1,4-Diazo­niabi­cyclo­[2.2.2]­octane tri­aqua­tri­chloro­nickelate(II) chloride monohydrate

The title compound, (C₆H₁₄N₂)[NiCl₃(H₂O)₃]Cl·H₂O, contains doubly protonated 1,4-diazo­niabi­cyclo­[2.2.2]­octane (dabconium) (C₆H₁₄N₂)²⁺ cations, mer-[Ni^II(H₂O)₃Cl₃]⁻ octahedra, [mean Ni—O = 2.054 (2) Å and mean Ni—Cl = 2.4272 (6) Å] and additional (non-coordinated) chloride ions and water mol­ecules. These species interact by way of numerous O—H...O, O—H...Cl and N—H...Cl hydrogen bonds and possible C—H...Cl interactions [mean H...Cl = 2.75 Å, mean C...Cl = 3.575 (3) Å and mean C—H...Cl = 142°] to result in a structure with a layered character. (C₆H₁₄N₂)[Ni(H₂O)₃Cl₃]Cl·H₂O is isostructural with its manganese(II)-containing congener.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.027
• wR factor = 0.075
• Data-to-parameter ratio = 21.3

checkCIF/PLATON results

No syntax errors found



Alert level C
CRYSC01_ALERT_1_C The word below has not been recognised as a standard
            identifier.
            bright
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.478
           From the CIF: _refine_ls_abs_structure_Flack_su    0.012
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.99
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.48
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O4     -   H9       =       1.01 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O

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           27.48
           From the CIF: _reflns_number_total               3303
           Count of symmetry unique reflns         1925
           Completeness (_total/calc)            171.58%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1378
           Fraction of Friedel pairs measured     0.716
           Are heavy atom types Z>Si present          yes

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

   2 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
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

The title compound, (I) (Fig. 1), arose as a by-product during our synthetic investigations of organically templated nickel(II) phosphate networks (Guillou et al., 2001). Compound (I) is isostructural with (C₆H₁₄N₂)[Mn(H₂O)₃X₃]·X·H₂O (X = Cl and Br) as described by Feist et al. (1997). Related compounds built up from (C₆H₁₄N₂)²⁺ 1,4-diazoniabicyclo[2.2.2]octane (dabconium) cations, metal-chloride/water polyhedra, and `extra' (non-coordinated) chloride ions include (C₆H₁₄N₂)[Cu(H₂O)₂Cl₃]·Cl·H₂O (Wei & Willett, 1996), containing trigonal bipyramidal [Cu^II(H₂O)₂Cl₃]⁻ groupings, and (C₆H₁₄N₂)[Fe(H₂O)₂Cl₄]·Cl (James et al., 2001), containing trans-[Fe^III(H₂O)₂Cl₄]⁻ octahedra. The structures, spectroscopic properties and thermal behaviour of these types of materials have been reviewed by Bentrup et al. (1999).

In (I), three water molecules [mean Ni—O = 2.054 (2) Å] and three chloride ions [mean Ni—Cl = 2.4272 (6) Å] surround the nickel(II) cation in meridional (mer) conformation [spread of cis bond angles is 86.47 (5)–95.36 (5)°]. The dabconium cation has typical (Bremner & Harrison, 2003) geometrical parameters [mean N—C = 1.502 (3) Å, mean C—C = 1.532 (3) Å, mean C—N—C = 109.6 (2)° and mean N—C—C = 108.1 (2)°]. In addition, an uncoordinated water molecule (O4) and chloride ion (Cl4) are present in the structure.

