Diaqua­(cyclo­hexane-1,2-diamine-κ²N,N′)(N,N,N′,N′-tetra­methyl­ethylenediamine-κ²N,N′)nickel(II) dichloride dihydrate

In the title compound, [Ni(C₆H₁₄N₂)(C₆H₁₆N₂)(H₂O)₂]Cl₂·2H₂O, the cation lies about a twofold rotation axis. The octa­hedral complex cation is linked to the Cl⁻ anions by hydrogen bonds to form a layer structure.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.025
• wR factor = 0.073
• Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT110_ALERT_2_B ADDSYM Detects Potential Lattice Centering or Halving .   ?

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
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 =          3
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N2     -   C6      ..       5.26 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   O1W     ..       8.20 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N2
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          6
PLAT732_ALERT_1_C Angle   Calc      111(4), Rep   111.4(18) ......       2.22 su-Ra
              H2W1 -O2W  -H2W2    1.555   1.555   1.555

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.50
           From the CIF: _reflns_number_total               2217
           Count of symmetry unique reflns         1274
           Completeness (_total/calc)            174.02%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       943
           Fraction of Friedel pairs measured     0.740
           Are heavy atom types Z>Si present        yes
PLAT792_ALERT_1_G Check the Absolute Configuration of C1     = ...          R
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (2)       1.78
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         11

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

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

---

S1. Comment

The crystal structures of few diamine complexes of nickel have been reported; a recent study described the mixed-ligand diaqua complex of substituted ethylenediamines (Liang et al., 2007). The present mixed ligand complex also has coordinated water. The six-coordinate cation and free chloride anions are linked by hydrogen bonds into a layers structure.

Related literature

For other nickel dichloride complexes of substituted ethylenediamines, see Liang et al. (2007).

S2. Experimental

To an ethanol solution (5 ml) of nickel chloride hexahydrate (0.238 g, 1 mmol) was added an ethanol solution (10 ml) of 1,2-diaminocyclohexane (0.12 ml, 1 mmol) and N,N,N',N'-tetramethyethylenediamine (0.15 ml, 1 mmol). The solution was filtered. Ether was diffused into the filtrate; blue crystals were isolated in 50% yield after a week.

S3. Refinement

Carbon-bound hydrogen atoms were placed at calculated positions in the riding model approximation [C—H 0.96 to 0.98 Å, U(H) = 1.2 or 1.5 U_eq(C)]. The water and amino H atoms were located in a difference Fourier map, and were refined with a distance restraint of O–H = N–H = 0.85±0.01 Å.

The C–C bond in the ethylenediamine part of the molecule was restrained to 1.500±0.002 Å; a somewhat tight restraint was necessary.

Computing details

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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

Fig. 1. Thermal ellipsoid plot. The molecule lies about a twofold rotation axis, and the unlabeled atoms are related to the labeled ones by 1 - x, 1 - y, z.

Diaqua(cyclohexane-1,2-diamine-κ²N,N')(N,N,N',N'- tetramethylethylenediamine-κ²N,N')nickel(II) dichloride dihydrate

Crystal data

[Ni(C6H14N2)(C6H16N2)(H2O)2]Cl2·2H2O	F(000) = 928
Mr = 432.07	Dx = 1.353 Mg m^−3
Orthorhombic, Aba2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A 2 -2ac	Cell parameters from 4527 reflections
a = 14.159 (1) Å	θ = 2.7–27.4°
b = 9.843 (1) Å	µ = 1.19 mm^−1
c = 15.221 (1) Å	T = 295 K
V = 2121.4 (3) Å^3	Prism, blue
Z = 4	0.30 × 0.30 × 0.20 mm

