Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704130X/zl2059sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704130X/zl2059Isup2.hkl |
CCDC reference: 660166
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.005 Å
- R factor = 0.041
- wR factor = 0.100
- Data-to-parameter ratio = 15.4
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 12
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The crystal structure of the organic part of the title compound was published by Arkenbout et al. (2007). Other examples of organic–inorganic hybrids are discussed by Papavassiliou (1997) and Mitzi (1999).
For related literature, see: Allen (2002); Bondi (1964).
The organic part was synthesized as described as in Arkenbout et al. (2007). The (2-phenylethyl)ammonium chloride was dissolved in water with NiCl2·6H2O in an approximate molar ratio of 2:1 with a slight excess of the Ni compound to account for the difference in solubility. After slow evaporation of the water blue crystals were obtained.
The hydrogen atoms of the C—H and N—H bonds were generated by geometrical considerations, constrained to idealized geometries, and allowed to ride on the carrier atoms with an isotropic displacement parameter related to the equivalent displacement parameter of their carrier atoms, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C and ammonium). The methyl-groups and ammonium were refined as rigid groups, which were allowed to rotate freely. Assigned values of bond distances: secondary C—H2 = 0.99 Å, methyl C—H3 = 0.98 Å and aromatic C—H = 0.95 Å, N—H = 0.91 Å. The hydrogen atoms of the O—H bonds were restrained to a target value of 0.84 (2) Å and their isotropic displacement parameters were set to 1.5 times the Ueq value of their parent atom.
There is an interest to develop new multifunctional semiconductors that are easy to process and contain magnetic components. We present here the crystal structure of the title compound, which is a solution grown system build of organic conjugated molecules and paramagnetic Ni(II) ions. Every nickel(II) ion is surrounded by an octahedron in which 4 water molecules and 2 chlorine atoms are present. These octahedra are part of a complex network of hydrogen bonds between the ammonium groups, the water molecules and the free clorine ions, which stabilize this structure. The blue crystals of the title compound loose 20% of their weight when heated up to 350 K, leaving a pink amorphous powder, suggesting the evaporation of the crystal water. The material is paramagnetic down to 5 K. This lack of magnetic ordering can be explained by the large separation between the magnetic ions (d>6.631 Å) due to which the magnetic interactions are small and thus no magnetic ordering occurs.
The crystal structure of the organic part of the title compound was published by Arkenbout et al. (2007). Other examples of organic–inorganic hybrids are discussed by Papavassiliou (1997) and Mitzi (1999).
For related literature, see: Allen (2002); Bondi (1964).
Data collection: SMART (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2006); data reduction: SAINT-Plus (Bruker, 2006); program(s) used to solve structure: DIRDIF99 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2006) and PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).
