In the title complex, [Ni(NCS)
2(H
2O)
4]·4C
6H
9N
3·2H
2O, the nickel(II) ion occupies an inversion centre and is octahedrally coordinated by two N-bonded thiocyanate ions and four water molecules. The two distinct 2-amino-4,6-dimethylpyrimidine molecules adopt distinct base-pairing dimerization patterns
via different pairs of N—H
N bonds. They are also hydrogen bonded to the coordinated and uncoordinated water molecules and thiocyanate ions through O—H
O, O—H
S(thiocyanate) and N—H
N(thiocyanate) hydrogen bonds.
Supporting information
CCDC reference: 254309
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.045
- wR factor = 0.115
- Data-to-parameter ratio = 20.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.96
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.66 mm
PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C7 .. 6.78 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni - N4 .. 5.18 su
PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2A ... ?
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 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
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker 2001); cell refinement: SMART; data reduction: SHELXTL (Bruker 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
Tetraaquadithiocyanatonickel(II) tetrakis(2-amino-4,6-dimethylpyrimidine)
dihydrate
top
Crystal data top
[Ni(C6H8N2O4S2)]·4C6H9N3·2H2O | Z = 1 |
Mr = 775.61 | F(000) = 410 |
Triclinic, P1 | Dx = 1.339 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8006 (5) Å | Cell parameters from 7595 reflections |
b = 11.6289 (8) Å | θ = 1.9–28.3° |
c = 11.9121 (8) Å | µ = 0.67 mm−1 |
α = 67.701 (1)° | T = 293 K |
β = 75.488 (1)° | Plate, pale green |
γ = 78.896 (1)° | 0.66 × 0.60 × 0.15 mm |
V = 962.12 (11) Å3 | |
Data collection top
Bruker SMART CCD diffractometer | 4605 independent reflections |
Radiation source: fine-focus sealed tube | 3465 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 28.3°, θmin = 1.9° |
Absorption correction: part of the refinement model (ΔF) (SHELXA; Bruker, 2001) | h = −10→10 |
Tmin = 0.667, Tmax = 0.906 | k = −14→15 |
7595 measured reflections | l = −15→14 |
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)] = 0.045 | Hydrogen site location: difmap (O-H) and geom (others) |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0548P)2 + 0.1851P] where P = (Fo2 + 2Fc2)/3 |
4605 reflections | (Δ/σ)max < 0.001 |
227 parameters | Δρmax = 0.23 e Å−3 |
