The title compound, [Ni(NCS)
2(C
6H
7NO)
2(H
2O)
2]·H
2O, consists of a mononuclear complex and an uncoordinated water molecule. The nickel(II) ion has a distorted octahedral coordination, formed by two N atoms from two thiocyanate anions and four O atoms from two water molecules and two 4-methylpyridine
N-oxide molecules. The uncoordinated water molecules and the complex are connected by O—H
O and O—H
S hydrogen bonds.
Supporting information
CCDC reference: 261032
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.035
- wR factor = 0.094
- Data-to-parameter ratio = 14.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.85 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C13 .. 5.70 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for S2 - C14 .. 6.44 su
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C3
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 1
N4 -NI1 -N3 -C13 22.60 1.30 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 6
N3 -NI1 -N4 -C14 22.70 1.40 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 37
O2 -NI1 -O1 -N1 104.00 0.80 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 44
O1 -NI1 -O2 -N2 83.70 0.90 1.555 1.555 1.555 1.555
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 4
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
9 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 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
0 ALERT type 3 Indicator that the structure quality may be low
5 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
Crystal data top
[Ni(C6H7NO)2(NCS)2(H2O)2]·H2O | Z = 2 |
Mr = 447.17 | F(000) = 464 |
Triclinic, P1 | Dx = 1.496 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5665 (16) Å | Cell parameters from 2545 reflections |
b = 9.701 (2) Å | θ = 2.3–27.1° |
c = 14.129 (3) Å | µ = 1.22 mm−1 |
α = 103.820 (3)° | T = 293 K |
β = 98.958 (3)° | Prism, blue |
γ = 91.721 (3)° | 0.14 × 0.09 × 0.08 mm |
V = 992.4 (4) Å3 | |
Data collection top
Bruker SMART CCD diffractometer | 3426 independent reflections |
Radiation source: fine-focus sealed tube | 3069 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
φ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.848, Tmax = 0.909 | k = −11→11 |
5120 measured reflections | l = −10→16 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0493P)2 + 0.2162P] where P = (Fo2 + 2Fc2)/3 |