(C8H12N)2[NiCl2(H2O)4]Cl2·2H2O | F(000) = 1160 |
Mr = 552.98 | The final unit cell was obtained from the xyz centroids of
3790 reflections after integration using the SAINTPLUS
software package (Bruker, 2000). Reduced cell calculations did not indicate any higher metric lattice symmetry and examination of the finalatomic coordinates of the structure did not yield extra symmetry elements [Spek, A. L. (1988). J. Appl. Cryst. 21, 578–579; Le Page, Y. (1987). J. Appl. Cryst. 20, 264–269; Le Page, Y. (1988). J. Appl. Cryst. 21, 983–984] |
Monoclinic, P21/c | Dx = 1.498 Mg m−3 |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6977 (10) Å | Cell parameters from 3790 reflections |
b = 29.540 (4) Å | θ = 2.8–28.3° |
c = 10.7808 (15) Å | µ = 1.26 mm−1 |
β = 90.760 (2)° | T = 100 K |
V = 2451.2 (6) Å3 | Platelet, green |
Z = 4 | 0.36 × 0.15 × 0.04 mm |
Bruker SMART APEX CCD area-detector diffractometer | 4617 independent reflections |
Radiation source: fine focus sealed Siemens Mo tube | 2752 reflections with I > 2σ(I) |
Parallel mounted graphite monochromator | Rint = 0.071 |
Detector resolution: 66.06 pixels mm-1 | θmax = 25.7°, θmin = 2.7° |
φ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | k = −36→36 |
Tmin = 0.625, Tmax = 0.951 | l = −13→12 |
17481 measured reflections |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | w = 1/[σ2(Fo2)] |
4617 reflections | (Δ/σ)max < 0.001 |
300 parameters | Δρmax = 0.49 e Å−3 |
12 restraints | Δρmin = −0.37 e Å−3 |
(C8H12N)2[NiCl2(H2O)4]Cl2·2H2O | V = 2451.2 (6) Å3 |
Mr = 552.98 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.6977 (10) Å | µ = 1.26 mm−1 |
b = 29.540 (4) Å | T = 100 K |
c = 10.7808 (15) Å | 0.36 × 0.15 × 0.04 mm |
β = 90.760 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 4617 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 2752 reflections with I > 2σ(I) |
Tmin = 0.625, Tmax = 0.951 | Rint = 0.071 |
17481 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 12 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.49 e Å−3 |
4617 reflections | Δρmin = −0.37 e Å−3 |
300 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | 0.75797 (5) | 0.00017 (2) | 0.25209 (4) | 0.0106 (1) | |
Cl11 | 0.73394 (10) | 0.08087 (3) | 0.25394 (8) | 0.0145 (3) | |
Cl12 | 0.78520 (10) | −0.08070 (3) | 0.25237 (8) | 0.0137 (3) | |
O11 | 0.7986 (3) | 0.00252 (9) | 0.0639 (3) | 0.0234 (10) | |
O12 | 1.0194 (3) | 0.00810 (8) | 0.2918 (3) | 0.0164 (9) | |
O13 | 0.4969 (3) | −0.00747 (8) | 0.2107 (3) | 0.0176 (9) | |
O14 | 0.7171 (3) | −0.00256 (9) | 0.4403 (2) | 0.0200 (9) | |
H11 | 0.788 (5) | −0.0197 (10) | 0.016 (3) | 0.0352* | |
H11' | 0.828 (5) | 0.0248 (9) | 0.022 (3) | 0.0352* | |
H12 | 1.069 (4) | −0.0170 (7) | 0.298 (4) | 0.0247* | |
H12' | 1.075 (4) | 0.0239 (11) | 0.242 (3) | 0.0247* | |
H13 | 0.441 (4) | 0.0152 (8) | 0.186 (4) | 0.0263* | |
H13' | 0.446 (4) | −0.0198 (12) | 0.269 (3) | 0.0263* | |
H14 | 0.678 (5) | −0.0252 (9) | 0.477 (3) | 0.0301* | |
H14' | 0.711 (5) | 0.0200 (9) | 0.487 (3) | 0.0301* | |
N2 | 0.0460 (3) | 0.09932 (10) | 0.4585 (3) | 0.0143 (10) | |
C21 | 0.0035 (4) | 0.14876 (12) | 0.4579 (3) | 0.0154 (11) | |
C22 | 0.0760 (4) | 0.17128 (12) | 0.3429 (3) | 0.0169 (11) | |
C23 | 0.0250 (4) | 0.22067 (12) | 0.3331 (3) | 0.0129 (11) | |
C24 | 0.0765 (4) | 0.25214 (12) | 0.4228 (3) | 0.0149 (11) | |
