The title compound, {[Ni(C2H8N2)3][Cd(C4N2S2)2]·H2O}n, contains chains of bis(1,2-dicyanoethylenedithiolato)cadmate(II) complex anions, tri(ethylenediamine)nickel(II) cations and uncoordinated water molecules. The CdII centre is in a very distorted CdS6 octahedral environment. Three bidentate ethylenediamine ligands are coordinated to the NiII atom, resulting in somewhat distorted NiN6 octahedra. The polymeric anionic chains, cations and water molecules are linked by hydrogen bonds into a three-dimensional framework.
Supporting information
CCDC reference: 287570
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.013 Å
- R factor = 0.051
- wR factor = 0.083
- Data-to-parameter ratio = 15.2
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Cd1 - S3_a .. 23.77 su
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - N5 .. 8.88 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - N7 .. 8.99 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - N8 .. 7.18 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - N9 .. 7.29 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - N10 .. 7.95 su
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Ni1
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 13
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C1 - C2 ... 1.43 Ang.
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C3 - C4 ... 1.46 Ang.
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C5 - C6 ... 1.43 Ang.
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C7 - C8 ... 1.44 Ang.
PLAT417_ALERT_2_C Short Inter D-H..H-D H1 .. H1 .. 2.14 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor N10 - H10B ... ?
PLAT731_ALERT_1_C Bond Calc 0.84(7), Rep 0.84(3) ...... 2.33 su-Rat
O1 -H2 1.555 1.555
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
17 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
13 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
H2mnt (1.00 mmol) and NaOH (2.00 mmol) were dissolved in ethanol (20 ml). To this solution, en (1.50 mmol) and an ethanol mixture (30 ml) of CdSO4 (1.00 mmol) and NiSO4 (0.50 mmol) were added dropwise at 313 K. The mixture was stirred for 6 h and part of the solvent was evaporated in a rotary vacuum evaporator. The resulting solution was filtered and left in air for about 20 days. Large green block-like crystals of (I) suitable for X-ray analysis were obtained. Analysis found: C 25.75, H 3.96, N 21.38, S 19.58%; calculated for C14H26CdN10NiOS4: C 25.88, H 4.03, N 21.55, S 19.74%.
