (16)	0.486 (2)	0.034 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01999 (17)	0.02258 (17)	0.02879 (18)	0.00071 (11)	0.00310 (12)	−0.00120 (12)
Cl1	0.0282 (3)	0.0379 (3)	0.0903 (5)	−0.0015 (2)	0.0104 (3)	−0.0152 (3)
O1W	0.0237 (7)	0.0315 (8)	0.0510 (9)	0.0016 (6)	0.0045 (6)	−0.0039 (6)
N1	0.0249 (8)	0.0259 (8)	0.0403 (9)	0.0000 (6)	0.0038 (6)	−0.0011 (6)
N2	0.0353 (9)	0.0365 (9)	0.0304 (8)	−0.0016 (7)	0.0047 (7)	0.0004 (7)
C1	0.0533 (15)	0.0329 (12)	0.0823 (18)	−0.0003 (10)	0.0025 (13)	0.0111 (11)
C2	0.0350 (11)	0.0296 (10)	0.0581 (14)	0.0022 (8)	−0.0045 (9)	0.0015 (9)
C3	0.0523 (13)	0.0337 (11)	0.0427 (12)	−0.0035 (9)	0.0016 (10)	−0.0100 (9)
C4	0.0495 (13)	0.0461 (13)	0.0377 (12)	0.0050 (10)	0.0099 (9)	−0.0077 (9)
C5	0.0536 (14)	0.0733 (18)	0.0436 (13)	−0.0183 (13)	0.0171 (11)	0.0022 (12)
C6	0.0577 (15)	0.0583 (14)	0.0351 (12)	0.0045 (12)	−0.0010 (10)	0.0042 (10)

Geometric parameters (Å, º) top

Ni1—O1W	2.103 (1)	C1—H1B	0.9600
Ni1—O1Wⁱ	2.103 (1)	C1—H1C	0.9600
Ni1—N1	2.122 (2)	C2—H2A	0.9700
Ni1—N1ⁱ	2.122 (2)	C2—H2B	0.9700
Ni1—N2	2.231 (2)	C3—C4	1.501 (3)
Ni1—N2ⁱ	2.231 (2)	C3—H3A	0.9700
O1W—H1W1	0.84 (1)	C3—H3B	0.9700
O1W—H1W2	0.84 (1)	C4—H4A	0.9700
N1—C2	1.480 (2)	C4—H4B	0.9700
N1—C3	1.484 (3)	C5—H5A	0.9600
N1—H1N	0.84 (1)	C5—H5B	0.9600
N2—C4	1.476 (3)	C5—H5C	0.9600
N2—C6	1.477 (3)	C6—H6A	0.9600
N2—C5	1.484 (3)	C6—H6B	0.9600
C1—C2	1.512 (3)	C6—H6C	0.9600
C1—H1A	0.9600