C25 | 0.0319 (4) | 0.29747 (12) | 0.4107 (4) | 0.0175 (11) | |
C26 | −0.0663 (4) | 0.31217 (12) | 0.3092 (3) | 0.0169 (11) | |
C27 | −0.1209 (4) | 0.28086 (12) | 0.2206 (3) | 0.0148 (11) | |
C28 | −0.0751 (4) | 0.23574 (12) | 0.2326 (3) | 0.0144 (11) | |
H20 | −0.01472 | 0.08523 | 0.39662 | 0.0214* | |
H20' | 0.01669 | 0.08712 | 0.53282 | 0.0214* | |
H20" | 0.16185 | 0.09556 | 0.44631 | 0.0214* | |
H21 | 0.05358 | 0.16323 | 0.53307 | 0.0183* | |
H21' | −0.12417 | 0.15281 | 0.45933 | 0.0183* | |
H22 | 0.20429 | 0.16891 | 0.34504 | 0.0202* | |
H22' | 0.03305 | 0.15500 | 0.26834 | 0.0202* | |
H24 | 0.14288 | 0.24245 | 0.49283 | 0.0180* | |
H25 | 0.06852 | 0.31859 | 0.47217 | 0.0211* | |
H26 | −0.09571 | 0.34325 | 0.30042 | 0.0202* | |
H27 | −0.18983 | 0.29046 | 0.15178 | 0.0175* | |
H28 | −0.11246 | 0.21468 | 0.17118 | 0.0171* | |
N3 | 0.5437 (3) | 0.09956 (10) | −0.0599 (3) | 0.0155 (10) | |
C31 | 0.5003 (4) | 0.14887 (12) | −0.0633 (3) | 0.0150 (11) | |
C32 | 0.5800 (4) | 0.17265 (12) | 0.0481 (3) | 0.0184 (11) | |
C33 | 0.5255 (4) | 0.22157 (12) | 0.0587 (3) | 0.0145 (11) | |
C34 | 0.4268 (4) | 0.23574 (12) | 0.1585 (3) | 0.0149 (11) | |
C35 | 0.3802 (4) | 0.28090 (12) | 0.1721 (3) | 0.0155 (11) | |
C36 | 0.4301 (4) | 0.31266 (13) | 0.0857 (3) | 0.0181 (11) | |
C37 | 0.5282 (4) | 0.29877 (12) | −0.0163 (3) | 0.0158 (11) | |
C38 | 0.5753 (4) | 0.25395 (12) | −0.0296 (3) | 0.0132 (11) | |
H30 | 0.66040 | 0.09592 | −0.06816 | 0.0231* | |
H30' | 0.48728 | 0.08513 | −0.12316 | 0.0231* | |
H30" | 0.50999 | 0.08761 | 0.01377 | 0.0231* | |
H31 | 0.37259 | 0.15280 | −0.06313 | 0.0183* | |
H31' | 0.54515 | 0.16247 | −0.14048 | 0.0183* | |
H32 | 0.54601 | 0.15640 | 0.12429 | 0.0223* | |
H32' | 0.70816 | 0.17119 | 0.04240 | 0.0223* | |
H34 | 0.39058 | 0.21422 | 0.21838 | 0.0176* | |
H35 | 0.31361 | 0.28998 | 0.24133 | 0.0184* | |
H36 | 0.39830 | 0.34353 | 0.09510 | 0.0219* | |
H37 | 0.56252 | 0.32035 | −0.07660 | 0.0188* | |
H38 | 0.64177 | 0.24491 | −0.09895 | 0.0158* | |
Cl4 | 0.72994 (10) | 0.07568 (3) | 0.64530 (8) | 0.0146 (3) | |
Cl5 | 0.24825 (10) | 0.07499 (3) | 0.13985 (8) | 0.0151 (3) | |
O6 | 0.4138 (3) | 0.08084 (9) | 0.4482 (2) | 0.0155 (8) | |
H6 | 0.489 (3) | 0.0848 (13) | 0.505 (2) | 0.0233* | |
H6' | 0.468 (4) | 0.0815 (12) | 0.3807 (19) | 0.0233* | |
O7 | 0.9133 (3) | 0.08230 (9) | 0.9544 (3) | 0.0180 (9) | |
H7 | 0.977 (4) | 0.0833 (13) | 0.892 (2) | 0.0271* | |
H7' | 0.986 (4) | 0.0897 (13) | 1.009 (3) | 0.0271* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N2 | 0.0120 (14) | 0.0184 (19) | 0.0124 (19) | −0.0021 (12) | 0.0006 (12) | 0.0001 (14) |
C21 | 0.0134 (16) | 0.014 (2) | 0.019 (2) | 0.0008 (14) | 0.0032 (16) | −0.0017 (17) |
C22 | 0.0158 (17) | 0.019 (2) | 0.016 (2) | −0.0001 (15) | 0.0022 (16) | −0.0003 (17) |
C23 | 0.0117 (16) | 0.016 (2) | 0.011 (2) | −0.0003 (14) | 0.0047 (15) | −0.0018 (17) |
C24 | 0.0138 (17) | 0.020 (2) | 0.011 (2) | 0.0001 (15) | 0.0003 (15) | 0.0007 (18) |
C25 | 0.0146 (17) | 0.019 (2) | 0.019 (2) | −0.0056 (15) | 0.0019 (16) | −0.0027 (18) |
C26 | 0.0169 (18) | 0.018 (2) | 0.016 (2) | 0.0015 (15) | 0.0031 (16) | 0.0034 (18) |
C27 | 0.0133 (17) | 0.023 (2) | 0.008 (2) | 0.0002 (15) | −0.0003 (15) | 0.0033 (17) |
C28 | 0.0122 (16) | 0.019 (2) | 0.012 (2) | −0.0019 (15) | 0.0043 (16) | −0.0037 (17) |