The water H atoms were found in difference maps. The O—H distances were restrained to 0.90 (1) Å and the Uiso(H) values were allowed to refine. Please check s.u. values in Table 2; they do not correspond to those in CIF. All other H atoms were placed in idealized positions (C—H = 0.97 Å and N—H = 0.90 Å) and refined as riding on their carrier atoms with Uiso(H) = 1.2Ueq(carrier).
Data collection: SMART (Bruker,1997); cell refinement: SAINT (Bruker,1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
catena-Poly[bis(ethylenediamine-
κ2N,
N')copper(II) (2,3-dimercaptobutenedinitrile-
κ2S,
S')(2,3-dimercaptobutenedinitrile-
κ4S,
S',
N,
N')cuprate(II)]
top
Crystal data top
[Ni(C2H8N2)3][Cd(C4N2S2)2]·H2O | F(000) = 1312 |
Mr = 649.80 | Dx = 1.749 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1561 reflections |
a = 7.5796 (15) Å | θ = 2.4–19.6° |
b = 19.255 (4) Å | µ = 1.99 mm−1 |
c = 17.201 (4) Å | T = 293 K |
β = 100.509 (4)° | Block, green |
V = 2468.3 (9) Å3 | 0.30 × 0.15 × 0.12 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD diffractometer | 4346 independent reflections |
Radiation source: fine-focus sealed tube | 2220 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −9→8 |
Tmin = 0.587, Tmax = 0.796 | k = −22→16 |
12887 measured reflections | l = −20→20 |
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)] = 0.051 | Hydrogen site location: difmap and geom |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0141P)2] where P = (Fo2 + 2Fc2)/3 |
4346 reflections | (Δ/σ)max = 0.001 |
286 parameters | Δρmax = 0.88 e Å−3 |
4 restraints | Δρmin = −0.77 e Å−3 |
Crystal data top
[Ni(C2H8N2)3][Cd(C4N2S2)2]·H2O | V = 2468.3 (9) Å3 |
Mr = 649.80 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.5796 (15) Å | µ = 1.99 mm−1 |
b = 19.255 (4) Å | T = 293 K |
c = 17.201 (4) Å | 0.30 × 0.15 × 0.12 mm |
β = 100.509 (4)° | |
Data collection top
Bruker SMART CCD diffractometer | 4346 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 2220 reflections with I > 2σ(I) |
Tmin = 0.587, Tmax = 0.796 | Rint = 0.069 |
12887 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 4 restraints |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.88 e Å−3 |
4346 reflections | Δρmin = −0.77 e Å−3 |
286 parameters | |
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 | |
Cd1 | 0.74918 (10) | 0.03798 (4) | 1.00912 (4) | 0.0590 (3) | |
Ni1 | 0.11839 (14) | 0.29140 (5) | 0.96600 (5) | 0.0294 (3) | |
N1 | 1.1518 (12) | 0.1300 (5) | 1.3106 (5) | 0.093 (3) | |
N2 | 1.1703 (12) | −0.0685 (5) | 1.3014 (5) | 0.088 (3) | |
