Bis(N-phenyl­ethane-1,2-diamine)dithio­cyanato­nickel(II)

The asymmetric unit of the title mononuclear Ni^II compound, [Ni(NCS)₂(C₈H₁₂N₂)₂], contains two independent half-mol­ecules, the Ni atoms of which lie on crystallographic inversion centres. Each Ni^II ion is chelated by two N atoms from two N-phenyl­ethane-1,2-diamine ligands and is also coordinated by two N atoms from two thio­cyanate ligands, giving a distorted octa­hedral geometry. In the crystal, mol­ecules are linked into a two-dimensional network parallel to (100) by N—H...S inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.037
• wR factor = 0.080
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT230_ALERT_2_B Hirshfeld Test Diff for    S1     --  C17     ..       7.81 su

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S2     --  C18     ..       6.36 su
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1B    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3B    ...          ?
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         41
PLAT731_ALERT_1_C Bond    Calc     0.89(3), Rep   0.889(10) ......       3.00 su-Ra
              N4   -H4A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.89(3), Rep   0.890(10) ......       3.00 su-Ra
              N4   -H4A     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.52(3), Rep   2.520(10) ......       3.00 su-Ra
              H4A  -S1      1.555   1.645
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        115

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT793_ALERT_4_G The Model has Chirality at N2      (Verify) ....          R
PLAT793_ALERT_4_G The Model has Chirality at N4      (Verify) ....          S

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

As part of our investigations into novel urease inhibitors, we have synthesized the title compound, a new Ni^II complex. There are two independent half-molecules in the asymmetric unit. Each Ni atom lies on an inversion centre and is chelated by two N atoms from two N-phenylethane-1,2-diamine ligands, and coordinated by two N atoms from two thiocyanate ligands (Fig. 1). While the three trans angles at each Ni centre are 180° by symmetry, the other angles are close to 90° [81.54 (8)°–98.46 (8)°], indicating a slightly distorted octahedral coordination. The Ni—N bond lengths (Table 1) are typical and are comparable with those observed in other similar nickel(II) complexes (Lever et al., 1983; Brown & Lingafelter, 1963; Sanni et al., 1987).

Related literature

For related structures, see: Lever et al. (1983); Brown & Lingafelter (1963); Sanni et al. (1987).

S2. Experimental

N-Phenylethane-1,2-diamine (0.2 mmol, 27.2 mg), ammonium thiocyanate (0.2 mmol, 15.2 mg), and Ni(CH₃COO)₂.4H₂O (0.1 mmol, 24.9 mg) were mixed in a MeOH solution with stirring for 30 min at room temperature. After keeping the filtrate in air for five days, green block-shaped crystals were formed at the bottom of the vessel.

S3. Refinement

Atoms H2 and H4A were located in a difference Fourier map and refined isotropically, with N-H distances restrained to 0.90 (1) Å. Other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C-H distances in the range 0.93–0.97 Å, N–H distances of 0.90 Å, and with U_iso(H) set at 1.2U_eq(C,N).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. View of the two independent half-molecules in the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Unlabelled atoms in the molecule containing Ni1 are at the symmetry position (-x, 2 - y, -z) and those in the other molecule are at (2 -x, 1 - y, 1 -z).

Bis(N-phenylethane-1,2-diamine)dithiocyanatonickel(II)