N3 | 0.0160 (15) | 0.0155 (18) | 0.015 (2) | −0.0020 (12) | 0.0018 (13) | −0.0008 (13) |
C31 | 0.0148 (16) | 0.015 (2) | 0.015 (2) | 0.0044 (15) | −0.0024 (15) | −0.0025 (17) |
C32 | 0.0190 (18) | 0.017 (2) | 0.019 (2) | 0.0013 (15) | −0.0014 (16) | −0.0002 (17) |
C33 | 0.0114 (16) | 0.020 (2) | 0.012 (2) | −0.0020 (14) | −0.0047 (15) | −0.0036 (17) |
C34 | 0.0125 (17) | 0.019 (2) | 0.013 (2) | −0.0011 (14) | −0.0034 (15) | 0.0018 (17) |
C35 | 0.0106 (16) | 0.021 (2) | 0.015 (2) | −0.0018 (14) | 0.0008 (15) | −0.0034 (18) |
C36 | 0.0151 (17) | 0.018 (2) | 0.021 (2) | 0.0028 (15) | −0.0044 (16) | −0.0026 (18) |
C37 | 0.0114 (17) | 0.021 (2) | 0.015 (2) | −0.0038 (14) | −0.0049 (15) | 0.0037 (18) |
C38 | 0.0117 (16) | 0.020 (2) | 0.008 (2) | 0.0020 (14) | −0.0008 (15) | −0.0024 (17) |
Ni1 | 0.0095 (2) | 0.0126 (2) | 0.0098 (3) | −0.0001 (2) | 0.0005 (2) | 0.0010 (2) |
Cl11 | 0.0146 (4) | 0.0134 (5) | 0.0155 (6) | 0.0001 (3) | −0.0002 (4) | 0.0009 (4) |
Cl12 | 0.0142 (4) | 0.0132 (5) | 0.0136 (5) | −0.0006 (3) | −0.0001 (4) | 0.0009 (4) |
O11 | 0.0407 (15) | 0.0185 (17) | 0.0113 (18) | −0.0108 (14) | 0.0076 (13) | −0.0010 (14) |
O12 | 0.0131 (12) | 0.0171 (16) | 0.0191 (18) | −0.0021 (10) | −0.0003 (11) | 0.0022 (13) |
O13 | 0.0137 (12) | 0.0177 (16) | 0.0214 (18) | 0.0014 (11) | 0.0005 (11) | 0.0081 (13) |
O14 | 0.0345 (14) | 0.0130 (16) | 0.0128 (18) | −0.0047 (13) | 0.0066 (12) | 0.0001 (14) |
O6 | 0.0166 (13) | 0.0197 (15) | 0.0102 (16) | 0.0001 (11) | −0.0008 (11) | −0.0002 (13) |
O7 | 0.0130 (12) | 0.0231 (16) | 0.0181 (18) | −0.0001 (11) | 0.0032 (11) | 0.0012 (14) |
Cl4 | 0.0131 (4) | 0.0162 (5) | 0.0144 (5) | −0.0013 (3) | 0.0011 (4) | 0.0001 (4) |
Cl5 | 0.0143 (4) | 0.0160 (5) | 0.0150 (6) | −0.0005 (3) | 0.0008 (4) | 0.0004 (4) |
Ni1—O13 | 2.065 (2) | C24—C25 | 1.388 (5) |
Ni1—O14 | 2.059 (2) | C25—C26 | 1.391 (5) |
Ni1—Cl12 | 2.3981 (11) | C26—C27 | 1.391 (5) |
Ni1—O11 | 2.058 (3) | C27—C28 | 1.384 (5) |
Ni1—Cl11 | 2.3912 (11) | C21—H21 | 0.9900 |
Ni1—O12 | 2.065 (2) | C21—H21' | 0.9900 |
O11—H11 | 0.84 (3) | C22—H22' | 0.9900 |
O11—H11' | 0.83 (3) | C22—H22 | 0.9900 |
O12—H12 | 0.84 (2) | C24—H24 | 0.9500 |
O12—H12' | 0.83 (3) | C25—H25 | 0.9500 |
O13—H13 | 0.84 (3) | C26—H26 | 0.9500 |
O13—H13' | 0.83 (3) | C27—H27 | 0.9500 |
O14—H14' | 0.84 (3) | C28—H28 | 0.9500 |
O14—H14 | 0.84 (3) | C31—C32 | 1.514 (5) |
O6—H6 | 0.85 (2) | C32—C33 | 1.510 (5) |
O6—H6' | 0.84 (2) | C33—C38 | 1.406 (5) |
O7—H7' | 0.84 (3) | C33—C34 | 1.390 (5) |
O7—H7 | 0.84 (3) | C34—C35 | 1.390 (5) |
N2—C21 | 1.497 (5) | C35—C36 | 1.380 (5) |
N2—H20" | 0.9100 | C36—C37 | 1.404 (5) |
N2—H20 | 0.9100 | C37—C38 | 1.381 (5) |
N2—H20' | 0.9100 | C31—H31 | 0.9900 |
N3—C31 | 1.495 (5) | C31—H31' | 0.9900 |
N3—H30 | 0.9100 | C32—H32 | 0.9900 |
N3—H30' | 0.9100 | C32—H32' | 0.9900 |
N3—H30" | 0.9100 | C34—H34 | 0.9500 |
C21—C22 | 1.520 (5) | C35—H35 | 0.9500 |
C22—C23 | 1.514 (5) | C36—H36 | 0.9500 |
C23—C28 | 1.394 (5) | C37—H37 | 0.9500 |
C23—C24 | 1.395 (5) | C38—H38 | 0.9500 |
Ni1···H30'i | 3.4300 | C31···H38 | 3.0600 |
Ni1···H7ii | 3.57 (3) | C32···H28iii | 2.9700 |
Ni1···H20iii | 3.4300 | C33···H28iii | 3.0300 |
Ni1···H6' | 3.57 (3) | C34···H24ix | 2.8800 |
Cl4···N2iii | 3.255 (3) | C35···H24ix | 2.7300 |
Cl4···O14 | 3.198 (3) | C35···H31'viii | 2.9000 |
