Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803018555/br6114sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803018555/br6114Isup2.hkl |
CCDC reference: 222824
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (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
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.
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 Uiso(H) = 1.2Ueq(parent atom) was applied in all cases. Refinement of the Flack (1983) absolute structure parameter to 0.478 (12) indicated a merohedrally twinned crystal.
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.
(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) Å3 | Block, bright green |
Z = 4 | 0.35 × 0.26 × 0.14 mm |
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 on F2 | 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[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.0414P)2 + 0.3311P] where P = (Fo2 + 2Fc2)/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) |
(C6H14N2)[NiCl3(H2O)3]Cl·H2O | V = 1449.86 (5) Å3 |
Mr = 386.77 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.7019 (1) Å | µ = 2.08 mm−1 |
b = 11.9573 (2) Å | T = 120 K |
c = 18.0923 (4) Å | 0.35 × 0.26 × 0.14 mm |
Nonius KappaCCD diffractometer | 3303 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 3224 reflections with I > 2σ(I) |
Tmin = 0.517, Tmax = 0.745 | Rint = 0.044 |
10211 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.075 | Δρmax = 0.44 e Å−3 |
S = 1.15 | Δρmin = −0.78 e Å−3 |
3303 reflections | Absolute structure: Flack (1983), 1395 Friedel pairs |
155 parameters | Absolute structure parameter: 0.478 (12) |
0 restraints |
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 | ||
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H3···Cl3i | 0.86 | 2.26 | 3.1231 (17) | 174 |
O1—H4···Cl4 | 0.94 | 2.14 | 3.0817 (18) | 179 |
O2—H5···Cl4ii | 0.82 | 2.33 | 3.1392 (18) | 168 |
O2—H6···O4iii | 0.74 | 2.08 | 2.815 (3) | 177 |
O3—H7···Cl4iv | 0.95 | 2.12 | 3.0623 (17) | 168 |
O3—H8···Cl3ii | 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···O1iv | 0.87 | 2.01 | 2.836 (2) | 158 |
N1—H1···Cl2 | 0.93 | 2.21 | 3.056 (2) | 151 |
N2—H2···Cl1v | 0.93 | 2.32 | 3.110 (2) | 143 |
N2—H2···Cl3v | 0.93 | 2.75 | 3.399 (2) | 128 |
C1—H11···Cl4vi | 0.99 | 2.70 | 3.470 (3) | 135 |
C1—H12···Cl4 | 0.99 | 2.70 | 3.510 (2) | 140 |
C2—H22···Cl4vi | 0.99 | 2.80 | 3.693 (3) | 150 |
C3—H32···Cl1iv | 0.99 | 2.79 | 3.682 (3) | 151 |
C4—H41···Cl4vii | 0.99 | 2.63 | 3.537 (3) | 153 |
C6—H62···Cl2viii | 0.99 | 2.78 | 3.544 (3) | 135 |
C4—H42···Cl4vi | 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. |
Experimental details
Crystal data | |
Chemical formula | (C6H14N2)[NiCl3(H2O)3]Cl·H2O |
Mr | 386.77 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 120 |
a, b, c (Å) | 6.7019 (1), 11.9573 (2), 18.0923 (4) |
V (Å3) | 1449.86 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.08 |
Crystal size (mm) | 0.35 × 0.26 × 0.14 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.517, 0.745 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10211, 3303, 3224 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.075, 1.15 |
No. of reflections | 3303 |
No. of parameters | 155 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.78 |
Absolute structure | Flack (1983), 1395 Friedel pairs |
Absolute structure parameter | 0.478 (12) |
Computer programs: COLLECT (Nonius, 1999), COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and ATOMS (Shape software, 1999), SHELXL97.
Ni1—O1 | 2.0451 (17) | Ni1—Cl1 | 2.4127 (6) |
Ni1—O2 | 2.0453 (17) | Ni1—Cl2 | 2.4178 (6) |
Ni1—O3 | 2.0713 (16) | Ni1—Cl3 | 2.4512 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H3···Cl3i | 0.86 | 2.26 | 3.1231 (17) | 174 |
O1—H4···Cl4 | 0.94 | 2.14 | 3.0817 (18) | 179 |
O2—H5···Cl4ii | 0.82 | 2.33 | 3.1392 (18) | 168 |
O2—H6···O4iii | 0.74 | 2.08 | 2.815 (3) | 177 |
O3—H7···Cl4iv | 0.95 | 2.12 | 3.0623 (17) | 168 |
O3—H8···Cl3ii | 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···O1iv | 0.87 | 2.01 | 2.836 (2) | 158 |
N1—H1···Cl2 | 0.93 | 2.21 | 3.056 (2) | 151 |
N2—H2···Cl1v | 0.93 | 2.32 | 3.110 (2) | 143 |
N2—H2···Cl3v | 0.93 | 2.75 | 3.399 (2) | 128 |
C1—H11···Cl4vi | 0.99 | 2.70 | 3.470 (3) | 135 |
C1—H12···Cl4 | 0.99 | 2.70 | 3.510 (2) | 140 |
C2—H22···Cl4vi | 0.99 | 2.80 | 3.693 (3) | 150 |
C3—H32···Cl1iv | 0.99 | 2.79 | 3.682 (3) | 151 |
C4—H41···Cl4vii | 0.99 | 2.63 | 3.537 (3) | 153 |
C6—H62···Cl2viii | 0.99 | 2.78 | 3.544 (3) | 135 |
C4—H42···Cl4vi | 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. |
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 [CuII(H2O)2Cl3]− groupings, and (C6H14N2)[Fe(H2O)2Cl4]·Cl (James et al., 2001), containing trans-[FeIII(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···Cl4iv, 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···Cl1v,Cl3v link (mean Cl1v···H2···Cl3v = 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).