3426 reflections | (Δ/σ)max = 0.001 |
243 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.72854 (4) | 0.78816 (3) | 0.96374 (2) | 0.02952 (12) | |
N1 | 0.4422 (3) | 0.7770 (2) | 0.79274 (15) | 0.0371 (5) | |
N2 | 1.0013 (3) | 0.8015 (2) | 1.13636 (14) | 0.0347 (5) | |
N3 | 0.8328 (3) | 0.7651 (2) | 0.83858 (16) | 0.0408 (5) | |
N4 | 0.6168 (3) | 0.7886 (2) | 1.08468 (15) | 0.0378 (5) | |
C1 | 0.4779 (4) | 0.8912 (3) | 0.7603 (2) | 0.0523 (8) | |
H1 | 0.5095 | 0.9789 | 0.8052 | 0.063* | |
C2 | 0.4683 (5) | 0.8799 (4) | 0.6612 (2) | 0.0628 (9) | |
H2 | 0.4938 | 0.9602 | 0.6393 | 0.075* | |
C3 | 0.4216 (4) | 0.7521 (4) | 0.5938 (2) | 0.0589 (8) | |
C4 | 0.4238 (6) | 0.7372 (6) | 0.4851 (3) | 0.0963 (15) | |
H4A | 0.5426 | 0.7194 | 0.4715 | 0.144* | |
H4B | 0.3885 | 0.8234 | 0.4678 | 0.144* | |
H4C | 0.3417 | 0.6592 | 0.4468 | 0.144* | |
C5 | 0.3816 (5) | 0.6373 (4) | 0.6303 (2) | 0.0663 (9) | |
H5 | 0.3465 | 0.5492 | 0.5867 | 0.080* | |
C6 | 0.3928 (4) | 0.6511 (3) | 0.7296 (2) | 0.0521 (7) | |
H6 | 0.3659 | 0.5726 | 0.7531 | 0.063* | |
C7 | 0.9994 (4) | 0.9239 (3) | 1.2041 (2) | 0.0503 (7) | |
H7 | 1.0038 | 1.0101 | 1.1863 | 0.060* | |
C8 | 0.9910 (5) | 0.9217 (4) | 1.2996 (2) | 0.0606 (9) | |
H8 | 0.9915 | 1.0072 | 1.3467 | 0.073* | |
C9 | 0.9819 (4) | 0.7952 (4) | 1.3277 (2) | 0.0539 (8) | |
C10 | 0.9557 (6) | 0.7893 (5) | 1.4297 (3) | 0.0921 (14) | |
H10A | 0.9755 | 0.6956 | 1.4384 | 0.138* | |
H10B | 0.8355 | 0.8114 | 1.4383 | 0.138* | |
H10C | 1.0393 | 0.8573 | 1.4776 | 0.138* | |
C11 | 0.9904 (4) | 0.6727 (3) | 1.2560 (2) | 0.0506 (7) | |
H11 | 0.9891 | 0.5855 | 1.2724 | 0.061* | |
C12 | 1.0007 (4) | 0.6769 (3) | 1.1612 (2) | 0.0400 (6) | |
H12 | 1.0073 | 0.5931 | 1.1138 | 0.048* | |
C13 | 0.8636 (4) | 0.7224 (3) | 0.7597 (2) | 0.0383 (6) | |
C14 | 0.5605 (3) | 0.7571 (3) | 1.14885 (18) | 0.0342 (6) | |
O1 | 0.4630 (2) | 0.78897 (19) | 0.89102 (12) | 0.0399 (4) | |
O2 | 0.9936 (2) | 0.80314 (18) | 1.04032 (12) | 0.0370 (4) | |
O3 | 0.7109 (3) | 0.56658 (19) | 0.93464 (15) | 0.0518 (5) | |
H3WA | 0.6546 | 0.5331 | 0.8789 | 0.078* | |
H3WB | 0.7113 | 0.5318 | 0.9772 | 0.048 (9)* | |
O4 | 0.7445 (3) | 1.01096 (18) | 0.99352 (15) | 0.0484 (5) | |
H4WA | 0.8409 | 1.0391 | 0.9826 | 0.073* | |