The component species in (I) interact by way of an extensive network of O—H···O, O—H···Cl, N—H···Cl and N—H···(Cl,Cl) hydrogen bonds and possible C—H···Cl interactions (Table 2). This results in sheets of stoichiometry {[Ni(H₂O)₃Cl₃]·Cl·H₂O}²⁻ propagating in the (001) plane (Fig. 2). The [Ni(H₂O)₃Cl₃]⁻ moieties interact in the [100] direction by way of interoctahedral O3—H8···Cl3ⁱⁱ bonds and a pair of unusual O2—H5···Cl4ⁱⁱ···H4ⁱⁱ—O1ⁱⁱ and O2—H6···O4ⁱⁱⁱ—H10ⁱⁱⁱ···O1ⁱⁱ bonds, which connect adjacent octahedra via the non-coordinated Cl4 and O4 (water) species, respectively. Crosslinking in the [010] direction is provided by O1—H3···Cl3ⁱ O3—H7···Cl4^iv, and O4—H9···Cl2 bonds (see Table 2 for the acceptor-atom symmetry codes). Thus, atom Cl4 accepts three conventional O—H···Cl hydrogen bonds [mean H···Cl4 = 2.20 Å, mean O···Cl4 = 3.094 (2) Å and mean O—H···Cl4 = 172°] in very asymmetric, roughly pyramidal, coordination.

The organic species serves to bridge the {[Ni(H₂O)₃Cl₃)]·Cl·H₂O}²⁻ sheets in the [001] direction. One N/H group makes a simple N1—H1···Cl2 link, and one makes a bifurcated N2—H2···Cl1^v,Cl3^v link (mean Cl1^v···H2···Cl3^v = 87°; see Table 2 for acceptor-atom symmetry codes). The energetics of N—H···Cl—M (M = metal atom) interactions, and their possible role as synthons in supramolecular chemistry are described in detail by Brammer et al. (2002).

A PLATON analysis (Spek, 2003) of (I) indicated the presence (Table 2) of a number of C—H···Cl interactions [mean H···Cl = 2.75 Å, mean C···Cl = 3.575 (3) Å and mean C—H···Cl = 142°]. If these are not merely artefacts of the crystal packing, then atom Cl4 accepts no fewer than five of these weak bonds, in addition to the three O—H···Cl4 links, as shown in Fig. 4 (PLATON van der Waals radius sum of H and Cl = 2.95 Å; next-nearest Cl4···H contact = 3.23 Å).

S2. Experimental

NiCl₂ (10 ml, 1 M), H₃PO₄ (10 ml, 1 M) and dabco (0.5 g, C₆H₁₂N₂) were mixed together in a plastic bottle and heated at 373 K for 24 h, producing a green solution. The solution was cooled to room temperature, and bright- green plate-shaped crystals of (I) grew as water evaporated slowly from the viscous liquors over several weeks.

S3. Refinement

H atoms attached to O atoms were located from difference maps and treated as riding in their as-found locations. H atoms attached to C and N atoms were placed in idealized locations (N—H = 0.93 Å and C—H = 0.99 Å) and treated as riding on their attached atom. The constraint U_iso(H) = 1.2U_eq(parent atom) was applied in all cases. Refinement of the Flack (1983) absolute structure parameter to 0.478 (12) indicated a merohedrally twinned crystal.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: COLLECT; data reduction: COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and ATOMS (Shape software, 1999); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The asymmetric unit of (I) (50% displacement ellipsoids) H atoms are shown as arbitrary spheres and H atoms attached to C atoms have been omitted for clarity Hydrogen bonds are indicated by dashed lines.
	Fig. 2. A detail of (I), showing part of an {[Ni(H2O)3Cl3]·Cl·H2O}^2− sheet viewed down [001]. Colour key: [Ni(H2O)3Cl3)]^− octahedra green, Cl atoms green, O atoms red and H atoms grey (all radii arbitrary). The H···A portions of the H···O and H···Cl hydrogen bonds are coloured yellow and orange, respectively. Symmetry codes as in Table 2.
	Fig. 3. The unit-cell packing in (I), viewed down [010]. Colour key as in Fig. 2; additionally, C atoms blue, N atoms purple. H atoms attached to C atoms have been omitted for clarity.
	Fig. 4. The environment of atom Cl4 in (I), showing the O—H···Cl hydrogen bonds and possible C—H···Cl interactions associated with this species. Colour key as in Fig. 2; additionally, the H···Cl portions of the C—H···Cl contacts are highlighted in blue. [Symmetry codes: (i) 1/2 + x, 1/2 − y, −z; (ii) 1 − x, 1/2 + y, 1/2 − z; (iii) x − 1/2, 1/2 − y, −z; (iv) x − 1, y, z.]