Cl4···O13iv | 3.097 (3) | C36···H21ix | 3.0300 |
Cl4···O6 | 3.213 (2) | C36···H27iii | 3.0700 |
Cl4···C21iii | 3.645 (3) | C36···H24ix | 2.9100 |
Cl5···N3 | 3.235 (3) | C37···H27iii | 2.8200 |
Cl5···O13 | 3.185 (3) | C37···H21'xi | 3.0500 |
Cl5···O11i | 3.190 (3) | C37···H22ix | 3.0400 |
Cl5···O12v | 3.125 (3) | C37···H34ix | 3.0600 |
Cl11···C21iii | 3.611 (3) | C38···H31' | 2.9600 |
Cl11···O14 | 3.183 (3) | C38···H27iii | 2.8600 |
Cl11···O6 | 3.255 (2) | H6···Cl4 | 2.39 (2) |
Cl11···N2iii | 3.285 (3) | H6···H36viii | 2.4400 |
Cl11···O13 | 3.215 (3) | H6···H14iv | 2.19 (5) |
Cl11···O11 | 3.135 (3) | H6···H14' | 2.58 (5) |
Cl11···O12 | 3.097 (3) | H6'···H20" | 2.5000 |
Cl12···O13 | 3.127 (3) | H6'···H14iv | 2.54 (4) |
Cl12···O14 | 3.120 (3) | H6'···Cl11 | 2.48 (3) |
Cl12···C31i | 3.595 (3) | H6'···Ni1 | 3.57 (3) |
Cl12···N2iv | 3.406 (3) | H6'···Cl5 | 3.09 (2) |
Cl12···O12 | 3.208 (3) | H11···Cl5i | 2.36 (3) |
Cl12···N3i | 3.300 (3) | H11'···H7vii | 2.51 (5) |
Cl12···O11 | 3.192 (3) | H11'···O7vii | 1.97 (3) |
Cl12···O7ii | 3.240 (3) | H11'···H7'vii | 2.28 (5) |
Cl4···H20'iii | 2.5500 | H12···Cl4ii | 2.40 (3) |
Cl4···H14' | 2.37 (3) | H12'···Cl5iii | 2.30 (3) |
Cl4···H6 | 2.39 (2) | H12'···H20iii | 2.5600 |
Cl4···H13'iv | 2.33 (3) | H13···Cl5 | 2.36 (3) |
Cl5···H13 | 2.36 (3) | H13'···Cl4iv | 2.33 (3) |
Cl5···H12'v | 2.30 (3) | H13'···H30'i | 2.5500 |
Cl5···H6' | 3.09 (2) | H14···H6iv | 2.19 (5) |
Cl5···H30" | 2.4700 | H14···O6iv | 1.97 (3) |
Cl5···H11i | 2.36 (3) | H14···H6'iv | 2.54 (4) |
Cl11···H20iii | 2.4600 | H14···H20"iv | 2.5500 |
Cl11···H14' | 3.10 (3) | H14'···Cl4 | 2.37 (3) |
Cl11···H13 | 3.06 (3) | H14'···H6 | 2.58 (5) |
Cl11···H6' | 2.48 (3) | H20···Cl11v | 2.4600 |
Cl11···H30" | 3.1000 | H20···Ni1v | 3.4300 |
Cl11···H32 | 3.0000 | H20···H22' | 2.5100 |
Cl11···H12' | 3.12 (3) | H20···H12'v | 2.5600 |
Cl11···H11' | 3.09 (3) | H20···O12v | 2.5600 |
Cl12···H12 | 2.92 (3) | H20'···Cl4v | 2.5500 |
Cl12···H14 | 3.05 (3) | H20'···Cl12iv | 2.7600 |
Cl12···H20'iv | 2.7600 | H20"···O6 | 1.9900 |
Cl12···H11 | 3.12 (3) | H20"···H6' | 2.5000 |
Cl12···H7ii | 2.42 (3) | H20"···H22 | 2.4500 |
Cl12···H36vi | 3.1300 | H20"···H14iv | 2.5500 |
Cl12···H30'i | 2.5100 | H21···H24 | 2.4800 |
O6···O14iv | 2.800 (4) | H21···C27viii | 2.9500 |
O6···Cl4 | 3.213 (2) | H21···C36viii | 3.0300 |
O6···Cl11 | 3.255 (2) | H21···C24 | 2.8900 |
O6···N2 | 2.887 (3) | H21'···C37x | 3.0500 |
O11···O13 | 2.843 (4) | H21'···H37x | 2.5600 |
O11···O7vii | 2.785 (4) | H22···H20" | 2.4500 |
O11···O12 | 2.974 (4) | H22···H34 | 2.4000 |
O11···Cl12 | 3.192 (3) | H22···C37viii | 3.0400 |
O11···Cl5i | 3.190 (3) | H22'···H20 | 2.5100 |
O11···Cl11 | 3.135 (3) | H22'···H28 | 2.3300 |
O12···N2iii | 3.244 (4) | H24···C34viii | 2.8800 |
O12···O14 | 2.859 (3) | H24···C35viii | 2.7300 |
O12···Cl4ii | 3.205 (3) | H24···C36viii | 2.9100 |
O12···Cl5iii | 3.125 (3) | H24···H21 | 2.4800 |
O12···O11 | 2.974 (4) | H24···C21 | 2.9900 |
O12···Cl11 | 3.097 (3) | H25···H31viii | 2.5200 |
O12···Cl12 | 3.208 (3) | H26···H7xii | 2.4500 |
O13···N3i | 3.182 (4) | H26···O7xii | 2.7600 |
O13···O14 | 2.985 (4) | H27···C38v | 2.8600 |
O13···Cl5 | 3.185 (3) | H27···C37v | 2.8200 |
O13···Cl12 | 3.127 (3) | H27···C36v | 3.0700 |
O13···Cl4iv | 3.097 (3) | H28···C32v | 2.9700 |
O13···Cl11 | 3.215 (3) | H28···H32'v | 2.3300 |