H4WB | 0.6788 | 1.0590 | 1.0143 | 0.051 (10)* | |
O5 | 0.2223 (3) | 0.6051 (2) | 0.94194 (15) | 0.0497 (5) | |
H5B | 0.3127 | 0.6457 | 0.9313 | 0.072 (12)* | |
H5A | 0.1501 | 0.6675 | 0.9677 | 0.083 (12)* | |
S1 | 0.90757 (14) | 0.66716 (10) | 0.64821 (6) | 0.0665 (3) | |
S2 | 0.48009 (11) | 0.71646 (8) | 1.24005 (5) | 0.0525 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0346 (2) | 0.02782 (18) | 0.0292 (2) | 0.00189 (13) | 0.01142 (13) | 0.00910 (13) |
N1 | 0.0356 (12) | 0.0419 (12) | 0.0369 (12) | 0.0065 (9) | 0.0082 (9) | 0.0138 (10) |
N2 | 0.0353 (12) | 0.0364 (11) | 0.0328 (12) | −0.0033 (9) | 0.0072 (9) | 0.0090 (9) |
N3 | 0.0479 (14) | 0.0425 (12) | 0.0382 (13) | 0.0055 (10) | 0.0176 (11) | 0.0152 (10) |
N4 | 0.0425 (13) | 0.0388 (12) | 0.0345 (12) | 0.0004 (9) | 0.0139 (10) | 0.0092 (9) |
C1 | 0.079 (2) | 0.0391 (15) | 0.0432 (16) | 0.0088 (14) | 0.0143 (15) | 0.0155 (13) |
C2 | 0.084 (3) | 0.064 (2) | 0.053 (2) | 0.0163 (18) | 0.0215 (17) | 0.0311 (17) |
C3 | 0.0500 (19) | 0.090 (3) | 0.0392 (17) | 0.0150 (17) | 0.0116 (14) | 0.0161 (17) |
C4 | 0.087 (3) | 0.159 (5) | 0.044 (2) | 0.016 (3) | 0.019 (2) | 0.020 (2) |
C5 | 0.062 (2) | 0.076 (2) | 0.0486 (19) | −0.0055 (18) | 0.0048 (16) | −0.0056 (17) |
C6 | 0.0515 (18) | 0.0484 (17) | 0.0524 (18) | −0.0095 (14) | 0.0059 (14) | 0.0081 (14) |
C7 | 0.069 (2) | 0.0354 (15) | 0.0436 (17) | −0.0049 (13) | 0.0062 (14) | 0.0065 (12) |
C8 | 0.083 (2) | 0.0567 (19) | 0.0339 (16) | −0.0041 (17) | 0.0132 (15) | −0.0049 (14) |
C9 | 0.0506 (18) | 0.075 (2) | 0.0384 (16) | −0.0025 (15) | 0.0093 (13) | 0.0179 (15) |
C10 | 0.105 (3) | 0.135 (4) | 0.047 (2) | 0.000 (3) | 0.024 (2) | 0.038 (2) |
C11 | 0.0486 (17) | 0.0579 (18) | 0.0531 (18) | −0.0038 (14) | 0.0070 (14) | 0.0307 (15) |
C12 | 0.0408 (15) | 0.0352 (14) | 0.0454 (16) | 0.0023 (11) | 0.0102 (12) | 0.0110 (12) |
C13 | 0.0390 (15) | 0.0380 (14) | 0.0445 (16) | 0.0060 (11) | 0.0153 (12) | 0.0170 (12) |
C14 | 0.0343 (14) | 0.0326 (13) | 0.0337 (14) | −0.0008 (10) | 0.0075 (11) | 0.0040 (10) |
O1 | 0.0396 (10) | 0.0523 (11) | 0.0327 (10) | 0.0043 (8) | 0.0100 (8) | 0.0173 (8) |
O2 | 0.0392 (10) | 0.0445 (10) | 0.0293 (9) | −0.0015 (8) | 0.0103 (7) | 0.0105 (7) |
O3 | 0.0858 (16) | 0.0306 (9) | 0.0397 (11) | 0.0004 (9) | 0.0094 (11) | 0.0114 (9) |
