Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705430X/sj2398sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680705430X/sj2398Isup2.hkl |
CCDC reference: 672591
The title compound was prepared by the direct reaction of NiCl2.6H2O, Na2mnt and (mCNBzTPP)+Br- in methanol. Red block-shaped single crystals were obtained by slow evaporation of a CH3CN solution at room temperature over two weeks.
All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic and 0.97 Å, Uiso = 1.2Ueq (C) for CH2 atoms.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
(C26H21NP)2[Ni(C4N2S2)2] | F(000) = 2264 |
Mr = 1095.89 | Dx = 1.369 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 957 reflections |
a = 19.158 (4) Å | θ = 2.6–22.9° |
b = 14.956 (3) Å | µ = 0.63 mm−1 |
c = 19.598 (4) Å | T = 298 K |
β = 108.785 (4)° | Block, red |
V = 5316.3 (19) Å3 | 0.34 × 0.22 × 0.15 mm |
Z = 4 |
Bruker Smart Apex CCD diffractometer | 9356 independent reflections |
Radiation source: fine-focus sealed tube | 6235 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −22→22 |
Tmin = 0.834, Tmax = 0.912 | k = −17→8 |
25624 measured reflections | l = −23→23 |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0541P)2] where P = (Fo2 + 2Fc2)/3 |
9356 reflections | (Δ/σ)max = 0.015 |
661 parameters | Δρmax = 0.83 e Å−3 |
0 restraints | Δρmin = −0.74 e Å−3 |
(C26H21NP)2[Ni(C4N2S2)2] | V = 5316.3 (19) Å3 |
Mr = 1095.89 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 19.158 (4) Å | µ = 0.63 mm−1 |
b = 14.956 (3) Å | T = 298 K |
c = 19.598 (4) Å | 0.34 × 0.22 × 0.15 mm |
β = 108.785 (4)° |
Bruker Smart Apex CCD diffractometer | 9356 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 6235 reflections with I > 2σ(I) |
Tmin = 0.834, Tmax = 0.912 | Rint = 0.076 |
25624 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.83 e Å−3 |
9356 reflections | Δρmin = −0.74 e Å−3 |
661 parameters |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.5000 | 0.0000 | 1.0000 | 0.05280 (19) | |
Ni2 | 1.0000 | 0.0000 | 1.0000 | 0.05428 (19) | |
C1 | 0.42984 (18) | 0.1858 (2) | 0.98368 (18) | 0.0558 (9) | |
C2 | 0.45351 (18) | 0.1800 (2) | 0.92638 (19) | 0.0589 (9) | |
C3 | 0.4419 (2) | 0.2543 (3) | 0.8777 (2) | 0.0668 (10) | |
C4 | 0.3917 (2) | 0.2625 (3) | 0.9953 (2) | 0.0682 (11) | |
C5 | 0.9070 (2) | 0.1704 (2) | 0.97231 (18) | 0.0587 (9) | |
C6 | 0.96210 (19) | 0.1926 (2) | 0.94730 (18) | 0.0568 (9) | |