N3 | 0.3509 (12) | −0.0100 (5) | 0.6924 (5) | 0.089 (3) | |
N4 | 0.4554 (16) | 0.1840 (5) | 0.7199 (5) | 0.122 (4) | |
N5 | 0.2319 (9) | 0.1972 (3) | 1.0178 (4) | 0.050 (2) | |
H5A | 0.1444 | 0.1687 | 1.0277 | 0.060* | |
H5B | 0.2922 | 0.1754 | 0.9844 | 0.060* | |
N6 | 0.3339 (9) | 0.3348 (4) | 1.0519 (4) | 0.059 (2) | |
H6A | 0.3923 | 0.3678 | 1.0296 | 0.071* | |
H6B | 0.2908 | 0.3537 | 1.0925 | 0.071* | |
N7 | −0.0792 (9) | 0.2953 (3) | 1.0410 (4) | 0.056 (2) | |
H7A | −0.1500 | 0.2575 | 1.0324 | 0.067* | |
H7B | −0.0240 | 0.2949 | 1.0919 | 0.067* | |
N8 | 0.0089 (10) | 0.3936 (3) | 0.9380 (4) | 0.059 (2) | |
H8A | 0.0970 | 0.4235 | 0.9323 | 0.071* | |
H8B | −0.0713 | 0.3925 | 0.8925 | 0.071* | |
N9 | −0.0619 (9) | 0.2407 (4) | 0.8724 (4) | 0.059 (2) | |
H9A | −0.0971 | 0.1996 | 0.8892 | 0.070* | |
H9B | −0.1600 | 0.2672 | 0.8569 | 0.070* | |
N10 | 0.2792 (9) | 0.2982 (3) | 0.8752 (4) | 0.062 (2) | |
H10A | 0.3330 | 0.3400 | 0.8766 | 0.074* | |
H10B | 0.3644 | 0.2651 | 0.8821 | 0.074* | |
O1 | 0.4310 (11) | 0.4543 (5) | 0.9367 (5) | 0.106 (3) | |
S1 | 0.9130 (3) | 0.12532 (12) | 1.10874 (14) | 0.0522 (7) | |
S2 | 0.9539 (3) | −0.05198 (11) | 1.09359 (12) | 0.0465 (7) | |
S3 | 0.5457 (3) | −0.03029 (12) | 0.90052 (12) | 0.0478 (7) | |
S4 | 0.5892 (3) | 0.14580 (12) | 0.92933 (13) | 0.0473 (7) | |
C1 | 1.0891 (12) | 0.1025 (5) | 1.2544 (6) | 0.055 (3) | |
C2 | 1.0132 (11) | 0.0692 (5) | 1.1819 (5) | 0.041 (2) | |
C3 | 1.0272 (10) | 0.0002 (5) | 1.1759 (4) | 0.038 (2) | |
C4 | 1.1077 (12) | −0.0390 (5) | 1.2463 (5) | 0.057 (3) | |
C5 | 0.4170 (13) | 0.0101 (5) | 0.7528 (6) | 0.060 (3) | |
C6 | 0.4939 (10) | 0.0350 (5) | 0.8301 (4) | 0.044 (2) | |
C7 | 0.5163 (11) | 0.1045 (5) | 0.8403 (5) | 0.044 (2) | |
C8 | 0.4785 (16) | 0.1491 (5) | 0.7722 (6) | 0.078 (4) | |
C9 | 0.3558 (12) | 0.2142 (5) | 1.0927 (5) | 0.056 (3) | |
H9C | 0.2884 | 0.2219 | 1.1347 | 0.067* | |
H9D | 0.4388 | 0.1762 | 1.1080 | 0.067* | |
C10 | 0.4539 (13) | 0.2770 (5) | 1.0794 (5) | 0.060 (3) | |
H10C | 0.5284 | 0.2674 | 1.0404 | 0.072* | |
H10D | 0.5323 | 0.2901 | 1.1282 | 0.072* | |
C11 | −0.1887 (12) | 0.3577 (4) | 1.0255 (5) | 0.057 (3) | |
H11A | −0.2355 | 0.3704 | 1.0724 | 0.069* | |
H11B | −0.2895 | 0.3489 | 0.9831 | 0.069* | |
C12 | −0.0780 (12) | 0.4157 (5) | 1.0028 (6) | 0.064 (3) | |
H12A | −0.1537 | 0.4557 | 0.9865 | 0.077* | |
H12B | 0.0121 | 0.4291 | 1.0478 | 0.077* | |
C13 | 0.0323 (14) | 0.2301 (5) | 0.8062 (5) | 0.072 (3) | |
H13A | −0.0550 | 0.2251 | 0.7577 | 0.086* | |