O4 | 0.0523 (13) | 0.0288 (9) | 0.0719 (14) | 0.0050 (9) | 0.0348 (11) | 0.0114 (9) |
O5 | 0.0553 (13) | 0.0368 (10) | 0.0625 (13) | −0.0001 (10) | 0.0208 (10) | 0.0165 (9) |
S1 | 0.0865 (7) | 0.0797 (6) | 0.0442 (5) | 0.0240 (5) | 0.0359 (4) | 0.0183 (4) |
S2 | 0.0652 (5) | 0.0580 (5) | 0.0389 (4) | −0.0092 (4) | 0.0230 (4) | 0.0136 (3) |
Geometric parameters (Å, º) top
Ni1—N3 | 2.014 (2) | C5—C6 | 1.365 (4) |
Ni1—N4 | 2.020 (2) | C5—H5 | 0.9300 |
Ni1—O3 | 2.0859 (18) | C6—H6 | 0.9300 |
Ni1—O4 | 2.0970 (18) | C7—C8 | 1.366 (4) |
Ni1—O2 | 2.1082 (18) | C7—H7 | 0.9300 |
Ni1—O1 | 2.1109 (18) | C8—C9 | 1.380 (5) |
N1—C1 | 1.331 (3) | C8—H8 | 0.9300 |
N1—C6 | 1.332 (4) | C9—C11 | 1.375 (4) |
N1—O1 | 1.349 (3) | C9—C10 | 1.499 (4) |
N2—C12 | 1.337 (3) | C10—H10A | 0.9600 |
N2—C7 | 1.338 (3) | C10—H10B | 0.9600 |
N2—O2 | 1.353 (2) | C10—H10C | 0.9600 |
N3—C13 | 1.155 (3) | C11—C12 | 1.364 (4) |
N4—C14 | 1.159 (3) | C11—H11 | 0.9300 |
C1—C2 | 1.370 (4) | C12—H12 | 0.9300 |
C1—H1 | 0.9300 | C13—S1 | 1.628 (3) |
C2—C3 | 1.368 (5) | C14—S2 | 1.630 (3) |
C2—H2 | 0.9300 | O3—H3WA | 0.8200 |
C3—C5 | 1.379 (5) | O3—H3WB | 0.7556 |
C3—C4 | 1.511 (4) | O4—H4WA | 0.8200 |
C4—H4A | 0.9600 | O4—H4WB | 0.7382 |
C4—H4B | 0.9600 | O5—H5B | 0.8301 |
C4—H4C | 0.9600 | O5—H5A | 0.8791 |
| | | |
N3—Ni1—N4 | 173.85 (8) | C6—C5—C3 | 121.0 (3) |
N3—Ni1—O3 | 86.78 (8) | C6—C5—H5 | 119.5 |
N4—Ni1—O3 | 87.20 (8) | C3—C5—H5 | 119.5 |
N3—Ni1—O4 | 93.60 (8) | N1—C6—C5 | 120.1 (3) |
N4—Ni1—O4 | 92.41 (8) | N1—C6—H6 | 120.0 |
O3—Ni1—O4 | 179.56 (8) | C5—C6—H6 | 120.0 |
N3—Ni1—O2 | 87.51 (8) | N2—C7—C8 | 119.7 (3) |
N4—Ni1—O2 | 93.96 (8) | N2—C7—H7 | 120.2 |
O3—Ni1—O2 | 92.28 (8) | C8—C7—H7 | 120.2 |
O4—Ni1—O2 | 87.97 (8) | C7—C8—C9 | 121.3 (3) |
N3—Ni1—O1 | 93.53 (8) | C7—C8—H8 | 119.4 |
N4—Ni1—O1 | 85.42 (8) | C9—C8—H8 | 119.4 |
O3—Ni1—O1 | 91.72 (8) | C11—C9—C8 | 116.7 (3) |
O4—Ni1—O1 | 88.03 (8) | C11—C9—C10 | 121.0 (3) |
O2—Ni1—O1 | 175.92 (7) | C8—C9—C10 | 122.2 (3) |
C1—N1—C6 | 120.8 (2) | C9—C10—H10A | 109.5 |
C1—N1—O1 | 119.1 (2) | C9—C10—H10B | 109.5 |
C6—N1—O1 | 120.1 (2) | H10A—C10—H10B | 109.5 |
C12—N2—C7 | 121.0 (2) | C9—C10—H10C | 109.5 |
C12—N2—O2 | 119.4 (2) | H10A—C10—H10C | 109.5 |
C7—N2—O2 | 119.5 (2) | H10B—C10—H10C | 109.5 |
C13—N3—Ni1 | 163.1 (2) | C12—C11—C9 | 121.2 (3) |