9 restraints | Δρmin = −0.25 e Å−3 |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'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 on F2 for ALL reflections except those flagged by the user
for potential systematic errors. Weighted R-factors wR
and all goodnesses of fit S are based on F2,
conventional R-factors R are based on F, with F
set to zero for negative F2. The observed criterion of F2 >
σ(F2) is used only for calculating -R-factor-obs
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 | |
Ni | 0.50000 | 0.00000 | 0.50000 | 0.0370 (1) | |
S1 | 0.18407 (10) | 0.34064 (7) | 0.21736 (7) | 0.0641 (3) | |
O1 | 0.6856 (2) | 0.10938 (15) | 0.49346 (14) | 0.0487 (6) | |
O2 | 0.3409 (2) | 0.02895 (15) | 0.65679 (14) | 0.0488 (5) | |
N4 | 0.3736 (3) | 0.15530 (19) | 0.38445 (19) | 0.0512 (7) | |
C7 | 0.2957 (3) | 0.2330 (2) | 0.3146 (2) | 0.0430 (7) | |
N1 | 0.6246 (2) | 0.14024 (16) | 0.90636 (16) | 0.0389 (5) | |
N2 | 0.6038 (3) | −0.01818 (18) | 0.84202 (17) | 0.0482 (7) | |
N3 | 0.7493 (3) | 0.14728 (18) | 0.69873 (16) | 0.0423 (6) | |
C1 | 0.6589 (3) | 0.0934 (2) | 0.81431 (19) | 0.0360 (6) | |
C2 | 0.8054 (3) | 0.2587 (2) | 0.6720 (2) | 0.0432 (7) | |
C3 | 0.7726 (3) | 0.3144 (2) | 0.7601 (2) | 0.0465 (8) | |
C4 | 0.6825 (3) | 0.2509 (2) | 0.8777 (2) | 0.0429 (7) | |
C5 | 0.6470 (4) | 0.3024 (3) | 0.9808 (3) | 0.0654 (10) | |
C6 | 0.9074 (4) | 0.3179 (3) | 0.5438 (2) | 0.0636 (10) | |
N1A | 0.2735 (2) | 0.24335 (15) | 0.71178 (16) | 0.0391 (6) | |
N2A | 0.4108 (3) | 0.35410 (18) | 0.51457 (18) | 0.0554 (7) | |
N3A | 0.3587 (3) | 0.44709 (16) | 0.65994 (17) | 0.0406 (6) | |
C1A | 0.3462 (3) | 0.34771 (19) | 0.63175 (19) | 0.0382 (6) | |
C2A | 0.2892 (3) | 0.4423 (2) | 0.7759 (2) | 0.0424 (7) | |
C3A | 0.2071 (3) | 0.3405 (2) | 0.8623 (2) | 0.0472 (8) | |
C4A | 0.2040 (3) | 0.2410 (2) | 0.82764 (19) | 0.0396 (6) | |
C5A | 0.1250 (4) | 0.1235 (2) | 0.9160 (2) | 0.0541 (8) | |
C6A | 0.3056 (4) | 0.5531 (3) | 0.8068 (3) | 0.0669 (11) | |
O3 | 1.0299 (3) | −0.0856 (2) | 0.6988 (2) | 0.0839 (9) | |
H11 | 0.70780 | 0.11570 | 0.56100 | 0.0590* | |
H12 | 0.79490 | 0.10600 | 0.44230 | 0.0590* | |
H21 | 0.23650 | −0.00530 | 0.68060 | 0.0590* | |
H22 | 0.30900 | 0.10500 | 0.66930 | 0.0590* | |
H2A | 0.62640 | −0.05270 | 0.78680 | 0.0580* | |
H2B | 0.54570 | −0.05520 | 0.91500 | 0.0580* | |
H3 | 0.80980 | 0.39210 | 0.74120 | 0.0560* | |
H5A | 0.71080 | 0.24820 | 1.04420 | 0.0980* | |
H5B | 0.52170 | 0.30760 | 1.01490 | 0.0980* | |
H5C | 0.68600 | 0.38420 | 0.94900 | 0.0980* | |
H6A | 1.01330 | 0.26380 | 0.52860 | 0.0950* | |