Crystal data

[Ni(NCS)2(C8H12N2)2]	Z = 2
Mr = 447.26	F(000) = 468
Triclinic, P1	Dx = 1.438 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9947 (2) Å	Cell parameters from 1847 reflections
b = 9.4708 (3) Å	θ = 2.5–25.0°
c = 13.8044 (3) Å	µ = 1.16 mm^−1
α = 93.045 (1)°	T = 298 K
β = 98.258 (1)°	Block, green
γ = 90.934 (1)°	0.18 × 0.17 × 0.17 mm
V = 1032.62 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4314 independent reflections
Radiation source: fine-focus sealed tube	3284 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scan	θmax = 27.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.819, Tmax = 0.828	k = −12→8
6197 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0256P)^2 + 0.3717P] where P = (Fo^2 + 2Fc^2)/3
4314 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.31 e Å^−3
2 restraints	Δρmin = −0.26 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.0000	1.0000	0.0000	0.03175 (12)
Ni2	1.0000	0.5000	0.5000	0.03243 (12)
S1	0.21085 (10)	1.40198 (7)	0.20456 (5)	0.0487 (2)
S2	1.28479 (10)	0.83224 (9)	0.32626 (6)	0.0600 (2)
N1	0.2337 (3)	0.9430 (2)	−0.04011 (16)	0.0424 (5)
H1A	0.2188	0.9022	−0.1012	0.051*
H1B	0.3009	1.0204	−0.0392	0.051*
N2	0.0504 (3)	0.8295 (2)	0.09707 (15)	0.0348 (5)
N3	1.2463 (3)	0.4484 (2)	0.56125 (16)	0.0444 (6)
H3A	1.3139	0.5263	0.5682	0.053*
H3B	1.2448	0.4147	0.6209	0.053*
N4	1.0325 (3)	0.3174 (2)	0.40317 (16)	0.0372 (5)
N5	0.1256 (3)	1.1389 (2)	0.10846 (17)	0.0460 (6)
N6	1.1013 (3)	0.6271 (2)	0.40688 (16)	0.0435 (6)
C1	0.3124 (3)	0.8433 (3)	0.0301 (2)	0.0452 (7)
H1C	0.3664	0.8947	0.0893	0.054*
H1D	0.3979	0.7902	0.0017	0.054*
C2	0.1773 (3)	0.7435 (3)	0.0544 (2)	0.0411 (6)
H2A	0.1247	0.6904	−0.0044	0.049*
H2B	0.2265	0.6772	0.1010	0.049*
C3	−0.0938 (3)	0.7571 (2)	0.12332 (18)	0.0345 (6)
C4	−0.1649 (3)	0.6357 (3)	0.0722 (2)	0.0419 (6)
H4	−0.1159	0.5953	0.0205	0.050*
C5	−0.3091 (4)	0.5748 (3)	0.0985 (2)	0.0514 (8)
H5	−0.3563	0.4933	0.0640	0.062*
C6	−0.3842 (4)	0.6325 (3)	0.1746 (2)	0.0541 (8)
H6	−0.4811	0.5906	0.1916	0.065*
C7	−0.3129 (4)	0.7538 (3)	0.2254 (2)	0.0498 (7)
H7	−0.3627	0.7941	0.2768	0.060*
C8	−0.1695 (3)	0.8152 (3)	0.2006 (2)	0.0427 (6)
H8	−0.1224	0.8963	0.2356	0.051*
C9	1.3121 (3)	0.3404 (3)	0.4961 (2)	0.0501 (7)
H9A	1.4042	0.2912	0.5325	0.060*
H9B	1.3546	0.3851	0.4426	0.060*
C10	1.1697 (3)	0.2371 (3)	0.4563 (2)	0.0486 (7)
H10A	1.2089	0.1657	0.4124	0.058*
H10B	1.1293	0.1902	0.5096	0.058*
C11	0.8788 (3)	0.2437 (3)	0.36351 (19)	0.0369 (6)
C12	0.8105 (4)	0.1359 (3)	0.4109 (2)	0.0448 (7)
H12	0.8716	0.1011	0.4667	0.054*
C13	0.6509 (4)	0.0801 (3)	0.3749 (2)	0.0532 (8)
H13	0.6059	0.0080	0.4071	0.064*