H13B | 0.1014 | 0.1875 | 0.8146 | 0.086* | |
C14 | 0.1531 (14) | 0.2882 (5) | 0.7976 (5) | 0.076 (3) | |
H14A | 0.0841 | 0.3302 | 0.7834 | 0.091* | |
H14B | 0.2206 | 0.2781 | 0.7562 | 0.091* | |
H1 | 0.534 (5) | 0.460 (4) | 0.962 (4) | 0.080* | |
H2 | 0.370 (11) | 0.476 (4) | 0.899 (4) | 0.080* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.0687 (5) | 0.0490 (5) | 0.0497 (5) | −0.0014 (4) | −0.0145 (4) | 0.0023 (4) |
Ni1 | 0.0350 (6) | 0.0320 (6) | 0.0224 (6) | −0.0019 (6) | 0.0088 (5) | −0.0017 (5) |
N1 | 0.092 (8) | 0.116 (8) | 0.060 (6) | −0.010 (6) | −0.011 (6) | −0.034 (6) |
N2 | 0.099 (8) | 0.111 (8) | 0.048 (6) | 0.008 (6) | −0.003 (6) | 0.024 (5) |
N3 | 0.099 (8) | 0.118 (8) | 0.048 (6) | −0.001 (6) | 0.005 (6) | −0.025 (6) |
N4 | 0.232 (13) | 0.089 (8) | 0.050 (6) | 0.047 (8) | 0.035 (8) | 0.027 (6) |
N5 | 0.054 (5) | 0.055 (5) | 0.049 (5) | −0.021 (4) | 0.027 (4) | −0.014 (4) |
N6 | 0.075 (6) | 0.059 (6) | 0.044 (5) | −0.013 (5) | 0.013 (4) | 0.005 (4) |
N7 | 0.070 (6) | 0.036 (5) | 0.059 (5) | 0.003 (5) | 0.005 (4) | 0.011 (4) |
N8 | 0.074 (6) | 0.063 (6) | 0.048 (5) | −0.014 (5) | 0.031 (5) | 0.000 (4) |
N9 | 0.062 (6) | 0.067 (6) | 0.050 (5) | −0.001 (4) | 0.021 (4) | 0.011 (4) |
N10 | 0.070 (6) | 0.039 (5) | 0.078 (6) | 0.001 (5) | 0.019 (5) | −0.003 (5) |
O1 | 0.102 (7) | 0.097 (7) | 0.102 (7) | 0.002 (6) | −0.031 (5) | 0.010 (5) |
S1 | 0.0634 (19) | 0.0404 (16) | 0.0494 (16) | −0.0092 (13) | 0.0009 (14) | 0.0005 (12) |
S2 | 0.0556 (17) | 0.0438 (16) | 0.0374 (14) | 0.0044 (13) | 0.0009 (12) | 0.0014 (12) |
S3 | 0.0546 (17) | 0.0475 (16) | 0.0399 (14) | −0.0072 (14) | 0.0046 (12) | 0.0017 (13) |
S4 | 0.0567 (17) | 0.0421 (15) | 0.0428 (15) | 0.0057 (13) | 0.0085 (13) | 0.0007 (12) |
C1 | 0.054 (7) | 0.062 (8) | 0.047 (7) | −0.008 (6) | 0.002 (6) | −0.003 (6) |
C2 | 0.042 (6) | 0.047 (6) | 0.036 (6) | −0.009 (5) | 0.008 (5) | −0.009 (5) |
C3 | 0.035 (6) | 0.052 (6) | 0.029 (5) | 0.004 (5) | 0.012 (4) | −0.001 (5) |
C4 | 0.054 (7) | 0.076 (8) | 0.040 (6) | −0.002 (6) | 0.011 (5) | 0.008 (6) |
C5 | 0.065 (8) | 0.067 (8) | 0.047 (7) | 0.012 (6) | 0.006 (6) | 0.001 (6) |
C6 | 0.040 (6) | 0.061 (7) | 0.031 (5) | 0.004 (5) | 0.003 (4) | −0.005 (5) |
C7 | 0.051 (6) | 0.048 (6) | 0.037 (6) | 0.013 (5) | 0.018 (5) | 0.003 (5) |
C8 | 0.134 (11) | 0.065 (8) | 0.038 (7) | 0.038 (8) | 0.019 (7) | 0.003 (6) |
C9 | 0.065 (7) | 0.050 (7) | 0.052 (6) | −0.002 (6) | 0.009 (5) | 0.001 (6) |
C10 | 0.080 (8) | 0.048 (7) | 0.054 (7) | −0.015 (6) | 0.018 (6) | −0.008 (5) |