O13···O11 | 2.843 (4) | H28···H22' | 2.3300 |
O14···Cl4 | 3.198 (3) | H28···C25ix | 3.0500 |
O14···O6iv | 2.800 (4) | H28···C33v | 3.0300 |
O14···Cl12 | 3.120 (3) | H30···O7vii | 2.0000 |
O14···O13 | 2.985 (4) | H30···H7vii | 2.5100 |
O14···Cl11 | 3.183 (3) | H30···H32' | 2.5500 |
O14···O12 | 2.859 (3) | H30'···Ni1i | 3.4300 |
O6···H14iv | 1.97 (3) | H30'···H13'i | 2.5500 |
O6···H20" | 1.9900 | H30'···Cl12i | 2.5100 |
O6···H36viii | 2.7400 | H30'···O13i | 2.4800 |
O11···H12' | 2.92 (3) | H30'···Cl4vii | 3.1500 |
O12···H20iii | 2.5600 | H30"···H32 | 2.3700 |
O13···H30'i | 2.4800 | H30"···Cl11 | 3.1000 |
O14···H13' | 2.82 (3) | H30"···Cl5 | 2.4700 |
N2···Cl12iv | 3.406 (3) | H31···H25ix | 2.5200 |
N2···O6 | 2.887 (3) | H31···C25ix | 3.0200 |
N2···O12v | 3.244 (4) | H31'···C35ix | 2.9000 |
N2···Cl11v | 3.285 (3) | H31'···C38 | 2.9600 |
N2···Cl4v | 3.255 (3) | H31'···H38 | 2.5800 |
N3···Cl12i | 3.300 (3) | H31'···H35ix | 2.5900 |
N3···O13i | 3.182 (4) | H32···H30" | 2.3700 |
N3···Cl5 | 3.235 (3) | H32···H34 | 2.3300 |
N3···O7vii | 2.893 (3) | H32···Cl11 | 3.0000 |
C21···Cl11v | 3.611 (3) | H32'···C25xi | 3.0300 |
C21···Cl4v | 3.645 (3) | H32'···H28iii | 2.3300 |
C24···C28viii | 3.571 (5) | H32'···H30 | 2.5500 |
C28···C24ix | 3.571 (5) | H34···C37viii | 3.0600 |
C31···Cl12i | 3.595 (3) | H34···H32 | 2.3300 |
C34···C38viii | 3.550 (5) | H34···H22 | 2.4000 |
C38···C34ix | 3.550 (5) | H34···C22 | 3.0600 |
C21···H24 | 2.9900 | H34···C23 | 3.0900 |
C22···H34 | 3.0600 | H35···C26 | 3.0900 |
C23···H34 | 3.0900 | H35···H31'viii | 2.5900 |
C24···H35 | 2.9200 | H35···C24 | 2.9200 |
C24···H21 | 2.8900 | H35···C25 | 2.8600 |
C25···H32'x | 3.0300 | H36···O6ix | 2.7400 |
C25···H31viii | 3.0200 | H36···Cl12xiii | 3.1300 |
C25···H28viii | 3.0500 | H36···H6ix | 2.4400 |
C25···H35 | 2.8600 | H37···H21'xi | 2.5600 |
C26···H38x | 2.9900 | H38···C28xi | 2.9100 |
C26···H35 | 3.0900 | H38···C27xi | 2.7900 |
C27···H21ix | 2.9500 | H38···C31 | 3.0600 |
C27···H38x | 2.7900 | H38···H31' | 2.5800 |
C28···H38x | 2.9100 | H38···C26xi | 2.9900 |
Cl12—Ni1—O12 | 91.59 (7) | H21—C21—H21' | 108.00 |
Cl12—Ni1—O13 | 88.64 (7) | C22—C21—H21' | 110.00 |
Cl12—Ni1—O14 | 88.52 (8) | N2—C21—H21 | 110.00 |
O11—Ni1—O12 | 92.30 (11) | C22—C21—H21 | 110.00 |
O11—Ni1—O13 | 87.18 (11) | N2—C21—H21' | 110.00 |
O11—Ni1—O14 | 179.68 (11) | C23—C22—H22 | 109.00 |
O12—Ni1—O13 | 179.44 (12) | C21—C22—H22' | 109.00 |
O12—Ni1—O14 | 87.79 (11) | C23—C22—H22' | 109.00 |
O13—Ni1—O14 | 92.73 (11) | C21—C22—H22 | 109.00 |
Cl11—Ni1—Cl12 | 179.21 (3) | H22—C22—H22' | 108.00 |
Cl11—Ni1—O11 | 89.28 (8) | C25—C24—H24 | 120.00 |
Cl11—Ni1—O12 | 87.73 (7) | C23—C24—H24 | 120.00 |
Cl11—Ni1—O13 | 92.04 (7) | C26—C25—H25 | 120.00 |
Cl11—Ni1—O14 | 91.03 (8) | C24—C25—H25 | 120.00 |
Cl12—Ni1—O11 | 91.17 (8) | C25—C26—H26 | 120.00 |
Ni1—O11—H11' | 128 (2) | C27—C26—H26 | 120.00 |
H11—O11—H11' | 108 (3) | C28—C27—H27 | 120.00 |
Ni1—O11—H11 | 125 (2) | C26—C27—H27 | 120.00 |
H12—O12—H12' | 108 (3) | C27—C28—H28 | 119.00 |
Ni1—O12—H12 | 111 (2) | C23—C28—H28 | 119.00 |
Ni1—O12—H12' | 116 (2) | N3—C31—C32 | 110.2 (3) |
H13—O13—H13' | 110 (3) | C31—C32—C33 | 113.2 (3) |
Ni1—O13—H13' | 111 (2) | C32—C33—C34 | 120.2 (3) |
Ni1—O13—H13 | 118 (2) | C34—C33—C38 | 118.4 (3) |
Ni1—O14—H14 | 124 (2) | C32—C33—C38 | 121.4 (3) |
Ni1—O14—H14' | 125 (2) | C33—C34—C35 | 121.0 (3) |
