Bis[(4-bromo­benz­yl)triphenyl­phosphonium] bis­(1,2-dicyano­ethane-1,2-dithiol­ato-κ²S,S′)nickel(II) monohydrate

The synthesis and crystal structure of the title complex, (C₂₅H₂₁BrP)₂[Ni(C₄N₂S₂)₂]·H₂O or [BrBzTPP]₂[Ni(mnt)₂]·H₂O [where BrBzTPP is (4-bromo­benz­yl)triphenyl­phosphonium and mnt is 1,2-dicyano­ethane-1,2-dithiol­ate or maleonitrile­dithiol­ate], is reported. The Ni^II ion of the [Ni(mnt)₂]²⁻ anion is coordinated by four S atoms of two mnt ligands and exhibits the expected square-planar coordination geometry. The [BrBzTPP]⁺ cation adopts a conformation where the four benzene rings are twisted with respect to the plane of the P—C—C chain which links them. The Ni atom lies on a centre of symmetry. Weak C—H...Ni and C—H...S inter­actions between the anions and cations may play a role in the packing and stabilization of the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in solvent or counterion
• R factor = 0.052
• wR factor = 0.149
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



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
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.44 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C4     ...       1.42 Ang.

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Bis[(4-bromobenzyl)triphenylphosphonium] bis(1,2-dicyanoethane-1,2-dithiolato-κ²S,S')nickel(II) monohydrate

Crystal data

(C25H21BrP)2[Ni(C4N2S2)2]·H2O	Z = 1
Mr = 1221.68	F(000) = 620
Triclinic, P1	Dx = 1.461 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.896 (2) Å	Cell parameters from 1337 reflections
b = 11.047 (2) Å	θ = 2.5–21.8°
c = 11.753 (2) Å	µ = 2.04 mm^−1
α = 82.251 (10)°	T = 293 K
β = 84.30 (1)°	Block, red
γ = 84.00 (1)°	0.4 × 0.3 × 0.2 mm
V = 1388.9 (4) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4782 independent reflections
Radiation source: fine-focus sealed tube	4049 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
φ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2000)	h = −12→12
Tmin = 0.49, Tmax = 0.66	k = −13→11
6889 measured reflections	l = −13→13