C7 | 0.9619 (2) | 0.2757 (3) | 0.9121 (2) | 0.0655 (10) | |
C8 | 0.8462 (2) | 0.2295 (3) | 0.9644 (2) | 0.0664 (10) | |
C9 | 0.6312 (2) | 0.2789 (3) | 0.07367 (19) | 0.0657 (10) | |
C10 | 0.6713 (3) | 0.3359 (4) | 0.0437 (2) | 0.0982 (16) | |
H10 | 0.7084 | 0.3127 | 0.0279 | 0.118* | |
C11 | 0.6563 (3) | 0.4260 (4) | 0.0376 (3) | 0.122 (2) | |
H11 | 0.6835 | 0.4630 | 0.0174 | 0.146* | |
C12 | 0.6027 (3) | 0.4618 (3) | 0.0604 (3) | 0.1008 (16) | |
H12 | 0.5934 | 0.5229 | 0.0566 | 0.121* | |
C13 | 0.5623 (3) | 0.4066 (3) | 0.0892 (2) | 0.0733 (11) | |
C14 | 0.5765 (2) | 0.3156 (3) | 0.09584 (18) | 0.0617 (10) | |
H14 | 0.5486 | 0.2790 | 0.1155 | 0.074* | |
C15 | 0.6486 (2) | 0.1806 (3) | 0.08122 (17) | 0.0658 (10) | |
H15A | 0.6652 | 0.1617 | 0.0416 | 0.079* | |
H15B | 0.6040 | 0.1477 | 0.0778 | 0.079* | |
C16 | 0.5037 (3) | 0.4444 (3) | 0.1115 (2) | 0.0886 (14) | |
C17 | 0.78815 (18) | 0.2373 (2) | 0.18514 (17) | 0.0524 (9) | |
C18 | 0.8438 (2) | 0.2316 (3) | 0.1540 (2) | 0.0670 (10) | |
H18 | 0.8475 | 0.1814 | 0.1274 | 0.080* | |
C19 | 0.8927 (2) | 0.2998 (3) | 0.1626 (2) | 0.0858 (13) | |
H19 | 0.9298 | 0.2958 | 0.1417 | 0.103* | |
C20 | 0.8882 (3) | 0.3739 (3) | 0.2014 (3) | 0.0920 (14) | |
H20 | 0.9223 | 0.4199 | 0.2070 | 0.110* | |
C21 | 0.8336 (3) | 0.3806 (3) | 0.2323 (2) | 0.0834 (13) | |
H21 | 0.8307 | 0.4311 | 0.2590 | 0.100* | |
C22 | 0.7827 (2) | 0.3126 (3) | 0.22363 (19) | 0.0653 (10) | |
H22 | 0.7450 | 0.3176 | 0.2437 | 0.078* | |
C23 | 0.76030 (19) | 0.0478 (2) | 0.15672 (18) | 0.0527 (9) | |
C24 | 0.7239 (2) | −0.0135 (3) | 0.1050 (2) | 0.0703 (11) | |
H24 | 0.6769 | −0.0011 | 0.0738 | 0.084* | |
C25 | 0.7578 (3) | −0.0931 (3) | 0.1001 (2) | 0.0819 (13) | |
H25 | 0.7337 | −0.1341 | 0.0647 | 0.098* | |
C26 | 0.8260 (3) | −0.1129 (3) | 0.1461 (3) | 0.0789 (12) | |
H26 | 0.8481 | −0.1672 | 0.1422 | 0.095* | |
C27 | 0.8621 (2) | −0.0529 (3) | 0.1983 (2) | 0.0777 (12) | |
H27 | 0.9088 | −0.0663 | 0.2298 | 0.093* | |
C28 | 0.8297 (2) | 0.0267 (3) | 0.2043 (2) | 0.0661 (10) | |
H28 | 0.8540 | 0.0670 | 0.2403 | 0.079* | |
C29 | 0.68050 (19) | 0.1447 (2) | 0.23794 (18) | 0.0498 (8) | |
C30 | 0.60572 (19) | 0.1288 (2) | 0.2250 (2) | 0.0593 (9) | |
H30 | 0.5734 | 0.1263 | 0.1781 | 0.071* | |
C31 | 0.5804 (2) | 0.1170 (3) | 0.2823 (2) | 0.0721 (11) | |
H31 | 0.5302 | 0.1083 | 0.2736 | 0.087* | |