(I)

Crystal data

(C6H14N2)[NiCl3(H2O)3]Cl·H2O	F(000) = 800
Mr = 386.77	Dx = 1.772 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6654 reflections
a = 6.7019 (1) Å	θ = 2.9–27.5°
b = 11.9573 (2) Å	µ = 2.08 mm^−1
c = 18.0923 (4) Å	T = 120 K
V = 1449.86 (5) Å^3	Block, bright green
Z = 4	0.35 × 0.26 × 0.14 mm

Data collection

Nonius KappaCCD diffractometer	3303 independent reflections
Radiation source: fine-focus sealed tube	3224 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ω and ϕ scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −8→8
Tmin = 0.517, Tmax = 0.745	k = −15→12
10211 measured reflections	l = −23→23

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap (O-H) and geom (N-H and C-H)
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0414P)^2 + 0.3311P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max = 0.001
3303 reflections	Δρmax = 0.44 e Å^−3
155 parameters	Δρmin = −0.78 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1395 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.478 (12)

Special details

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	0.68573 (4)	0.16979 (2)	0.255292 (16)	0.00813 (9)
Cl1	0.69310 (9)	0.19536 (5)	0.38754 (3)	0.01208 (12)
Cl2	0.71416 (9)	0.14849 (5)	0.12281 (3)	0.01140 (13)
Cl3	0.37583 (8)	0.06130 (5)	0.26128 (3)	0.01241 (13)
Cl4	0.20610 (9)	0.35228 (5)	0.12028 (3)	0.01266 (13)
O1	0.5091 (2)	0.30839 (14)	0.24509 (9)	0.0106 (3)
H3	0.5508	0.3767	0.2441	0.013*
H4	0.4154	0.3219	0.2073	0.013*
O2	0.9300 (3)	0.27199 (15)	0.25002 (10)	0.0151 (4)
H5	0.9889	0.3000	0.2147	0.018*
H6	1.0020	0.2924	0.2777	0.018*
O3	0.8736 (3)	0.03279 (14)	0.26334 (9)	0.0127 (4)
H7	0.8345	−0.0165	0.3020	0.015*
H8	1.0022	0.0558	0.2596	0.015*
O4	0.7891 (3)	−0.14541 (15)	0.14797 (9)	0.0158 (4)
H9	0.7936	−0.0702	0.1739	0.019*
H10	0.6946	−0.1759	0.1742	0.019*
N1	0.3542 (3)	0.03774 (18)	0.04940 (11)	0.0125 (4)
H1	0.4358	0.0657	0.0867	0.015*
N2	0.1371 (3)	−0.03752 (17)	−0.05157 (10)	0.0104 (4)
H2	0.0554	−0.0653	−0.0888	0.013*