H6B | 0.93960 | 0.39660 | 0.53580 | 0.0950* | |
H6C | 0.83470 | 0.33110 | 0.48490 | 0.0950* | |
H21A | 0.45760 | 0.41960 | 0.46130 | 0.0660* | |
H22B | 0.40560 | 0.29270 | 0.49250 | 0.0660* | |
H31A | 0.15530 | 0.33930 | 0.94200 | 0.0570* | |
H51A | 0.03600 | 0.10730 | 0.88260 | 0.0810* | |
H52B | 0.07150 | 0.13360 | 0.99400 | 0.0810* | |
H53C | 0.21700 | 0.05450 | 0.92770 | 0.0810* | |
H61A | 0.26450 | 0.62850 | 0.74600 | 0.1000* | |
H62B | 0.42800 | 0.55500 | 0.80690 | 0.1000* | |
H63C | 0.23480 | 0.54670 | 0.88700 | 0.1000* | |
H31 | 0.92590 | −0.03380 | 0.70910 | 0.1010* | |
H32 | 0.99220 | −0.16540 | 0.74750 | 0.1010* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.0433 (2) | 0.0385 (2) | 0.0349 (2) | −0.0090 (2) | −0.0065 (2) | −0.0176 (2) |
S1 | 0.0690 (5) | 0.0602 (4) | 0.0543 (4) | −0.0009 (3) | −0.0201 (3) | −0.0081 (3) |
O1 | 0.0520 (10) | 0.0619 (10) | 0.0448 (9) | −0.0203 (8) | −0.0024 (7) | −0.0300 (8) |
O2 | 0.0541 (10) | 0.0511 (9) | 0.0485 (9) | −0.0166 (8) | 0.0037 (8) | −0.0288 (8) |
N4 | 0.0577 (13) | 0.0488 (11) | 0.0510 (12) | −0.0061 (10) | −0.0146 (10) | −0.0191 (10) |
C7 | 0.0489 (14) | 0.0448 (12) | 0.0397 (12) | −0.0107 (10) | −0.0027 (10) | −0.0207 (10) |
N1 | 0.0435 (10) | 0.0434 (9) | 0.0334 (9) | −0.0051 (8) | −0.0063 (8) | −0.0181 (8) |
N2 | 0.0637 (13) | 0.0507 (11) | 0.0363 (10) | −0.0206 (10) | 0.0007 (9) | −0.0216 (9) |
N3 | 0.0441 (11) | 0.0557 (11) | 0.0328 (9) | −0.0158 (9) | −0.0028 (8) | −0.0197 (8) |
C1 | 0.0330 (11) | 0.0450 (11) | 0.0332 (10) | −0.0062 (9) | −0.0058 (9) | −0.0166 (9) |
C2 | 0.0393 (12) | 0.0541 (13) | 0.0374 (12) | −0.0106 (10) | −0.0083 (10) | −0.0141 (10) |
C3 | 0.0528 (14) | 0.0423 (12) | 0.0484 (13) | −0.0114 (10) | −0.0122 (11) | −0.0159 (10) |
C4 | 0.0440 (13) | 0.0466 (12) | 0.0448 (12) | −0.0024 (10) | −0.0101 (10) | −0.0237 (10) |
C5 | 0.085 (2) | 0.0654 (16) | 0.0593 (17) | −0.0139 (15) | −0.0046 (15) | −0.0397 (14) |
C6 | 0.0695 (19) | 0.0775 (18) | 0.0420 (14) | −0.0310 (15) | −0.0057 (13) | −0.0111 (13) |
N1A | 0.0440 (11) | 0.0345 (9) | 0.0383 (10) | −0.0099 (8) | −0.0041 (8) | −0.0121 (7) |
N2A | 0.0853 (16) | 0.0428 (10) | 0.0405 (11) | −0.0280 (11) | 0.0079 (10) | −0.0198 (9) |
N3A | 0.0479 (11) | 0.0369 (9) | 0.0401 (10) | −0.0103 (8) | −0.0053 (8) | −0.0162 (8) |
C1A | 0.0417 (12) | 0.0363 (10) | 0.0387 (11) | −0.0072 (9) | −0.0060 (9) | −0.0152 (9) |
C2A | 0.0447 (13) | 0.0464 (12) | 0.0427 (12) | −0.0026 (10) | −0.0107 (10) | −0.0224 (10) |