C14	0.5582 (4)	0.1295 (3)	0.2925 (2)	0.0551 (8)
H14	0.4505	0.0923	0.2697	0.066*
C15	0.6271 (4)	0.2353 (3)	0.2438 (2)	0.0492 (7)
H15	0.5663	0.2686	0.1874	0.059*
C16	0.7864 (3)	0.2914 (3)	0.2791 (2)	0.0428 (6)
H16	0.8321	0.3621	0.2459	0.051*
C17	0.1622 (3)	1.2472 (3)	0.14957 (18)	0.0353 (6)
C18	1.1772 (3)	0.7109 (3)	0.37193 (18)	0.0372 (6)
H2	0.104 (4)	0.874 (3)	0.1524 (14)	0.080*
H4A	1.076 (4)	0.353 (3)	0.3537 (17)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0354 (3)	0.0256 (2)	0.0348 (3)	−0.00085 (18)	0.00618 (19)	0.00362 (18)
Ni2	0.0350 (3)	0.0293 (2)	0.0333 (3)	−0.00465 (19)	0.00483 (19)	0.00667 (19)
S1	0.0621 (5)	0.0367 (4)	0.0477 (4)	−0.0126 (3)	0.0130 (4)	−0.0036 (3)
S2	0.0544 (5)	0.0756 (6)	0.0502 (5)	−0.0305 (4)	0.0059 (4)	0.0199 (4)
N1	0.0442 (13)	0.0376 (12)	0.0484 (14)	0.0029 (10)	0.0135 (11)	0.0114 (10)
N2	0.0373 (12)	0.0311 (11)	0.0371 (13)	−0.0011 (9)	0.0079 (10)	0.0054 (9)
N3	0.0426 (13)	0.0445 (13)	0.0439 (14)	−0.0035 (10)	−0.0003 (10)	0.0028 (11)
N4	0.0372 (12)	0.0370 (12)	0.0374 (13)	−0.0042 (10)	0.0050 (10)	0.0053 (10)
N5	0.0558 (15)	0.0365 (13)	0.0436 (14)	−0.0056 (11)	0.0019 (11)	0.0002 (11)
N6	0.0518 (15)	0.0391 (13)	0.0415 (13)	−0.0066 (11)	0.0126 (11)	0.0075 (10)
C1	0.0382 (16)	0.0445 (16)	0.0552 (18)	0.0092 (12)	0.0096 (13)	0.0145 (13)
C2	0.0434 (16)	0.0325 (14)	0.0494 (17)	0.0092 (12)	0.0090 (13)	0.0120 (12)
C3	0.0353 (14)	0.0312 (13)	0.0375 (14)	0.0001 (11)	0.0026 (11)	0.0132 (11)
C4	0.0494 (17)	0.0345 (14)	0.0419 (16)	0.0006 (12)	0.0049 (13)	0.0080 (12)
C5	0.0481 (18)	0.0373 (16)	0.067 (2)	−0.0073 (13)	−0.0003 (15)	0.0110 (14)
C6	0.0368 (16)	0.0563 (19)	0.071 (2)	−0.0027 (14)	0.0066 (15)	0.0288 (17)
C7	0.0505 (18)	0.0519 (18)	0.0511 (18)	0.0062 (14)	0.0161 (14)	0.0153 (14)
C8	0.0485 (17)	0.0408 (15)	0.0411 (16)	0.0003 (12)	0.0124 (13)	0.0089 (12)
C9	0.0384 (16)	0.0549 (18)	0.0569 (19)	0.0059 (13)	0.0047 (14)	0.0046 (15)
C10	0.0473 (17)	0.0423 (16)	0.0556 (19)	0.0067 (13)	0.0061 (14)	−0.0004 (14)
C11	0.0413 (15)	0.0308 (13)	0.0386 (15)	−0.0011 (11)	0.0084 (12)	−0.0030 (11)
C12	0.0545 (18)	0.0361 (15)	0.0440 (16)	−0.0061 (13)	0.0080 (13)	0.0040 (12)
C13	0.061 (2)	0.0409 (16)	0.059 (2)	−0.0167 (14)	0.0143 (16)	0.0009 (14)
C14	0.0462 (18)	0.0518 (18)	0.065 (2)	−0.0127 (14)	0.0053 (15)	−0.0053 (16)
C15	0.0478 (18)	0.0529 (18)	0.0453 (17)	0.0017 (14)	0.0027 (13)	−0.0008 (14)
C16	0.0440 (16)	0.0426 (15)	0.0422 (16)	−0.0039 (12)	0.0070 (13)	0.0059 (12)
C17	0.0330 (14)	0.0420 (15)	0.0318 (14)	−0.0013 (11)	0.0054 (11)	0.0091 (12)
C18	0.0376 (15)	0.0402 (15)	0.0335 (14)	−0.0013 (12)	0.0048 (11)	0.0014 (11)