O1Wⁱ—Ni1—O1W	180.0	C2—C1—H1C	109.5
O1Wⁱ—Ni1—N1	92.95 (6)	H1A—C1—H1C	109.5
O1W—Ni1—N1	87.05 (6)	H1B—C1—H1C	109.5
O1Wⁱ—Ni1—N1ⁱ	87.05 (6)	N1—C2—C1	114.00 (17)
O1W—Ni1—N1ⁱ	92.95 (6)	N1—C2—H2A	108.8
N1—Ni1—N1ⁱ	180.0	C1—C2—H2A	108.8
O1Wⁱ—Ni1—N2	90.05 (6)	N1—C2—H2B	108.8
O1W—Ni1—N2	89.95 (6)	C1—C2—H2B	108.8
N1—Ni1—N2	83.08 (6)	H2A—C2—H2B	107.6
N1ⁱ—Ni1—N2	96.92 (6)	N1—C3—C4	110.26 (16)
O1Wⁱ—Ni1—N2ⁱ	89.95 (6)	N1—C3—H3A	109.6
O1W—Ni1—N2ⁱ	90.05 (6)	C4—C3—H3A	109.6
N1—Ni1—N2ⁱ	96.92 (6)	N1—C3—H3B	109.6
N1ⁱ—Ni1—N2ⁱ	83.08 (6)	C4—C3—H3B	109.6
N2—Ni1—N2ⁱ	180.0	H3A—C3—H3B	108.1
Ni1—O1W—H1W1	116.9 (18)	N2—C4—C3	110.61 (17)
Ni1—O1W—H1W2	125.3 (17)	N2—C4—H4A	109.5
H1W1—O1W—H1W2	104 (3)	C3—C4—H4A	109.5
C2—N1—C3	112.42 (16)	N2—C4—H4B	109.5
C2—N1—Ni1	118.68 (13)	C3—C4—H4B	109.5
C3—N1—Ni1	107.30 (12)	H4A—C4—H4B	108.1
C2—N1—H1N	106.3 (14)	N2—C5—H5A	109.5
C3—N1—H1N	109.3 (15)	N2—C5—H5B	109.5
Ni1—N1—H1N	102.1 (14)	H5A—C5—H5B	109.5
C4—N2—C6	109.24 (17)	N2—C5—H5C	109.5
C4—N2—C5	108.09 (17)	H5A—C5—H5C	109.5
C6—N2—C5	106.93 (18)	H5B—C5—H5C	109.5
C4—N2—Ni1	102.09 (12)	N2—C6—H6A	109.5
C6—N2—Ni1	115.32 (13)	N2—C6—H6B	109.5
C5—N2—Ni1	114.83 (13)	H6A—C6—H6B	109.5
C2—C1—H1A	109.5	N2—C6—H6C	109.5
C2—C1—H1B	109.5	H6A—C6—H6C	109.5
H1A—C1—H1B	109.5	H6B—C6—H6C	109.5

O1Wⁱ—Ni1—N1—C2	29.32 (15)	N1ⁱ—Ni1—N2—C6	−80.96 (15)
O1W—Ni1—N1—C2	−150.68 (15)	O1Wⁱ—Ni1—N2—C5	−42.98 (16)
N2—Ni1—N1—C2	119.01 (15)	O1W—Ni1—N2—C5	137.02 (16)
N2ⁱ—Ni1—N1—C2	−60.99 (15)	N1—Ni1—N2—C5	−135.94 (16)
O1Wⁱ—Ni1—N1—C3	−99.41 (13)	N1ⁱ—Ni1—N2—C5	44.06 (16)
O1W—Ni1—N1—C3	80.59 (13)	N2ⁱ—Ni1—N2—C5	114 (100)
N2—Ni1—N1—C3	−9.72 (13)	C3—N1—C2—C1	−72.2 (2)
N2ⁱ—Ni1—N1—C3	170.28 (13)	Ni1—N1—C2—C1	161.47 (17)
O1Wⁱ—Ni1—N2—C4	73.70 (13)	C2—N1—C3—C4	−94.2 (2)
O1W—Ni1—N2—C4	−106.30 (13)	Ni1—N1—C3—C4	38.0 (2)
N1—Ni1—N2—C4	−19.27 (12)	C6—N2—C4—C3	−76.6 (2)
N1ⁱ—Ni1—N2—C4	160.74 (12)	C5—N2—C4—C3	167.39 (18)
O1Wⁱ—Ni1—N2—C6	−168.00 (15)	Ni1—N2—C4—C3	45.94 (19)
O1W—Ni1—N2—C6	12.00 (15)	N1—C3—C4—N2	−59.9 (2)
N1—Ni1—N2—C6	99.04 (15)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···Cl1	0.84 (1)	2.26 (1)	3.095 (2)	174 (2)
O1W—H1W2···Cl1ⁱⁱ	0.84 (1)	2.26 (1)	3.090 (2)	169 (2)
N1—H1N···Cl1	0.84 (1)	2.58 (1)	3.349 (2)	154 (2)

Symmetry code: (ii) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Ni(C₆H₁₆N₂)₂(H₂O)₂]Cl₂
M_r	398.06
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	7.802 (1), 12.550 (1), 9.935 (1)
β (°)	95.750 (1)
V (Å³)	967.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.20 × 0.20 × 0.15

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.856, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5912, 2203, 1843
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.078, 1.04
No. of reflections	2203
No. of parameters	109
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.36

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).

Selected bond lengths (Å) top

Ni1—O1W	2.103 (1)	Ni1—N2	2.231 (2)
Ni1—N1	2.122 (2)