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.09P)^2 + 1.95P] where P = (Fo^2 + 2Fc^2)/3
4782 reflections	(Δ/σ)max = 0.001
332 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.39 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	Occ. (<1)
Ni1	0.5000	1.0000	0.5000	0.0449 (2)
N1	0.1560 (4)	1.2051 (4)	0.1928 (4)	0.0576 (10)
N2	0.5737 (4)	0.5604 (4)	0.7797 (4)	0.0562 (10)
S1	0.33590 (12)	1.00608 (11)	0.40846 (11)	0.0547 (3)
S2	0.45402 (11)	0.82477 (11)	0.58898 (11)	0.0540 (3)
P1	0.64890 (9)	0.70151 (9)	0.19998 (8)	0.0365 (2)
Br1	0.92124 (5)	0.32971 (4)	0.67751 (4)	0.05731 (18)
C1	0.2326 (5)	1.1806 (5)	0.2525 (5)	0.0587 (12)
C2	0.3338 (4)	1.1463 (4)	0.3244 (4)	0.0476 (10)
C3	0.5764 (5)	0.6582 (5)	0.7344 (4)	0.0550 (11)
C4	0.5765 (4)	0.7786 (4)	0.6741 (4)	0.0467 (10)
C5	0.5872 (4)	0.6566 (4)	0.3459 (4)	0.0451 (9)
H5A	0.5585	0.7304	0.3807	0.054*
H5B	0.5156	0.6121	0.3432	0.054*
C6	0.6744 (4)	0.5788 (4)	0.4231 (3)	0.0401 (9)
C7	0.6719 (5)	0.4536 (4)	0.4383 (4)	0.0557 (11)
H7	0.6189	0.4185	0.3976	0.067*
C8	0.7463 (4)	0.3784 (4)	0.5127 (4)	0.0546 (11)
H8	0.7428	0.2938	0.5229	0.066*
C9	0.8246 (4)	0.4307 (5)	0.5705 (4)	0.0572 (12)
C10	0.8320 (5)	0.5559 (5)	0.5550 (4)	0.0587 (12)
H10	0.8869	0.5906	0.5940	0.070*
C11	0.7564 (4)	0.6290 (4)	0.4805 (4)	0.0492 (10)
H11	0.7612	0.7134	0.4691	0.059*
C12	0.7226 (4)	0.5718 (3)	0.1367 (3)	0.0371 (8)
C13	0.6715 (4)	0.5254 (4)	0.0516 (4)	0.0507 (10)
H13	0.5981	0.5633	0.0241	0.061*
C14	0.7281 (5)	0.4237 (4)	0.0070 (4)	0.0555 (11)
H14	0.6931	0.3923	−0.0506	0.067*
C15	0.8343 (5)	0.3692 (4)	0.0465 (5)	0.0587 (12)
H15	0.8723	0.3002	0.0153	0.070*
C16	0.8878 (5)	0.4121 (4)	0.1311 (4)	0.0555 (11)
H16	0.9609	0.3725	0.1580	0.067*
C17	0.8318 (4)	0.5160 (4)	0.1768 (4)	0.0533 (11)
H17	0.8677	0.5475	0.2337	0.064*
C18	0.5241 (3)	0.7762 (3)	0.1211 (3)	0.0343 (8)
C19	0.5436 (4)	0.8126 (4)	0.0043 (4)	0.0480 (10)
H19	0.6211	0.7955	−0.0340	0.058*
C20	0.4490 (5)	0.8741 (4)	−0.0557 (4)	0.0537 (11)
H20	0.4619	0.8967	−0.1348	0.064*
C21	0.3356 (5)	0.9022 (4)	0.0012 (5)	0.0593 (12)
H21	0.2720	0.9447	−0.0394	0.071*
C22	0.3156 (4)	0.8684 (5)	0.1164 (5)	0.0585 (12)
H22	0.2385	0.8881	0.1544	0.070*
C23	0.4086 (4)	0.8052 (4)	0.1769 (4)	0.0505 (10)
H23	0.3942	0.7817	0.2557	0.061*
C24	0.7618 (3)	0.8095 (3)	0.1991 (3)	0.0331 (8)
C25	0.8653 (4)	0.8091 (4)	0.1213 (4)	0.0457 (9)
H25	0.8791	0.7506	0.0703	0.055*
C26	0.9484 (4)	0.8961 (5)	0.1195 (4)	0.0540 (11)
H26	1.0182	0.8959	0.0671	0.065*
C27	0.9285 (5)	0.9819 (5)	0.1939 (5)	0.0629 (13)
H27	0.9850	1.0396	0.1931	0.075*
C28	0.8244 (5)	0.9829 (5)	0.2701 (5)	0.0634 (13)
H28	0.8103	1.0417	0.3207	0.076*
C29	0.7420 (4)	0.8983 (4)	0.2720 (4)	0.0524 (11)
H29	0.6714	0.9005	0.3233	0.063*