C3A | 0.0508 (14) | 0.0568 (14) | 0.0357 (12) | −0.0083 (11) | −0.0028 (10) | −0.0204 (10) |
C4A | 0.0353 (11) | 0.0422 (11) | 0.0370 (11) | −0.0039 (9) | −0.0072 (9) | −0.0090 (9) |
C5A | 0.0540 (15) | 0.0502 (13) | 0.0447 (13) | −0.0118 (12) | −0.0013 (11) | −0.0042 (11) |
C6A | 0.086 (2) | 0.0649 (17) | 0.0660 (18) | −0.0158 (15) | −0.0081 (16) | −0.0413 (15) |
O3 | 0.0488 (12) | 0.0948 (16) | 0.1185 (19) | −0.0208 (11) | 0.0125 (12) | −0.0606 (15) |
Geometric parameters (Å, º) top
Ni—O1 | 2.0731 (17) | N3A—C2A | 1.335 (3) |
Ni—O2 | 2.0728 (16) | N2A—H22B | 0.8600 |
Ni—N4 | 2.058 (2) | N2A—H21A | 0.8604 |
Ni—O1i | 2.0731 (17) | C2—C3 | 1.380 (3) |
Ni—O2i | 2.0728 (16) | C2—C6 | 1.498 (3) |
Ni—N4i | 2.058 (2) | C3—C4 | 1.387 (3) |
S1—C7 | 1.629 (2) | C4—C5 | 1.506 (4) |
O1—H11 | 0.8957 | C3—H3 | 0.9302 |
O1—H12 | 0.9191 | C5—H5C | 0.9598 |
O2—H21 | 0.9087 | C5—H5A | 0.9600 |
O2—H22 | 0.9289 | C5—H5B | 0.9596 |
O3—H32 | 0.9462 | C6—H6C | 0.9600 |
O3—H31 | 0.9241 | C6—H6B | 0.9592 |
N4—C7 | 1.162 (3) | C6—H6A | 0.9604 |
N1—C4 | 1.338 (3) | C2A—C6A | 1.503 (4) |
N1—C1 | 1.349 (3) | C2A—C3A | 1.381 (3) |
N2—C1 | 1.340 (3) | C3A—C4A | 1.374 (3) |
N3—C2 | 1.344 (3) | C4A—C5A | 1.504 (3) |
N3—C1 | 1.347 (3) | C3A—H31A | 0.9299 |
N2—H2B | 0.8603 | C5A—H52B | 0.9596 |
N2—H2A | 0.8602 | C5A—H53C | 0.9601 |
N1A—C1A | 1.349 (3) | C5A—H51A | 0.9599 |
N1A—C4A | 1.342 (3) | C6A—H63C | 0.9595 |
N2A—C1A | 1.338 (3) | C6A—H61A | 0.9604 |
N3A—C1A | 1.346 (3) | C6A—H62B | 0.9596 |
| | | |
O1—Ni—O2 | 91.75 (6) | N1—C4—C3 | 122.1 (2) |
O1—Ni—N4 | 89.45 (8) | N1—C4—C5 | 116.4 (2) |
O1—Ni—O1i | 180.00 | C3—C4—C5 | 121.5 (2) |
O1—Ni—O2i | 88.25 (6) | C2—C3—H3 | 121.03 |
O1—Ni—N4i | 90.55 (8) | C4—C3—H3 | 121.05 |
O2—Ni—N4 | 92.20 (8) | C4—C5—H5B | 109.45 |
O1i—Ni—O2 | 88.25 (6) | C4—C5—H5A | 109.47 |
O2—Ni—O2i | 180.00 | H5A—C5—H5B | 109.50 |
O2—Ni—N4i | 87.80 (8) | C4—C5—H5C | 109.47 |
O1i—Ni—N4 | 90.55 (8) | H5B—C5—H5C | 109.51 |
O2i—Ni—N4 | 87.80 (8) | H5A—C5—H5C | 109.43 |
N4—Ni—N4i | 180.00 | C2—C6—H6B | 109.46 |
O1i—Ni—O2i | 91.75 (6) | C2—C6—H6C | 109.47 |
O1i—Ni—N4i | 89.45 (8) | C2—C6—H6A | 109.44 |
O2i—Ni—N4i | 92.20 (8) | H6A—C6—H6B | 109.47 |
Ni—O1—H12 | 118.16 | H6B—C6—H6C | 109.50 |
H11—O1—H12 | 105.38 | H6A—C6—H6C | 109.48 |
Ni—O1—H11 | 123.29 | N1A—C1A—N3A | 125.24 (19) |
H21—O2—H22 | 103.87 | N2A—C1A—N3A | 116.9 (2) |
Ni—O2—H21 | 112.91 | N1A—C1A—N2A | 117.9 (2) |
Ni—O2—H22 | 126.32 | N3A—C2A—C3A | 121.4 (2) |
H31—O3—H32 | 101.61 | N3A—C2A—C6A | 116.4 (2) |
Ni—N4—C7 | 171.8 (2) | C3A—C2A—C6A | 122.1 (2) |