Geometric parameters (Å, º)

Ni1—N5	2.073 (2)	C1—H1D	0.97
Ni1—N5^i	2.073 (2)	C2—H2A	0.97
Ni1—N1^i	2.094 (2)	C2—H2B	0.97
Ni1—N1	2.094 (2)	C3—C4	1.386 (3)
Ni1—N2^i	2.159 (2)	C3—C8	1.393 (4)
Ni1—N2	2.159 (2)	C4—C5	1.384 (4)
Ni2—N6^ii	2.047 (2)	C4—H4	0.93
Ni2—N6	2.047 (2)	C5—C6	1.376 (4)
Ni2—N3^ii	2.104 (2)	C5—H5	0.93
Ni2—N3	2.104 (2)	C6—C7	1.384 (4)
Ni2—N4^ii	2.171 (2)	C6—H6	0.93
Ni2—N4	2.171 (2)	C7—C8	1.372 (4)
S1—C17	1.629 (3)	C7—H7	0.93
S2—C18	1.630 (3)	C8—H8	0.93
N1—C1	1.473 (3)	C9—C10	1.511 (4)
N1—H1A	0.90	C9—H9A	0.97
N1—H1B	0.90	C9—H9B	0.97
N2—C3	1.432 (3)	C10—H10A	0.97
N2—C2	1.479 (3)	C10—H10B	0.97
N2—H2	0.898 (10)	C11—C12	1.387 (3)
N3—C9	1.479 (3)	C11—C16	1.388 (4)
N3—H3A	0.90	C12—C13	1.386 (4)
N3—H3B	0.90	C12—H12	0.93
N4—C11	1.426 (3)	C13—C14	1.374 (4)
N4—C10	1.475 (3)	C13—H13	0.93
N4—H4A	0.889 (10)	C14—C15	1.386 (4)
N5—C17	1.158 (3)	C14—H14	0.93
N6—C18	1.158 (3)	C15—C16	1.383 (4)
C1—C2	1.508 (3)	C15—H15	0.93
C1—H1C	0.97	C16—H16	0.93
N5—Ni1—N5^i	180	N1—C1—H1D	109.9
N5—Ni1—N1^i	90.87 (9)	C2—C1—H1D	109.9
N5^i—Ni1—N1^i	89.13 (9)	H1C—C1—H1D	108.3
N5—Ni1—N1	89.13 (9)	N2—C2—C1	107.7 (2)
N5^i—Ni1—N1	90.87 (9)	N2—C2—H2A	110.2
N1^i—Ni1—N1	180	C1—C2—H2A	110.2
N5—Ni1—N2^i	90.77 (8)	N2—C2—H2B	110.2
N5^i—Ni1—N2^i	89.23 (8)	C1—C2—H2B	110.2
N1^i—Ni1—N2^i	82.40 (8)	H2A—C2—H2B	108.5
N1—Ni1—N2^i	97.60 (8)	C4—C3—C8	119.0 (2)
N5—Ni1—N2	89.23 (8)	C4—C3—N2	122.6 (2)
N5^i—Ni1—N2	90.77 (8)	C8—C3—N2	118.3 (2)
N1^i—Ni1—N2	97.60 (8)	C5—C4—C3	119.6 (3)
N1—Ni1—N2	82.40 (8)	C5—C4—H4	120.2
N2^i—Ni1—N2	180	C3—C4—H4	120.2
N6^ii—Ni2—N6	180	C6—C5—C4	121.3 (3)
N6^ii—Ni2—N3^ii	89.13 (9)	C6—C5—H5	119.3
N6—Ni2—N3^ii	90.87 (9)	C4—C5—H5	119.3
N6^ii—Ni2—N3	90.87 (9)	C5—C6—C7	118.8 (3)
N6—Ni2—N3	89.13 (9)	C5—C6—H6	120.6