O1	0.0125 (7)	0.0722 (7)	0.4572 (6)	0.0664 (18)	0.50
H1B	0.0274	0.1470	0.4435	0.080*	0.50
H1A	−0.0033	0.0532	0.5293	0.080*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0500 (4)	0.0415 (4)	0.0451 (4)	−0.0053 (3)	−0.0019 (3)	−0.0127 (3)
N1	0.057 (2)	0.047 (2)	0.071 (3)	−0.0114 (18)	−0.011 (2)	−0.0068 (19)
N2	0.057 (2)	0.049 (2)	0.064 (2)	−0.0114 (18)	−0.0086 (19)	−0.007 (2)
S1	0.0565 (7)	0.0458 (6)	0.0643 (7)	−0.0104 (5)	−0.0108 (5)	−0.0070 (5)
S2	0.0551 (7)	0.0454 (6)	0.0632 (7)	−0.0095 (5)	−0.0092 (5)	−0.0071 (5)
P1	0.0354 (5)	0.0367 (5)	0.0367 (5)	0.0000 (4)	−0.0029 (4)	−0.0045 (4)
Br1	0.0582 (3)	0.0499 (3)	0.0653 (3)	−0.0101 (2)	−0.0125 (2)	−0.0035 (2)
C1	0.057 (3)	0.061 (3)	0.058 (3)	−0.008 (2)	−0.004 (2)	−0.005 (2)
C2	0.051 (2)	0.054 (3)	0.036 (2)	−0.001 (2)	0.0011 (18)	−0.0096 (18)
C3	0.055 (3)	0.064 (3)	0.047 (2)	−0.005 (2)	−0.004 (2)	−0.009 (2)
C4	0.053 (2)	0.042 (2)	0.043 (2)	−0.0031 (19)	0.0085 (18)	−0.0076 (17)
C5	0.039 (2)	0.050 (2)	0.046 (2)	−0.0059 (18)	−0.0004 (17)	−0.0021 (18)
C6	0.044 (2)	0.042 (2)	0.033 (2)	−0.0094 (17)	−0.0064 (16)	0.0036 (16)
C7	0.057 (3)	0.048 (3)	0.064 (3)	−0.011 (2)	−0.010 (2)	−0.008 (2)
C8	0.055 (3)	0.045 (2)	0.066 (3)	−0.009 (2)	−0.014 (2)	−0.001 (2)
C9	0.044 (2)	0.071 (3)	0.051 (3)	−0.005 (2)	−0.010 (2)	0.014 (2)
C10	0.051 (3)	0.078 (3)	0.050 (3)	−0.015 (2)	−0.012 (2)	−0.004 (2)
C11	0.051 (2)	0.052 (2)	0.045 (2)	−0.013 (2)	−0.0043 (19)	−0.0009 (19)
C12	0.0365 (19)	0.0314 (19)	0.044 (2)	0.0013 (15)	−0.0051 (16)	−0.0090 (16)
C13	0.054 (3)	0.039 (2)	0.059 (3)	0.0054 (19)	−0.011 (2)	−0.0111 (19)
C14	0.061 (3)	0.044 (2)	0.064 (3)	−0.007 (2)	−0.012 (2)	−0.011 (2)
C15	0.060 (3)	0.048 (3)	0.070 (3)	−0.007 (2)	−0.009 (2)	−0.008 (2)
C16	0.055 (3)	0.045 (2)	0.069 (3)	−0.009 (2)	−0.011 (2)	−0.010 (2)
C17	0.050 (3)	0.049 (3)	0.062 (3)	0.008 (2)	−0.011 (2)	−0.016 (2)
C18	0.0277 (17)	0.0313 (18)	0.044 (2)	0.0017 (14)	−0.0015 (15)	−0.0082 (15)
C19	0.045 (2)	0.046 (2)	0.048 (2)	0.0135 (18)	0.0004 (18)	−0.0027 (18)
C20	0.068 (3)	0.045 (2)	0.046 (2)	0.007 (2)	−0.016 (2)	−0.0014 (19)
C21	0.052 (3)	0.048 (3)	0.077 (3)	0.007 (2)	−0.021 (2)	−0.001 (2)
C22	0.034 (2)	0.066 (3)	0.069 (3)	0.008 (2)	−0.001 (2)	−0.001 (2)
C23	0.042 (2)	0.055 (3)	0.048 (2)	0.0031 (19)	−0.0023 (19)	0.008 (2)
C24	0.0329 (18)	0.0301 (18)	0.0365 (19)	0.0010 (14)	−0.0050 (14)	−0.0064 (14)
C25	0.043 (2)	0.043 (2)	0.050 (2)	−0.0001 (18)	−0.0006 (18)	−0.0052 (18)
C26	0.039 (2)	0.058 (3)	0.059 (3)	−0.006 (2)	0.000 (2)	0.008 (2)
C27	0.059 (3)	0.048 (3)	0.082 (4)	−0.018 (2)	−0.014 (3)	0.006 (2)
C28	0.079 (4)	0.048 (3)	0.070 (3)	−0.016 (2)	−0.003 (3)	−0.027 (2)
C29	0.050 (2)	0.049 (3)	0.057 (3)	−0.007 (2)	0.002 (2)	−0.006 (2)
O1	0.072 (5)	0.061 (4)	0.069 (5)	−0.016 (4)	−0.010 (4)	−0.010 (3)