C1—N1—C4 | 116.26 (18) | C2A—C3A—C4A | 118.4 (2) |
C1—N3—C2 | 117.2 (2) | N1A—C4A—C5A | 116.1 (2) |
H2A—N2—H2B | 120.03 | C3A—C4A—C5A | 122.63 (19) |
C1—N2—H2B | 119.98 | N1A—C4A—C3A | 121.3 (2) |
C1—N2—H2A | 119.99 | C4A—C3A—H31A | 120.81 |
C1A—N1A—C4A | 116.75 (19) | C2A—C3A—H31A | 120.81 |
C1A—N3A—C2A | 116.8 (2) | C4A—C5A—H51A | 109.45 |
C1A—N2A—H22B | 119.99 | C4A—C5A—H52B | 109.51 |
C1A—N2A—H21A | 120.03 | H51A—C5A—H52B | 109.46 |
H21A—N2A—H22B | 119.97 | H51A—C5A—H53C | 109.39 |
S1—C7—N4 | 179.1 (2) | C4A—C5A—H53C | 109.51 |
N1—C1—N2 | 116.96 (19) | H52B—C5A—H53C | 109.51 |
N1—C1—N3 | 125.4 (2) | C2A—C6A—H62B | 109.45 |
N2—C1—N3 | 117.6 (2) | C2A—C6A—H63C | 109.55 |
N3—C2—C3 | 121.1 (2) | C2A—C6A—H61A | 109.41 |
C3—C2—C6 | 121.8 (2) | H61A—C6A—H63C | 109.46 |
N3—C2—C6 | 117.1 (2) | H62B—C6A—H63C | 109.51 |
C2—C3—C4 | 117.9 (2) | H61A—C6A—H62B | 109.44 |
| | | |
O2—Ni—O1—H11 | 31.49 | C2—N3—C1—N1 | −2.1 (4) |
O2—Ni—O1—H12 | 166.82 | C2—N3—C1—N2 | −179.5 (2) |
N4—Ni—O1—H11 | 123.67 | C1—N3—C2—C3 | 0.6 (4) |
N4—Ni—O1—H12 | −100.99 | C1—N3—C2—C6 | 179.4 (2) |
O2i—Ni—O1—H11 | −148.51 | C4A—N1A—C1A—N2A | −177.7 (2) |
O2i—Ni—O1—H12 | −13.18 | C4A—N1A—C1A—N3A | 2.0 (3) |
N4i—Ni—O1—H11 | −56.33 | C1A—N1A—C4A—C3A | 0.1 (3) |
N4i—Ni—O1—H12 | 79.01 | C1A—N1A—C4A—C5A | −179.5 (2) |
O1—Ni—O2—H21 | 175.29 | C1A—N3A—C2A—C3A | −0.5 (4) |
O1—Ni—O2—H22 | 45.96 | C1A—N3A—C2A—C6A | 179.4 (2) |
N4—Ni—O2—H21 | 85.77 | C2A—N3A—C1A—N1A | −1.7 (4) |
N4—Ni—O2—H22 | −43.55 | C2A—N3A—C1A—N2A | 178.0 (2) |
O1i—Ni—O2—H21 | −4.71 | N3—C2—C3—C4 | 1.0 (4) |
O1i—Ni—O2—H22 | −134.04 | C6—C2—C3—C4 | −177.8 (2) |
N4i—Ni—O2—H21 | −94.23 | C2—C3—C4—N1 | −1.4 (4) |
N4i—Ni—O2—H22 | 136.45 | C2—C3—C4—C5 | 177.7 (2) |
C4—N1—C1—N2 | 179.1 (2) | C6A—C2A—C3A—C4A | −177.5 (2) |
C4—N1—C1—N3 | 1.7 (3) | N3A—C2A—C3A—C4A | 2.4 (4) |
C1—N1—C4—C3 | 0.1 (3) | C2A—C3A—C4A—N1A | −2.1 (4) |
C1—N1—C4—C5 | −179.0 (2) | C2A—C3A—C4A—C5A | 177.3 (2) |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···N1ii | 0.86 | 2.18 | 3.040 (3) | 175 |
O1—H11···N3 | 0.90 | 1.92 | 2.816 (3) | 174 |
O1—H12···O3iii | 0.92 | 1.94 | 2.818 (3) | 159 |
O2—H21···O3iv | 0.91 | 1.94 | 2.836 (3) | 168 |
N2A—H21A···N3Av | 0.86 | 2.16 | 2.997 (3) | 164 |
O2—H22···N1A | 0.93 | 1.82 | 2.736 (3) | 170 |
N2A—H22B···N4 | 0.86 | 2.48 | 3.322 (3) | 167 |
O3—H31···N3 | 0.92 | 2.26 | 3.137 (3) | 158 |
O3—H32···S1i | 0.95 | 2.52 | 3.377 (3) | 150 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z+2; (iii) −x+2, −y, −z+1; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1. |