H14—O14—H14' | 109 (3) | C34—C35—C36 | 120.5 (3) |
H6—O6—H6' | 106 (2) | C35—C36—C37 | 119.2 (3) |
H7—O7—H7' | 99 (3) | C36—C37—C38 | 120.4 (3) |
C21—N2—H20' | 109.00 | C33—C38—C37 | 120.5 (3) |
C21—N2—H20" | 109.00 | C32—C31—H31 | 110.00 |
H20—N2—H20" | 109.00 | C32—C31—H31' | 110.00 |
H20'—N2—H20" | 110.00 | N3—C31—H31 | 110.00 |
C21—N2—H20 | 109.00 | N3—C31—H31' | 110.00 |
H20—N2—H20' | 109.00 | H31—C31—H31' | 108.00 |
C31—N3—H30" | 109.00 | H32—C32—H32' | 108.00 |
H30—N3—H30' | 109.00 | C31—C32—H32' | 109.00 |
H30'—N3—H30" | 109.00 | C31—C32—H32 | 109.00 |
C31—N3—H30 | 109.00 | C33—C32—H32 | 109.00 |
H30—N3—H30" | 109.00 | C33—C32—H32' | 109.00 |
C31—N3—H30' | 110.00 | C33—C34—H34 | 120.00 |
N2—C21—C22 | 110.4 (3) | C35—C34—H34 | 119.00 |
C21—C22—C23 | 112.4 (3) | C34—C35—H35 | 120.00 |
C24—C23—C28 | 118.4 (3) | C36—C35—H35 | 120.00 |
C22—C23—C28 | 120.1 (3) | C37—C36—H36 | 120.00 |
C22—C23—C24 | 121.5 (3) | C35—C36—H36 | 120.00 |
C23—C24—C25 | 120.7 (3) | C36—C37—H37 | 120.00 |
C24—C25—C26 | 120.4 (3) | C38—C37—H37 | 120.00 |
C25—C26—C27 | 119.3 (3) | C37—C38—H38 | 120.00 |
C26—C27—C28 | 120.1 (3) | C33—C38—H38 | 120.00 |
C23—C28—C27 | 121.2 (3) | ||
N2—C21—C22—C23 | 175.8 (2) | N3—C31—C32—C33 | −173.6 (2) |
C21—C22—C23—C24 | 62.1 (4) | C31—C32—C33—C34 | 115.0 (3) |
C21—C22—C23—C28 | −118.2 (3) | C31—C32—C33—C38 | −66.3 (4) |
C22—C23—C24—C25 | 178.5 (3) | C32—C33—C34—C35 | 177.9 (3) |
C28—C23—C24—C25 | −1.3 (5) | C38—C33—C34—C35 | −0.9 (5) |
C22—C23—C28—C27 | −178.9 (3) | C32—C33—C38—C37 | −178.2 (3) |
C24—C23—C28—C27 | 0.8 (5) | C34—C33—C38—C37 | 0.6 (5) |
C23—C24—C25—C26 | 0.5 (5) | C33—C34—C35—C36 | 0.6 (5) |
C24—C25—C26—C27 | 0.7 (5) | C34—C35—C36—C37 | 0.2 (5) |
C25—C26—C27—C28 | −1.1 (5) | C35—C36—C37—C38 | −0.5 (5) |
C26—C27—C28—C23 | 0.4 (5) | C36—C37—C38—C33 | 0.1 (5) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y, −z+1; (iii) x+1, y, z; (iv) −x+1, −y, −z+1; (v) x−1, y, z; (vi) −x+1, y−1/2, −z+1/2; (vii) x, y, z−1; (viii) x, −y+1/2, z+1/2; (ix) x, −y+1/2, z−1/2; (x) x−1, −y+1/2, z+1/2; (xi) x+1, −y+1/2, z−1/2; (xii) x−1, −y+1/2, z−1/2; (xiii) −x+1, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···Cl4 | 0.85 (2) | 2.39 (2) | 3.213 (2) | 164 (3) |
O6—H6′···Cl11 | 0.84 (2) | 2.48 (3) | 3.255 (2) | 154 (2) |
O11—H11···Cl5i | 0.84 (3) | 2.36 (3) | 3.190 (3) | 172 (3) |
O11—H11′···O7vii | 0.83 (3) | 1.97 (3) | 2.785 (4) | 169 (3) |
O12—H12···Cl4ii | 0.84 (2) | 2.40 (3) | 3.205 (3) | 163 (3) |
O12—H12′···Cl5iii | 0.83 (3) | 2.30 (3) | 3.125 (3) | 168 (3) |
O13—H13···Cl5 | 0.84 (3) | 2.36 (3) | 3.185 (3) | 171 (3) |
O13—H13′···Cl4iv | 0.83 (3) | 2.33 (3) | 3.097 (3) | 153 (3) |
O14—H14···O6iv | 0.84 (3) | 1.97 (3) | 2.800 (4) | 176 (3) |
O14—H14′···Cl4 | 0.84 (3) | 2.37 (3) | 3.198 (3) | 169 (3) |
N2—H20···Cl11v | 0.9100 | 2.4600 | 3.285 (3) | 151.00 |
N2—H20···O12v | 0.9100 | 2.5600 | 3.244 (4) | 133.00 |
N2—H20′···Cl4v | 0.9100 | 2.5500 | 3.255 (3) | 134.00 |
N2—H20′···Cl12iv | 0.9100 | 2.7600 | 3.406 (3) | 129.00 |
N2—H20"···O6 | 0.9100 | 1.9900 | 2.887 (3) | 170.00 |
N3—H30···O7vii | 0.9100 | 2.0000 | 2.893 (3) | 166.00 |
N3—H30′···Cl12i | 0.9100 | 2.5100 | 3.300 (3) | 146.00 |
N3—H30′···O13i | 0.9100 | 2.4800 | 3.182 (4) | 134.00 |