C11 | 0.066 (8) | 0.048 (7) | 0.059 (7) | 0.005 (6) | 0.017 (6) | 0.011 (5) |
C12 | 0.065 (8) | 0.052 (7) | 0.080 (8) | 0.004 (6) | 0.023 (6) | −0.003 (6) |
C13 | 0.104 (9) | 0.062 (8) | 0.047 (7) | −0.038 (7) | 0.005 (6) | −0.013 (6) |
C14 | 0.097 (9) | 0.089 (9) | 0.048 (7) | −0.003 (8) | 0.028 (6) | 0.000 (7) |
Geometric parameters (Å, º) top
Cd1—S1 | 2.555 (2) | N10—C14 | 1.506 (9) |
Cd1—S3 | 2.558 (2) | N10—H10A | 0.9000 |
Cd1—S2 | 2.588 (2) | N10—H10B | 0.9000 |
Cd1—S4 | 2.657 (2) | O1—H1 | 0.83 (3) |
Cd1—S3i | 2.949 (3) | O1—H2 | 0.84 (3) |
Cd1—S2ii | 3.116 (3) | S1—C2 | 1.725 (9) |
Ni1—N5 | 2.133 (6) | S2—C3 | 1.742 (8) |
Ni1—N9 | 2.147 (7) | S3—C6 | 1.739 (8) |
Ni1—N7 | 2.149 (7) | S3—Cd1i | 2.949 (2) |
Ni1—N10 | 2.153 (7) | S4—C7 | 1.725 (8) |
Ni1—N8 | 2.156 (7) | C1—C2 | 1.427 (11) |
Ni1—N6 | 2.161 (6) | C2—C3 | 1.339 (10) |
N1—C1 | 1.128 (10) | C3—C4 | 1.462 (11) |
N2—C4 | 1.133 (10) | C5—C6 | 1.434 (11) |
N3—C5 | 1.136 (10) | C6—C7 | 1.357 (11) |
N4—C8 | 1.111 (11) | C7—C8 | 1.438 (12) |
N5—C9 | 1.485 (9) | C9—C10 | 1.459 (10) |
N5—H5A | 0.9000 | C9—H9C | 0.9700 |
N5—H5B | 0.9000 | C9—H9D | 0.9700 |
N6—C10 | 1.460 (9) | C10—H10C | 0.9700 |
N6—H6A | 0.9000 | C10—H10D | 0.9700 |
N6—H6B | 0.9000 | C11—C12 | 1.492 (11) |
N7—C11 | 1.457 (9) | C11—H11A | 0.9700 |
N7—H7A | 0.9000 | C11—H11B | 0.9700 |
N7—H7B | 0.9000 | C12—H12A | 0.9700 |
N8—C12 | 1.457 (10) | C12—H12B | 0.9700 |
N8—H8A | 0.9000 | C13—C14 | 1.470 (11) |
N8—H8B | 0.9000 | C13—H13A | 0.9700 |
N9—C13 | 1.464 (10) | C13—H13B | 0.9700 |
N9—H9A | 0.9000 | C14—H14A | 0.9700 |
N9—H9B | 0.9000 | C14—H14B | 0.9700 |
| | | |
S1—Cd1—S3 | 169.19 (8) | C14—N10—H10B | 110.4 |
S1—Cd1—S2 | 84.01 (7) | Ni1—N10—H10B | 110.4 |
S3—Cd1—S2 | 106.61 (7) | H10A—N10—H10B | 108.6 |
S1—Cd1—S4 | 87.27 (8) | H1—O1—H2 | 132 (10) |
S3—Cd1—S4 | 82.34 (7) | C2—S1—Cd1 | 99.9 (3) |
S2—Cd1—S4 | 169.62 (8) | C3—S2—Cd1 | 98.0 (3) |
S1—Cd1—S3i | 90.12 (8) | C6—S3—Cd1 | 99.6 (3) |
S3—Cd1—S3i | 86.85 (7) | C6—S3—Cd1i | 107.9 (3) |
S2—Cd1—S3i | 96.03 (8) | Cd1—S3—Cd1i | 93.15 (7) |
S4—Cd1—S3i | 89.60 (7) | C7—S4—Cd1 | 98.1 (3) |
S1—Cd1—S2ii | 90.60 (8) | N1—C1—C2 | 178.0 (12) |
S3—Cd1—S2ii | 91.83 (7) | C3—C2—C1 | 119.2 (8) |
S2—Cd1—S2ii | 87.42 (7) | C3—C2—S1 | 126.6 (7) |
S4—Cd1—S2ii | 87.04 (7) | C1—C2—S1 | 114.2 (7) |
S3i—Cd1—S2ii | 176.53 (6) | C2—C3—C4 | 118.4 (8) |
N5—Ni1—N9 | 94.6 (3) | C2—C3—S2 | 128.1 (7) |
N5—Ni1—N7 | 92.9 (2) | C4—C3—S2 | 113.5 (7) |
N9—Ni1—N7 | 92.8 (3) | N2—C4—C3 | 179.1 (11) |