C14—N4—Ni1 | 164.7 (2) | C12—C11—H11 | 119.4 |
N1—C1—C2 | 120.2 (3) | C9—C11—H11 | 119.4 |
N1—C1—H1 | 119.9 | N2—C12—C11 | 120.0 (3) |
C2—C1—H1 | 119.9 | N2—C12—H12 | 120.0 |
C3—C2—C1 | 121.0 (3) | C11—C12—H12 | 120.0 |
C3—C2—H2 | 119.5 | N3—C13—S1 | 178.3 (2) |
C1—C2—H2 | 119.5 | N4—C14—S2 | 178.7 (2) |
C2—C3—C5 | 117.0 (3) | N1—O1—Ni1 | 116.01 (14) |
C2—C3—C4 | 121.0 (4) | N2—O2—Ni1 | 112.85 (13) |
C5—C3—C4 | 121.9 (4) | Ni1—O3—H3WA | 109.5 |
C3—C4—H4A | 109.5 | Ni1—O3—H3WB | 119.0 |
C3—C4—H4B | 109.5 | H3WA—O3—H3WB | 124.0 |
H4A—C4—H4B | 109.5 | Ni1—O4—H4WA | 109.5 |
C3—C4—H4C | 109.5 | Ni1—O4—H4WB | 126.9 |
H4A—C4—H4C | 109.5 | H4WA—O4—H4WB | 123.5 |
H4B—C4—H4C | 109.5 | H5B—O5—H5A | 110.9 |
| | | |
N4—Ni1—N3—C13 | 22.6 (13) | N2—C7—C8—C9 | −0.9 (5) |
O3—Ni1—N3—C13 | 34.2 (7) | C7—C8—C9—C11 | 3.0 (5) |
O4—Ni1—N3—C13 | −145.6 (7) | C7—C8—C9—C10 | −174.3 (3) |
O2—Ni1—N3—C13 | 126.6 (7) | C8—C9—C11—C12 | −2.3 (5) |
O1—Ni1—N3—C13 | −57.4 (7) | C10—C9—C11—C12 | 175.0 (3) |
N3—Ni1—N4—C14 | 22.7 (14) | C7—N2—C12—C11 | 2.8 (4) |
O3—Ni1—N4—C14 | 11.1 (8) | O2—N2—C12—C11 | −173.5 (2) |
O4—Ni1—N4—C14 | −169.1 (8) | C9—C11—C12—N2 | −0.5 (4) |
O2—Ni1—N4—C14 | −81.0 (8) | C1—N1—O1—Ni1 | −79.0 (3) |
O1—Ni1—N4—C14 | 103.0 (8) | C6—N1—O1—Ni1 | 98.7 (2) |
C6—N1—C1—C2 | −1.5 (5) | N3—Ni1—O1—N1 | −0.75 (16) |
O1—N1—C1—C2 | 176.1 (3) | N4—Ni1—O1—N1 | −174.68 (16) |
N1—C1—C2—C3 | 0.2 (5) | O3—Ni1—O1—N1 | −87.62 (16) |
C1—C2—C3—C5 | 1.3 (5) | O4—Ni1—O1—N1 | 92.74 (15) |
C1—C2—C3—C4 | −175.6 (3) | O2—Ni1—O1—N1 | 104.0 (8) |
C2—C3—C5—C6 | −1.5 (5) | C12—N2—O2—Ni1 | 88.0 (2) |
C4—C3—C5—C6 | 175.3 (3) | C7—N2—O2—Ni1 | −88.3 (2) |
C1—N1—C6—C5 | 1.3 (4) | N3—Ni1—O2—N2 | −171.32 (15) |
O1—N1—C6—C5 | −176.3 (3) | N4—Ni1—O2—N2 | 2.71 (15) |
C3—C5—C6—N1 | 0.3 (5) | O3—Ni1—O2—N2 | −84.65 (15) |
C12—N2—C7—C8 | −2.1 (4) | O4—Ni1—O2—N2 | 94.99 (14) |
O2—N2—C7—C8 | 174.2 (3) | O1—Ni1—O2—N2 | 83.7 (9) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3WA···S2i | 0.82 | 2.66 | 3.337 (2) | 140 |
O3—H3WB···O5i | 0.76 | 1.98 | 2.690 (3) | 157 |
O4—H4WA···O2ii | 0.82 | 2.07 | 2.811 (2) | 151 |
O4—H4WB···O1iii | 0.74 | 2.17 | 2.892 (3) | 165 |
O5—H5A···O2iv | 0.88 | 2.00 | 2.879 (3) | 174 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+2, −y+2, −z+2; (iii) −x+1, −y+2, −z+2; (iv) x−1, y, z. |