Data collection

Bruker APEX area-detector diffractometer	2217 independent reflections
Radiation source: fine-focus sealed tube	2103 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
φ and ω scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→16
Tmin = 0.702, Tmax = 0.797	k = −12→8
6267 measured reflections	l = −19→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.073	w = 1/[σ^2(Fo^2) + (0.0479P)^2 + 0.4568P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
2217 reflections	Δρmax = 0.50 e Å^−3
129 parameters	Δρmin = −0.37 e Å^−3
11 restraints	Absolute structure: Flack (1983), with 944 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (1)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.49999 (2)	0.02217 (10)
Cl1	0.31836 (4)	0.83038 (6)	0.61089 (9)	0.05226 (16)
O1W	0.49376 (9)	0.71842 (15)	0.5054 (2)	0.0329 (3)
O2W	0.63652 (17)	0.8514 (2)	0.5887 (2)	0.0839 (10)
N1	0.4022 (2)	0.49706 (13)	0.60291 (18)	0.0270 (5)
N2	0.3974 (2)	0.49513 (15)	0.3947 (2)	0.0339 (6)
C1	0.45361 (14)	0.4615 (2)	0.68462 (15)	0.0283 (4)
H1	0.4667	0.3638	0.6847	0.034*
C2	0.3966 (2)	0.49752 (19)	0.76682 (18)	0.0408 (6)
H2A	0.3804	0.5932	0.7654	0.049*
H2B	0.3383	0.4457	0.7671	0.049*
C3	0.4519 (2)	0.4673 (3)	0.85041 (18)	0.0520 (6)
H3A	0.4164	0.4998	0.9007	0.062*
H3B	0.4592	0.3697	0.8565	0.062*
C4	0.32382 (19)	0.5997 (3)	0.4023 (2)	0.0580 (8)
H4A	0.2809	0.5920	0.3537	0.087*
H4B	0.3525	0.6881	0.4018	0.087*
H4C	0.2899	0.5874	0.4563	0.087*
C5	0.3493 (2)	0.3631 (3)	0.3864 (2)	0.0549 (7)
H5A	0.3051	0.3668	0.3387	0.082*
H5B	0.3164	0.3430	0.4400	0.082*
H5C	0.3952	0.2934	0.3751	0.082*
C6	0.45062 (13)	0.5269 (4)	0.3154 (2)	0.0640 (9)
H6A	0.4529	0.6248	0.3084	0.077*
H6B	0.4173	0.4899	0.2652	0.077*
H1W1	0.5390 (12)	0.760 (3)	0.5303 (18)	0.062 (10)*
H1W2	0.4418 (10)	0.748 (3)	0.5284 (19)	0.070 (11)*
H2W1	0.6916 (15)	0.818 (4)	0.589 (5)	0.17 (3)*
H2W2	0.638 (3)	0.9368 (10)	0.587 (3)	0.103 (14)*
H1N1	0.3817 (15)	0.5779 (11)	0.6136 (18)	0.035 (6)*
H1N2	0.3567 (14)	0.4420 (18)	0.609 (3)	0.068 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01982 (15)	0.02320 (15)	0.02349 (15)	0.00020 (10)	0.000	0.000
Cl1	0.0385 (3)	0.0394 (3)	0.0788 (4)	0.0064 (2)	0.0048 (3)	−0.0112 (3)
O1W	0.0306 (6)	0.0288 (6)	0.0393 (9)	0.0005 (5)	0.0005 (7)	0.0019 (10)
O2W	0.0492 (11)	0.0482 (11)	0.154 (3)	−0.0034 (10)	−0.0260 (14)	−0.0254 (14)
N1	0.0215 (12)	0.0280 (11)	0.0313 (13)	−0.0018 (5)	0.0014 (11)	−0.0013 (6)
N2	0.0307 (14)	0.0373 (13)	0.0338 (15)	−0.0002 (6)	−0.0075 (13)	−0.0009 (6)
C1	0.0297 (11)	0.0261 (8)	0.0290 (10)	−0.0011 (9)	0.0014 (9)	0.0009 (9)
C2	0.0420 (14)	0.0450 (13)	0.0354 (13)	0.0001 (7)	0.0129 (11)	−0.0014 (9)
C3	0.0686 (19)	0.0550 (13)	0.0325 (12)	0.0040 (14)	0.0104 (12)	0.0025 (11)
C4	0.0478 (14)	0.0505 (14)	0.0756 (19)	0.0168 (11)	−0.0311 (14)	−0.0161 (13)
C5	0.0621 (15)	0.0419 (12)	0.0608 (15)	−0.0105 (11)	−0.0321 (14)	−0.0009 (11)
C6	0.060 (2)	0.097 (2)	0.0350 (16)	0.0045 (17)	−0.0107 (15)	0.0078 (15)

Geometric parameters (Å, º)