C32 | 0.6266 (3) | 0.1177 (3) | 0.3513 (2) | 0.0750 (12) | |
H32 | 0.6084 | 0.1089 | 0.3894 | 0.090* | |
C33 | 0.7008 (2) | 0.1317 (3) | 0.3643 (2) | 0.0729 (11) | |
H33 | 0.7330 | 0.1313 | 0.4114 | 0.088* | |
C34 | 0.7278 (2) | 0.1462 (2) | 0.30799 (19) | 0.0638 (10) | |
H34 | 0.7778 | 0.1570 | 0.3172 | 0.077* | |
C35 | 0.1902 (2) | 0.3078 (3) | 0.07543 (17) | 0.0595 (9) | |
C36 | 0.2387 (2) | 0.3790 (3) | 0.0796 (2) | 0.0723 (11) | |
H36 | 0.2871 | 0.3675 | 0.0818 | 0.087* | |
C37 | 0.2153 (3) | 0.4658 (3) | 0.0803 (2) | 0.0841 (13) | |
H37 | 0.2482 | 0.5123 | 0.0829 | 0.101* | |
C38 | 0.1447 (3) | 0.4850 (3) | 0.0772 (2) | 0.0800 (13) | |
H38 | 0.1294 | 0.5439 | 0.0779 | 0.096* | |
C39 | 0.0969 (2) | 0.4154 (3) | 0.0731 (2) | 0.0683 (11) | |
C40 | 0.1188 (2) | 0.3278 (3) | 0.07163 (17) | 0.0623 (10) | |
H40 | 0.0851 | 0.2818 | 0.0680 | 0.075* | |
C41 | 0.2163 (2) | 0.2123 (2) | 0.07693 (17) | 0.0617 (10) | |
H41A | 0.2541 | 0.2090 | 0.0539 | 0.074* | |
H41B | 0.1754 | 0.1749 | 0.0498 | 0.074* | |
C42 | 0.0227 (3) | 0.4321 (3) | 0.0721 (2) | 0.0849 (13) | |
C43 | 0.32015 (19) | 0.2503 (2) | 0.21637 (18) | 0.0550 (9) | |
C44 | 0.3895 (2) | 0.2469 (3) | 0.20863 (19) | 0.0642 (10) | |
H44 | 0.4022 | 0.1993 | 0.1845 | 0.077* | |
C45 | 0.4392 (2) | 0.3137 (3) | 0.2365 (2) | 0.0781 (12) | |
H45 | 0.4858 | 0.3114 | 0.2315 | 0.094* | |
C46 | 0.4205 (3) | 0.3839 (3) | 0.2717 (2) | 0.0821 (13) | |
H46 | 0.4545 | 0.4291 | 0.2905 | 0.099* | |
C47 | 0.3521 (3) | 0.3884 (3) | 0.2798 (2) | 0.0799 (12) | |
H47 | 0.3399 | 0.4361 | 0.3042 | 0.096* | |
C48 | 0.3014 (2) | 0.3214 (3) | 0.25145 (19) | 0.0669 (10) | |
H48 | 0.2546 | 0.3244 | 0.2561 | 0.080* | |
C49 | 0.2971 (2) | 0.0648 (2) | 0.1677 (2) | 0.0581 (9) | |
C50 | 0.2752 (2) | 0.0107 (3) | 0.1084 (2) | 0.0779 (12) | |
H50 | 0.2386 | 0.0297 | 0.0669 | 0.094* | |
C51 | 0.3071 (3) | −0.0713 (3) | 0.1102 (3) | 0.0985 (16) | |
H51 | 0.2919 | −0.1078 | 0.0697 | 0.118* | |
C52 | 0.3601 (3) | −0.1002 (3) | 0.1694 (4) | 0.0963 (16) | |
H52 | 0.3815 | −0.1561 | 0.1697 | 0.116* | |
C53 | 0.3825 (3) | −0.0470 (3) | 0.2295 (3) | 0.0910 (14) | |
H53 | 0.4193 | −0.0667 | 0.2705 | 0.109* | |
C54 | 0.3509 (2) | 0.0355 (3) | 0.2293 (2) | 0.0768 (11) | |
H54 | 0.3656 | 0.0713 | 0.2702 | 0.092* | |
C55 | 0.18144 (19) | 0.1573 (2) | 0.20786 (18) | 0.0534 (9) | |
C56 | 0.1109 (2) | 0.1369 (2) | 0.1647 (2) | 0.0597 (9) | |