N5—Ni1—N10 | 96.7 (3) | N3—C5—C6 | 177.8 (12) |
N9—Ni1—N10 | 81.4 (3) | C7—C6—C5 | 118.0 (8) |
N7—Ni1—N10 | 169.1 (3) | C7—C6—S3 | 128.0 (7) |
N5—Ni1—N8 | 168.4 (2) | C5—C6—S3 | 114.0 (7) |
N9—Ni1—N8 | 94.6 (3) | C6—C7—C8 | 118.9 (8) |
N7—Ni1—N8 | 79.6 (3) | C6—C7—S4 | 125.6 (7) |
N10—Ni1—N8 | 91.6 (3) | C8—C7—S4 | 115.6 (7) |
N5—Ni1—N6 | 81.1 (3) | N4—C8—C7 | 177.6 (15) |
N9—Ni1—N6 | 170.7 (3) | C10—C9—N5 | 107.9 (7) |
N7—Ni1—N6 | 95.7 (3) | C10—C9—H9C | 110.1 |
N10—Ni1—N6 | 90.9 (3) | N5—C9—H9C | 110.1 |
N8—Ni1—N6 | 90.7 (3) | C10—C9—H9D | 110.1 |
C9—N5—Ni1 | 108.5 (5) | N5—C9—H9D | 110.1 |
C9—N5—H5A | 110.0 | H9C—C9—H9D | 108.4 |
Ni1—N5—H5A | 110.0 | C9—C10—N6 | 112.1 (8) |
C9—N5—H5B | 110.0 | C9—C10—H10C | 109.2 |
Ni1—N5—H5B | 110.0 | N6—C10—H10C | 109.2 |
H5A—N5—H5B | 108.4 | C9—C10—H10D | 109.2 |
C10—N6—Ni1 | 106.0 (5) | N6—C10—H10D | 109.2 |
C10—N6—H6A | 110.5 | H10C—C10—H10D | 107.9 |
Ni1—N6—H6A | 110.5 | N7—C11—C12 | 109.7 (8) |
C10—N6—H6B | 110.5 | N7—C11—H11A | 109.7 |
Ni1—N6—H6B | 110.5 | C12—C11—H11A | 109.7 |
H6A—N6—H6B | 108.7 | N7—C11—H11B | 109.7 |
C11—N7—Ni1 | 110.8 (5) | C12—C11—H11B | 109.7 |
C11—N7—H7A | 109.5 | H11A—C11—H11B | 108.2 |
Ni1—N7—H7A | 109.5 | N8—C12—C11 | 109.6 (8) |
C11—N7—H7B | 109.5 | N8—C12—H12A | 109.7 |
Ni1—N7—H7B | 109.5 | C11—C12—H12A | 109.7 |
H7A—N7—H7B | 108.1 | N8—C12—H12B | 109.7 |
C12—N8—Ni1 | 107.7 (5) | C11—C12—H12B | 109.7 |
C12—N8—H8A | 110.2 | H12A—C12—H12B | 108.2 |
Ni1—N8—H8A | 110.2 | N9—C13—C14 | 111.9 (8) |
C12—N8—H8B | 110.2 | N9—C13—H13A | 109.2 |
Ni1—N8—H8B | 110.2 | C14—C13—H13A | 109.2 |
H8A—N8—H8B | 108.5 | N9—C13—H13B | 109.2 |
C13—N9—Ni1 | 108.2 (5) | C14—C13—H13B | 109.2 |
C13—N9—H9A | 110.1 | H13A—C13—H13B | 107.9 |
Ni1—N9—H9A | 110.1 | C13—C14—N10 | 108.3 (8) |
C13—N9—H9B | 110.1 | C13—C14—H14A | 110.0 |
Ni1—N9—H9B | 110.1 | N10—C14—H14A | 110.0 |
H9A—N9—H9B | 108.4 | C13—C14—H14B | 110.0 |
C14—N10—Ni1 | 106.5 (5) | N10—C14—H14B | 110.0 |
C14—N10—H10A | 110.4 | H14A—C14—H14B | 108.4 |
Ni1—N10—H10A | 110.4 | | |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+2, −y, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1iii | 0.83 (5) | 2.38 (7) | 2.847 (13) | 116 (5) |
O1—H2···N3iv | 0.84 (7) | 2.10 (8) | 2.870 (12) | 154 (8) |
N5—H5A···S1v | 0.90 | 2.57 | 3.404 (7) | 154 |
N5—H5B···S4 | 0.90 | 2.66 | 3.483 (7) | 153 |
N6—H6A···O1 | 0.90 | 2.36 | 3.209 (12) | 157 |
N6—H6B···N2vi | 0.90 | 2.34 | 3.141 (11) | 149 |
N7—H7A···S1v | 0.90 | 2.86 | 3.478 (6) | 127 |
N7—H7B···N4vii | 0.90 | 2.27 | 3.066 (11) | 147 |