Ni1—N1^i	2.091 (3)	C1—C2	1.530 (3)
Ni1—N1	2.091 (3)	C1—H1	0.9800
Ni1—O1W^i	2.153 (2)	C2—C3	1.523 (4)
Ni1—N2^i	2.163 (3)	C2—H2A	0.9700
Ni1—N2	2.163 (3)	C2—H2B	0.9700
Ni1—O1W	2.153 (2)	C3—C3^i	1.506 (7)
O1W—H1W1	0.850 (10)	C3—H3A	0.9700
O1W—H1W2	0.865 (10)	C3—H3B	0.9700
O2W—H2W1	0.846 (10)	C4—H4A	0.9600
O2W—H2W2	0.841 (10)	C4—H4B	0.9600
N1—C1	1.483 (4)	C4—H4C	0.9600
N1—H1N1	0.862 (9)	C5—H5A	0.9600
N1—H1N2	0.847 (10)	C5—H5B	0.9600
N2—C6	1.457 (4)	C5—H5C	0.9600
N2—C4	1.470 (3)	C6—C6^i	1.496 (2)
N2—C5	1.473 (3)	C6—H6A	0.9700
C1—C1^i	1.516 (4)	C6—H6B	0.9700
N1^i—Ni1—N1	82.98 (15)	N1—C1—H1	109.0
N1^i—Ni1—O1W^i	87.59 (7)	C1^i—C1—H1	109.0
N1—Ni1—O1W^i	89.12 (7)	C2—C1—H1	109.0
N1^i—Ni1—O1W	89.12 (7)	C3—C2—C1	111.5 (2)
N1—Ni1—O1W	87.59 (7)	C3—C2—H2A	109.3
O1W^i—Ni1—O1W	175.61 (16)	C1—C2—H2A	109.3
N1^i—Ni1—N2^i	96.31 (6)	C3—C2—H2B	109.3
N1—Ni1—N2^i	179.15 (13)	C1—C2—H2B	109.3
O1W^i—Ni1—N2^i	91.32 (8)	H2A—C2—H2B	108.0
O1W—Ni1—N2^i	91.94 (7)	C3^i—C3—C2	112.41 (18)
N1^i—Ni1—N2	179.15 (12)	C3^i—C3—H3A	109.1
N1—Ni1—N2	96.31 (6)	C2—C3—H3A	109.1
O1W^i—Ni1—N2	91.94 (7)	C3^i—C3—H3B	109.1
O1W—Ni1—N2	91.32 (8)	C2—C3—H3B	109.1
N2^i—Ni1—N2	84.41 (16)	H3A—C3—H3B	107.9
Ni1—O1W—H1W1	118 (2)	N2—C4—H4A	109.5
Ni1—O1W—H1W2	113 (2)	N2—C4—H4B	109.5
H1W1—O1W—H1W2	107.3 (16)	H4A—C4—H4B	109.5
H2W1—O2W—H2W2	111.4 (18)	N2—C4—H4C	109.5
C1—N1—Ni1	107.83 (18)	H4A—C4—H4C	109.5
C1—N1—H1N1	103.0 (19)	H4B—C4—H4C	109.5
Ni1—N1—H1N1	110.5 (16)	N2—C5—H5A	109.5
C1—N1—H1N2	97 (3)	N2—C5—H5B	109.5
Ni1—N1—H1N2	127 (2)	H5A—C5—H5B	109.5
H1N1—N1—H1N2	108.3 (15)	N2—C5—H5C	109.5
C6—N2—C4	106.3 (2)	H5A—C5—H5C	109.5
C6—N2—C5	110.9 (3)	H5B—C5—H5C	109.5
C4—N2—C5	107.3 (3)	N2—C6—C6^i	114.0 (2)
C6—N2—Ni1	105.19 (19)	N2—C6—H6A	108.7
C4—N2—Ni1	113.75 (19)	C6^i—C6—H6A	108.7
C5—N2—Ni1	113.20 (17)	N2—C6—H6B	108.7
N1—C1—C1^i	107.93 (16)	C6^i—C6—H6B	108.7
N1—C1—C2	111.8 (2)	H6A—C6—H6B	107.6
C1^i—C1—C2	109.96 (16)
N1^i—Ni1—N1—C1	−14.97 (10)	N1—Ni1—N2—C5	−71.0 (2)
O1W^i—Ni1—N1—C1	72.71 (13)	O1W^i—Ni1—N2—C5	18.3 (2)
O1W—Ni1—N1—C1	−104.38 (13)	O1W—Ni1—N2—C5	−158.7 (2)
N2—Ni1—N1—C1	164.56 (12)	N2^i—Ni1—N2—C5	109.5 (2)
N1—Ni1—N2—C6	167.72 (18)	Ni1—N1—C1—C1^i	41.8 (2)
O1W^i—Ni1—N2—C6	−102.95 (18)	Ni1—N1—C1—C2	162.90 (13)
O1W—Ni1—N2—C6	80.00 (19)	N1—C1—C2—C3	−177.1 (2)
N2^i—Ni1—N2—C6	−11.82 (16)	C1^i—C1—C2—C3	−57.3 (3)
N1—Ni1—N2—C4	51.8 (2)	C1—C2—C3—C3^i	53.0 (3)
O1W^i—Ni1—N2—C4	141.1 (2)	C4—N2—C6—C6^i	155.4 (4)
O1W—Ni1—N2—C4	−35.9 (2)	C5—N2—C6—C6^i	−88.3 (5)
N2^i—Ni1—N2—C4	−127.8 (2)	Ni1—N2—C6—C6^i	34.5 (5)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O2W	0.85 (1)	1.87 (1)	2.721 (3)	178 (3)
O1W—H1W2···Cl1	0.87 (1)	2.30 (1)	3.156 (2)	170 (3)
O2W—H2W1···Cl1^ii	0.85 (1)	2.34 (2)	3.153 (2)	162 (5)
O2W—H2W2···Cl1^iii	0.84 (1)	2.40 (2)	3.215 (2)	163 (4)
N1—H1N1···Cl1	0.86 (1)	2.64 (1)	3.4910 (17)	168 (3)
N1—H1N2···Cl1^iv	0.85 (1)	2.71 (1)	3.529 (3)	163 (3)

Symmetry codes: (ii) x+1/2, −y+3/2, z; (iii) −x+1, −y+2, z; (iv) −x+1/2, y−1/2, z.