C1	0.2988 (4)	0.13090 (19)	−0.00241 (13)	0.0132 (4)
H11	0.4194	0.1736	−0.0167	0.016*
H12	0.2043	0.1827	0.0220	0.016*
C2	0.4651 (4)	−0.0518 (2)	0.00744 (14)	0.0139 (5)
H21	0.5248	−0.1060	0.0424	0.017*
H22	0.5738	−0.0178	−0.0220	0.017*
C3	0.1691 (4)	−0.0099 (2)	0.08298 (13)	0.0155 (5)
H31	0.1094	0.0443	0.1179	0.019*
H32	0.2008	−0.0794	0.1104	0.019*
C4	0.2018 (4)	0.0790 (2)	−0.07099 (13)	0.0123 (5)
H41	0.0852	0.1241	−0.0865	0.015*
H42	0.2985	0.0770	−0.1123	0.015*
C5	0.3169 (4)	−0.1113 (2)	−0.04365 (13)	0.0139 (5)
H51	0.3784	−0.1247	−0.0926	0.017*
H52	0.2780	−0.1843	−0.0223	0.017*
C6	0.0230 (4)	−0.0351 (2)	0.02005 (13)	0.0157 (5)
H61	−0.0424	−0.1082	0.0285	0.019*
H62	−0.0815	0.0233	0.0180	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.00727 (15)	0.00854 (15)	0.00858 (14)	−0.00022 (10)	0.00030 (12)	0.00027 (11)
Cl1	0.0137 (3)	0.0143 (3)	0.0082 (2)	−0.0029 (2)	0.0006 (2)	0.0003 (2)
Cl2	0.0111 (3)	0.0149 (3)	0.0083 (2)	−0.0014 (2)	−0.0002 (2)	−0.00116 (19)
Cl3	0.0097 (3)	0.0113 (3)	0.0162 (3)	−0.0018 (2)	0.0002 (2)	0.0008 (2)
Cl4	0.0112 (3)	0.0166 (3)	0.0102 (2)	0.0004 (2)	0.0000 (2)	−0.0017 (2)
O1	0.0096 (7)	0.0098 (7)	0.0126 (8)	−0.0011 (6)	−0.0006 (7)	0.0006 (6)
O2	0.0136 (8)	0.0221 (9)	0.0097 (7)	−0.0091 (7)	0.0012 (8)	0.0005 (7)
O3	0.0092 (7)	0.0150 (9)	0.0141 (8)	0.0026 (6)	0.0022 (7)	0.0035 (7)
O4	0.0143 (9)	0.0201 (9)	0.0131 (8)	−0.0013 (8)	0.0027 (8)	0.0009 (7)
N1	0.0114 (10)	0.0143 (10)	0.0118 (9)	−0.0004 (8)	−0.0059 (8)	−0.0016 (8)
N2	0.0099 (10)	0.0144 (10)	0.0071 (8)	−0.0029 (8)	0.0001 (8)	−0.0026 (7)
C1	0.0135 (11)	0.0102 (10)	0.0160 (11)	0.0000 (9)	−0.0009 (11)	0.0001 (9)
C2	0.0123 (11)	0.0154 (11)	0.0141 (11)	0.0039 (10)	0.0009 (10)	0.0002 (10)
C3	0.0140 (13)	0.0214 (13)	0.0112 (10)	−0.0039 (11)	0.0005 (10)	−0.0011 (10)
C4	0.0115 (11)	0.0130 (11)	0.0124 (10)	0.0015 (10)	−0.0019 (10)	0.0032 (9)
C5	0.0143 (11)	0.0139 (11)	0.0136 (10)	0.0025 (10)	−0.0024 (11)	−0.0030 (9)
C6	0.0115 (12)	0.0258 (14)	0.0097 (11)	−0.0051 (10)	0.0044 (10)	−0.0045 (9)