N8—H8A···O1 | 0.90 | 2.59 | 3.410 (11) | 152 |
N8—H8A···N3iv | 0.90 | 2.59 | 3.237 (11) | 129 |
N8—H8B···N1viii | 0.90 | 2.34 | 3.189 (11) | 156 |
N9—H9A···S4v | 0.90 | 2.79 | 3.498 (8) | 136 |
N9—H9B···N1viii | 0.90 | 2.48 | 3.346 (12) | 160 |
N10—H10A···O1 | 0.90 | 2.49 | 3.322 (11) | 154 |
Symmetry codes: (iii) −x+1, −y+1, −z+2; (iv) −x+1/2, y+1/2, −z+3/2; (v) x−1, y, z; (vi) −x+3/2, y+1/2, −z+5/2; (vii) x−1/2, −y+1/2, z+1/2; (viii) x−3/2, −y+1/2, z−1/2. |
Experimental details
Crystal data |
Chemical formula | [Ni(C2H8N2)3][Cd(C4N2S2)2]·H2O |
Mr | 649.80 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.5796 (15), 19.255 (4), 17.201 (4) |
β (°) | 100.509 (4) |
V (Å3) | 2468.3 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.99 |
Crystal size (mm) | 0.30 × 0.15 × 0.12 |
|
Data collection |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.587, 0.796 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12887, 4346, 2220 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.083, 1.00 |
No. of reflections | 4346 |
No. of parameters | 286 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.88, −0.77 |
Selected bond lengths (Å) topCd1—S1 | 2.555 (2) | Ni1—N5 | 2.133 (6) |
Cd1—S3 | 2.558 (2) | Ni1—N9 | 2.147 (7) |
Cd1—S2 | 2.588 (2) | Ni1—N7 | 2.149 (7) |
Cd1—S4 | 2.657 (2) | Ni1—N10 | 2.153 (7) |
Cd1—S3i | 2.949 (3) | Ni1—N8 | 2.156 (7) |
Cd1—S2ii | 3.116 (3) | Ni1—N6 | 2.161 (6) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+2, −y, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1iii | 0.83 (5) | 2.38 (7) | 2.847 (13) | 116 (5) |
O1—H2···N3iv | 0.84 (7) | 2.10 (8) | 2.870 (12) | 154 (8) |
N5—H5A···S1v | 0.90 | 2.57 | 3.404 (7) | 154 |
N5—H5B···S4 | 0.90 | 2.66 | 3.483 (7) | 153 |
N6—H6A···O1 | 0.90 | 2.36 | 3.209 (12) | 157 |
N6—H6B···N2vi | 0.90 | 2.34 | 3.141 (11) | 149 |
N7—H7A···S1v | 0.90 | 2.86 | 3.478 (6) | 127 |
N7—H7B···N4vii | 0.90 | 2.27 | 3.066 (11) | 147 |
N8—H8A···O1 | 0.90 | 2.59 | 3.410 (11) | 152 |
N8—H8A···N3iv | 0.90 | 2.59 | 3.237 (11) | 129 |
N8—H8B···N1viii | 0.90 | 2.34 | 3.189 (11) | 156 |
N9—H9A···S4v | 0.90 | 2.79 | 3.498 (8) | 136 |
N9—H9B···N1viii | 0.90 | 2.48 | 3.346 (12) | 160 |
N10—H10A···O1 | 0.90 | 2.49 | 3.322 (11) | 154 |
Symmetry codes: (iii) −x+1, −y+1, −z+2; (iv) −x+1/2, y+1/2, −z+3/2; (v) x−1, y, z; (vi) −x+3/2, y+1/2, −z+5/2; (vii) x−1/2, −y+1/2, z+1/2; (viii) x−3/2, −y+1/2, z−1/2. |