N3^ii—Ni2—N3	180	C7—C6—H6	120.6
N6^ii—Ni2—N4^ii	89.54 (8)	C8—C7—C6	120.6 (3)
N6—Ni2—N4^ii	90.46 (8)	C8—C7—H7	119.7
N3^ii—Ni2—N4^ii	81.54 (8)	C6—C7—H7	119.7
N3—Ni2—N4^ii	98.46 (8)	C7—C8—C3	120.6 (3)
N6^ii—Ni2—N4	90.46 (8)	C7—C8—H8	119.7
N6—Ni2—N4	89.54 (8)	C3—C8—H8	119.7
N3^ii—Ni2—N4	98.46 (8)	N3—C9—C10	108.3 (2)
N3—Ni2—N4	81.54 (8)	N3—C9—H9A	110.0
N4^ii—Ni2—N4	180	C10—C9—H9A	110.0
C1—N1—Ni1	108.38 (16)	N3—C9—H9B	110.0
C1—N1—H1A	110.0	C10—C9—H9B	110.0
Ni1—N1—H1A	110.0	H9A—C9—H9B	108.4
C1—N1—H1B	110.0	N4—C10—C9	107.8 (2)
Ni1—N1—H1B	110.0	N4—C10—H10A	110.1
H1A—N1—H1B	108.4	C9—C10—H10A	110.1
C3—N2—C2	117.70 (19)	N4—C10—H10B	110.1
C3—N2—Ni1	116.59 (15)	C9—C10—H10B	110.1
C2—N2—Ni1	104.74 (15)	H10A—C10—H10B	108.5
C3—N2—H2	107 (2)	C12—C11—C16	118.8 (2)
C2—N2—H2	107 (2)	C12—C11—N4	122.6 (2)
Ni1—N2—H2	103 (2)	C16—C11—N4	118.2 (2)
C9—N3—Ni2	109.24 (16)	C13—C12—C11	119.9 (3)
C9—N3—H3A	109.8	C13—C12—H12	120.1
Ni2—N3—H3A	109.8	C11—C12—H12	120.1
C9—N3—H3B	109.8	C14—C13—C12	121.2 (3)
Ni2—N3—H3B	109.8	C14—C13—H13	119.4
H3A—N3—H3B	108.3	C12—C13—H13	119.4
C11—N4—C10	118.3 (2)	C13—C14—C15	119.2 (3)
C11—N4—Ni2	114.31 (16)	C13—C14—H14	120.4
C10—N4—Ni2	105.40 (16)	C15—C14—H14	120.4
C11—N4—H4A	108 (2)	C16—C15—C14	120.0 (3)
C10—N4—H4A	105 (2)	C16—C15—H15	120.0
Ni2—N4—H4A	104 (2)	C14—C15—H15	120.0
C17—N5—Ni1	156.7 (2)	C15—C16—C11	120.9 (3)
C18—N6—Ni2	165.9 (2)	C15—C16—H16	119.6
N1—C1—C2	108.8 (2)	C11—C16—H16	119.6
N1—C1—H1C	109.9	N5—C17—S1	178.3 (3)
C2—C1—H1C	109.9	N6—C18—S2	178.0 (2)

Symmetry codes: (i) −x, −y+2, −z; (ii) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···S1^iii	0.89 (1)	2.52 (1)	3.393 (2)	168 (3)
N2—H2···S2^iv	0.90 (1)	2.67 (2)	3.436 (2)	144 (3)

Symmetry codes: (iii) x+1, y−1, z; (iv) x−1, y, z.