Geometric parameters (Å, º)

Ni1—O1	2.0451 (17)	N2—C4	1.501 (3)
Ni1—O2	2.0453 (17)	N2—C6	1.505 (3)
Ni1—O3	2.0713 (16)	N2—H2	0.9300
Ni1—Cl1	2.4127 (6)	C1—C4	1.532 (3)
Ni1—Cl2	2.4178 (6)	C1—H11	0.9900
Ni1—Cl3	2.4512 (6)	C1—H12	0.9900
O1—H3	0.8631	C2—C5	1.533 (3)
O1—H4	0.9427	C2—H21	0.9900
O2—H5	0.8217	C2—H22	0.9900
O2—H6	0.7372	C3—C6	1.531 (3)
O3—H7	0.9516	C3—H31	0.9900
O3—H8	0.9074	C3—H32	0.9900
O4—H9	1.0153	C4—H41	0.9900
O4—H10	0.8714	C4—H42	0.9900
N1—C3	1.495 (3)	C5—H51	0.9900
N1—C1	1.503 (3)	C5—H52	0.9900
N1—C2	1.508 (3)	C6—H61	0.9900
N1—H1	0.9300	C6—H62	0.9900
N2—C5	1.500 (3)
O1—Ni1—O2	88.58 (7)	N1—C1—C4	108.04 (18)
O1—Ni1—O3	177.70 (7)	N1—C1—H11	110.1
O2—Ni1—O3	89.38 (7)	C4—C1—H11	110.1
O1—Ni1—Cl1	89.92 (5)	N1—C1—H12	110.1
O2—Ni1—Cl1	87.37 (5)	C4—C1—H12	110.1
O3—Ni1—Cl1	91.04 (5)	H11—C1—H12	108.4
O1—Ni1—Cl2	92.38 (5)	N1—C2—C5	108.28 (19)
O2—Ni1—Cl2	87.34 (5)	N1—C2—H21	110.0
O3—Ni1—Cl2	86.47 (5)	C5—C2—H21	110.0
Cl1—Ni1—Cl2	174.18 (2)	N1—C2—H22	110.0
O1—Ni1—Cl3	86.69 (5)	C5—C2—H22	110.0
O2—Ni1—Cl3	175.26 (6)	H21—C2—H22	108.4
O3—Ni1—Cl3	95.36 (5)	N1—C3—C6	107.66 (19)
Cl1—Ni1—Cl3	92.33 (2)	N1—C3—H31	110.2
Cl2—Ni1—Cl3	93.14 (2)	C6—C3—H31	110.2
Ni1—O1—H3	125.5	N1—C3—H32	110.2
Ni1—O1—H4	126.2	C6—C3—H32	110.2
H3—O1—H4	92.2	H31—C3—H32	108.5
Ni1—O2—H5	131.6	N2—C4—C1	108.01 (18)
Ni1—O2—H6	133.6	N2—C4—H41	110.1
H5—O2—H6	94.6	C1—C4—H41	110.1
Ni1—O3—H7	112.0	N2—C4—H42	110.1
Ni1—O3—H8	109.4	C1—C4—H42	110.1
H7—O3—H8	120.2	H41—C4—H42	108.4
H9—O4—H10	98.0	N2—C5—C2	107.77 (19)
C3—N1—C1	109.3 (2)	N2—C5—H51	110.2
C3—N1—C2	110.08 (19)	C2—C5—H51	110.2
C1—N1—C2	109.50 (19)	N2—C5—H52	110.2
C3—N1—H1	109.3	C2—C5—H52	110.2
C1—N1—H1	109.3	H51—C5—H52	108.5
C2—N1—H1	109.3	N2—C6—C3	108.6 (2)
C5—N2—C4	109.7 (2)	N2—C6—H61	110.0
C5—N2—C6	109.70 (18)	C3—C6—H61	110.0
C4—N2—C6	109.29 (19)	N2—C6—H62	110.0
C5—N2—H2	109.4	C3—C6—H62	110.0
C4—N2—H2	109.4	H61—C6—H62	108.3
C6—N2—H2	109.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H3···Cl3^i	0.86	2.26	3.1231 (17)	174
O1—H4···Cl4	0.94	2.14	3.0817 (18)	179
O2—H5···Cl4^ii	0.82	2.33	3.1392 (18)	168
O2—H6···O4^iii	0.74	2.08	2.815 (3)	177
O3—H7···Cl4^iv	0.95	2.12	3.0623 (17)	168
O3—H8···Cl3^ii	0.91	2.50	3.3833 (17)	163
O4—H9···O3	1.02	2.10	3.036 (2)	152
O4—H9···Cl2	1.02	2.82	3.5791 (18)	132
O4—H10···O1^iv	0.87	2.01	2.836 (2)	158
N1—H1···Cl2	0.93	2.21	3.056 (2)	151
N2—H2···Cl1^v	0.93	2.32	3.110 (2)	143
N2—H2···Cl3^v	0.93	2.75	3.399 (2)	128
C1—H11···Cl4^vi	0.99	2.70	3.470 (3)	135
C1—H12···Cl4	0.99	2.70	3.510 (2)	140
C2—H22···Cl4^vi	0.99	2.80	3.693 (3)	150
C3—H32···Cl1^iv	0.99	2.79	3.682 (3)	151
C4—H41···Cl4^vii	0.99	2.63	3.537 (3)	153
C6—H62···Cl2^viii	0.99	2.78	3.544 (3)	135
C4—H42···Cl4^vi	0.99	2.86	3.591 (3)	131

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