Geometric parameters (Å, º)

Ni1—S2^i	2.1552 (12)	C13—H13	0.9300
Ni1—S2	2.1552 (12)	C14—C15	1.343 (7)
Ni1—S1^i	2.1672 (13)	C14—H14	0.9300
Ni1—S1	2.1672 (13)	C15—C16	1.362 (7)
N1—C1	1.131 (6)	C15—H15	0.9300
N2—C3	1.140 (6)	C16—C17	1.390 (7)
S1—C2	1.720 (5)	C16—H16	0.9300
S2—C4	1.740 (5)	C17—H17	0.9300
P1—C12	1.783 (4)	C18—C19	1.379 (6)
P1—C18	1.789 (4)	C18—C23	1.387 (5)
P1—C24	1.799 (4)	C19—C20	1.375 (6)
P1—C5	1.803 (4)	C19—H19	0.9300
Br1—C9	1.890 (4)	C20—C21	1.373 (7)
C1—C2	1.445 (7)	C20—H20	0.9300
C2—C4^i	1.349 (7)	C21—C22	1.357 (7)
C3—C4	1.420 (7)	C21—H21	0.9300
C4—C2^i	1.349 (7)	C22—C23	1.371 (6)
C5—C6	1.501 (6)	C22—H22	0.9300
C5—H5A	0.9700	C23—H23	0.9300
C5—H5B	0.9700	C24—C29	1.373 (6)
C6—C7	1.373 (6)	C24—C25	1.380 (6)
C6—C11	1.373 (6)	C25—C26	1.385 (6)
C7—C8	1.384 (7)	C25—H25	0.9300
C7—H7	0.9300	C26—C27	1.362 (8)
C8—C9	1.359 (7)	C26—H26	0.9300
C8—H8	0.9300	C27—C28	1.374 (8)
C9—C10	1.381 (8)	C27—H27	0.9300
C10—C11	1.382 (7)	C28—C29	1.359 (7)
C10—H10	0.9300	C28—H28	0.9300
C11—H11	0.9300	C29—H29	0.9300
C12—C13	1.372 (6)	O1—O1^ii	1.798 (15)
C12—C17	1.378 (6)	O1—H1B	0.8500
C13—C14	1.366 (7)	O1—H1A	0.8500
S2^i—Ni1—S2	180.0	C15—C14—C13	119.8 (5)
S2^i—Ni1—S1^i	88.07 (5)	C15—C14—H14	120.1
S2—Ni1—S1^i	91.93 (5)	C13—C14—H14	120.1
S2^i—Ni1—S1	91.93 (5)	C14—C15—C16	121.7 (5)
S2—Ni1—S1	88.07 (5)	C14—C15—H15	119.1
S1^i—Ni1—S1	180.0	C16—C15—H15	119.1
C2—S1—Ni1	103.35 (16)	C15—C16—C17	119.1 (5)
C4—S2—Ni1	103.52 (15)	C15—C16—H16	120.4
C12—P1—C18	111.88 (18)	C17—C16—H16	120.4
C12—P1—C24	108.30 (18)	C12—C17—C16	119.3 (4)
C18—P1—C24	108.17 (17)	C12—C17—H17	120.4
C12—P1—C5	110.8 (2)	C16—C17—H17	120.4
C18—P1—C5	107.89 (18)	C19—C18—C23	118.9 (4)
C24—P1—C5	109.77 (19)	C19—C18—P1	120.1 (3)
N1—C1—C2	177.1 (6)	C23—C18—P1	120.9 (3)
C4^i—C2—C1	121.3 (4)	C20—C19—C18	120.2 (4)
C4^i—C2—S1	121.1 (4)	C20—C19—H19	119.9
C1—C2—S1	117.6 (4)	C18—C19—H19	119.9
N2—C3—C4	177.4 (5)	C21—C20—C19	119.9 (4)
C2^i—C4—C3	124.4 (5)	C21—C20—H20	120.0
C2^i—C4—S2	120.0 (4)	C19—C20—H20	120.0
C3—C4—S2	115.5 (4)	C22—C21—C20	120.4 (4)
C6—C5—P1	116.2 (3)	C22—C21—H21	119.8
C6—C5—H5A	108.2	C20—C21—H21	119.8
P1—C5—H5A	108.2	C21—C22—C23	120.2 (4)
C6—C5—H5B	108.2	C21—C22—H22	119.9
P1—C5—H5B	108.2	C23—C22—H22	119.9
H5A—C5—H5B	107.4	C22—C23—C18	120.3 (4)
C7—C6—C11	118.5 (4)	C22—C23—H23	119.8
C7—C6—C5	119.5 (4)	C18—C23—H23	119.8
C11—C6—C5	122.0 (4)	C29—C24—C25	119.1 (4)
C6—C7—C8	121.7 (4)	C29—C24—P1	120.0 (3)
C6—C7—H7	119.2	C25—C24—P1	120.8 (3)
C8—C7—H7	119.2	C24—C25—C26	119.7 (4)
C9—C8—C7	118.6 (4)	C24—C25—H25	120.2
C9—C8—H8	120.7	C26—C25—H25	120.2
C7—C8—H8	120.7	C27—C26—C25	120.4 (4)
C8—C9—C10	121.3 (4)	C27—C26—H26	119.8
C8—C9—Br1	119.0 (4)	C25—C26—H26	119.8
C10—C9—Br1	119.7 (4)	C26—C27—C28	119.7 (4)
C9—C10—C11	118.9 (5)	C26—C27—H27	120.2
C9—C10—H10	120.5	C28—C27—H27	120.2
C11—C10—H10	120.5	C29—C28—C27	120.3 (5)
C6—C11—C10	121.0 (4)	C29—C28—H28	119.9
C6—C11—H11	119.5	C27—C28—H28	119.9
C10—C11—H11	119.5	C28—C29—C24	120.9 (4)
C13—C12—C17	119.8 (4)	C28—C29—H29	119.6
C13—C12—P1	121.5 (3)	C24—C29—H29	119.6
C17—C12—P1	118.7 (3)	O1^ii—O1—H1B	157.1
C14—C13—C12	120.3 (4)	O1^ii—O1—H1A	48.3
C14—C13—H13	119.8	H1B—O1—H1A	109.5
C12—C13—H13	119.8

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