N3—H30"···Cl5 | 0.9100 | 2.4700 | 3.235 (3) | 141.00 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y, −z+1; (iii) x+1, y, z; (iv) −x+1, −y, −z+1; (v) x−1, y, z; (vii) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | (C8H12N)2[NiCl2(H2O)4]Cl2·2H2O |
Mr | 552.98 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 7.6977 (10), 29.540 (4), 10.7808 (15) |
β (°) | 90.760 (2) |
V (Å3) | 2451.2 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.26 |
Crystal size (mm) | 0.36 × 0.15 × 0.04 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2006) |
Tmin, Tmax | 0.625, 0.951 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17481, 4617, 2752 |
Rint | 0.071 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.100, 0.96 |
No. of reflections | 4617 |
No. of parameters | 300 |
No. of restraints | 12 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.49, −0.37 |
Computer programs: SMART (Bruker, 2006), SAINT-Plus (Bruker, 2006), DIRDIF99 (Beurskens et al., 1999), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2006) and PLATON (Spek, 2003), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···Cl4 | 0.85 (2) | 2.39 (2) | 3.213 (2) | 164 (3) |
O6—H6'···Cl11 | 0.84 (2) | 2.48 (3) | 3.255 (2) | 154 (2) |
O11—H11···Cl5i | 0.84 (3) | 2.36 (3) | 3.190 (3) | 172 (3) |
O11—H11'···O7ii | 0.83 (3) | 1.97 (3) | 2.785 (4) | 169 (3) |
O12—H12···Cl4iii | 0.84 (2) | 2.40 (3) | 3.205 (3) | 163 (3) |
O12—H12'···Cl5iv | 0.83 (3) | 2.30 (3) | 3.125 (3) | 168 (3) |
O13—H13···Cl5 | 0.84 (3) | 2.36 (3) | 3.185 (3) | 171 (3) |
O13—H13'···Cl4v | 0.83 (3) | 2.33 (3) | 3.097 (3) | 153 (3) |
O14—H14···O6v | 0.84 (3) | 1.97 (3) | 2.800 (4) | 176 (3) |
O14—H14'···Cl4 | 0.84 (3) | 2.37 (3) | 3.198 (3) | 169 (3) |
N2—H20···Cl11vi | 0.9100 | 2.4600 | 3.285 (3) | 151.00 |
N2—H20···O12vi | 0.9100 | 2.5600 | 3.244 (4) | 133.00 |
N2—H20'···Cl4vi | 0.9100 | 2.5500 | 3.255 (3) | 134.00 |
N2—H20'···Cl12v | 0.9100 | 2.7600 | 3.406 (3) | 129.00 |
N2—H20"···O6 | 0.9100 | 1.9900 | 2.887 (3) | 170.00 |
N3—H30···O7ii | 0.9100 | 2.0000 | 2.893 (3) | 166.00 |
N3—H30'···Cl12i | 0.9100 | 2.5100 | 3.300 (3) | 146.00 |
N3—H30'···O13i | 0.9100 | 2.4800 | 3.182 (4) | 134.00 |
N3—H30"···Cl5 | 0.9100 | 2.4700 | 3.235 (3) | 141.00 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, y, z−1; (iii) −x+2, −y, −z+1; (iv) x+1, y, z; (v) −x+1, −y, −z+1; (vi) x−1, y, z. |
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There is an interest to develop new multifunctional semiconductors that are easy to process and contain magnetic components. We present here the crystal structure of the title compound, which is a solution grown system build of organic conjugated molecules and paramagnetic Ni(II) ions. Every nickel(II) ion is surrounded by an octahedron in which 4 water molecules and 2 chlorine atoms are present. These octahedra are part of a complex network of hydrogen bonds between the ammonium groups, the water molecules and the free clorine ions, which stabilize this structure. The blue crystals of the title compound loose 20% of their weight when heated up to 350 K, leaving a pink amorphous powder, suggesting the evaporation of the crystal water. The material is paramagnetic down to 5 K. This lack of magnetic ordering can be explained by the large separation between the magnetic ions (d>6.631 Å) due to which the magnetic interactions are small and thus no magnetic ordering occurs.