Recently we have reported a number of d-block metal ion complexes with ethylenediamine (en) and 1,2-dicyanoethylenedithiolate (mnt) (Fu et al., 2004, 2004a,b; Wang, Fu & Wei, 2004; Wang, Fu & He, 2004), which display a plethora of interesting structures. We now report the crystal structure of the title compound, (I), which has a distinct crystal structure from those previously determined.
Compound (I) can be formulated as {[Ni (C2H8N2)3][Cd(C4N2S2)2]·H2O}n and consists of chains of bis(µ2-1,2-dicyanoethylenedithiolato-κ3S,S':S')cadmium(II) complex anions, tri(ethylenediamine-κ2N,N')nickel(II) complex cations and uncoordinated water molecules (Fig. 1).
The central NiII atom of the cation is in an octahedral geometry, coordinated by three bidentate en ligands via six N atoms. The three trans angles for the octahedron are 169.1 (3), 168.4 (2) and 170.7 (3)°, and the other angles range from 81.1 (3)° to 96.7 (3)°, indicating a somewhat distorted octahedral geometry. The Ni—N distances (Table 1) are comparable to the values of 2.110 (3)–2.151 (2) Å observed in related complexes (Fu et al., 2004, 2004a,b; Wang, Fu & Wei, 2004; Wang, Fu & He, 2004).
Atom Cd1 of the anionic chain is coordinated by six S atoms, of which S1–S4 are from two chelating mnt ligands and constitute the basal plane of the coordination octahedron [mean Cd—S = 2.589 (2) Å]. The two longer Cd—S bonds [mean Cd—S = 3.032 (3) Å; Table 1], to atoms S3i and S2ii [symmetry codes: (i) 1 − x, −y, 2 − z; (ii) 2 − x, −y, 2 − z], are from additional mnt bridging ligands and occupy the apical positions of the octahedron. The CdS4 basal plane of the octahedron is not completely planar and displays a puckered shape. Dihedral angles of 17.39 (19)° between the planar CdS4 group and the N1/C1–C4/N2 (mnt2−) mean plane, and 26.78 (18)° between the planar CdS4 group and the N3/C5–C8/N4 (mnt2−) mean plane, arise. The S—Cd—S bond angles within the basal plane are 84.01 (7) and 82.34 (7)°
Bridging atoms S3i and S2ii coordinate to two neighboring Cd atoms simultaneously, and these four atoms (as –S3—Cd1—S3i—Cd1i–) construct an essentially planar four-membered ring. In this way each mnt bivalent anion bridges two cadmium(II) ions to form a one-dimensional chain along the a axis, as shown in Fig. 2. The distances between neighbouring Cd atoms in the chain are 4.009 (9) and 4.139 (9) Å.
The water H atoms and the NH groups of the en ligands serve as hydrogen-bond donors (Table 2). The acceptor species include water O and mnt N and S atoms. Some of these bonds connect adjacent inversion-related chains, forming a three-dimensional network (Table 2 and Fig. 3).