H56 | 0.1003 | 0.1313 | 0.1151 | 0.072* | |
C57 | 0.0561 (2) | 0.1250 (3) | 0.1953 (2) | 0.0723 (11) | |
H57 | 0.0084 | 0.1118 | 0.1662 | 0.087* | |
C58 | 0.0715 (3) | 0.1324 (3) | 0.2675 (3) | 0.0786 (12) | |
H58 | 0.0338 | 0.1257 | 0.2875 | 0.094* | |
C59 | 0.1418 (3) | 0.1498 (3) | 0.3114 (2) | 0.0778 (12) | |
H59 | 0.1521 | 0.1529 | 0.3611 | 0.093* | |
C60 | 0.1974 (2) | 0.1626 (2) | 0.2818 (2) | 0.0658 (10) | |
H60 | 0.2451 | 0.1747 | 0.3113 | 0.079* | |
N1 | 0.4317 (2) | 0.3151 (3) | 0.84045 (19) | 0.0875 (11) | |
N2 | 0.3606 (2) | 0.3238 (3) | 1.0040 (2) | 0.1000 (13) | |
N3 | 0.9608 (2) | 0.3414 (2) | 0.8829 (2) | 0.0867 (11) | |
N4 | 0.7969 (2) | 0.2761 (3) | 0.9571 (2) | 0.0936 (12) | |
N5 | 0.4584 (3) | 0.4751 (3) | 0.1290 (3) | 0.1336 (19) | |
N6 | −0.0351 (2) | 0.4436 (3) | 0.0736 (2) | 0.1084 (14) | |
P1 | 0.71916 (5) | 0.15259 (6) | 0.16601 (5) | 0.0517 (2) | |
P2 | 0.25325 (5) | 0.17021 (6) | 0.16846 (5) | 0.0535 (3) | |
S1 | 0.44310 (5) | 0.09780 (7) | 1.04475 (5) | 0.0612 (3) | |
S2 | 0.49732 (6) | 0.08587 (7) | 0.91018 (5) | 0.0721 (3) | |
S3 | 0.90439 (5) | 0.06748 (7) | 1.01219 (6) | 0.0694 (3) | |
S4 | 1.03274 (5) | 0.11747 (7) | 0.95286 (5) | 0.0627 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0455 (4) | 0.0584 (4) | 0.0527 (4) | 0.0018 (3) | 0.0133 (3) | 0.0064 (3) |
Ni2 | 0.0468 (4) | 0.0560 (4) | 0.0551 (4) | 0.0025 (3) | 0.0096 (3) | 0.0013 (3) |
C1 | 0.0410 (19) | 0.061 (2) | 0.063 (2) | 0.0029 (18) | 0.0134 (17) | 0.0062 (19) |
C2 | 0.051 (2) | 0.062 (2) | 0.063 (2) | 0.0034 (19) | 0.0166 (18) | 0.009 (2) |
C3 | 0.063 (3) | 0.069 (3) | 0.073 (3) | 0.007 (2) | 0.028 (2) | 0.007 (2) |
C4 | 0.066 (3) | 0.069 (3) | 0.073 (3) | 0.004 (2) | 0.027 (2) | 0.003 (2) |
C5 | 0.055 (2) | 0.057 (2) | 0.056 (2) | 0.012 (2) | 0.0077 (18) | 0.0009 (18) |
C6 | 0.054 (2) | 0.058 (2) | 0.056 (2) | 0.0011 (19) | 0.0143 (18) | 0.0000 (19) |
C7 | 0.070 (3) | 0.065 (3) | 0.063 (2) | 0.006 (2) | 0.025 (2) | 0.001 (2) |
C8 | 0.070 (3) | 0.066 (3) | 0.061 (2) | 0.004 (2) | 0.018 (2) | 0.002 (2) |
C9 | 0.059 (2) | 0.078 (3) | 0.054 (2) | 0.012 (2) | 0.0104 (19) | 0.010 (2) |
C10 | 0.085 (3) | 0.122 (5) | 0.097 (3) | 0.024 (3) | 0.043 (3) | 0.045 (3) |
C11 | 0.123 (5) | 0.116 (5) | 0.142 (5) | 0.015 (4) | 0.064 (4) | 0.070 (4) |
C12 | 0.127 (5) | 0.075 (3) | 0.102 (4) | 0.008 (3) | 0.039 (3) | 0.035 (3) |
C13 | 0.096 (3) | 0.061 (3) | 0.058 (2) | 0.007 (3) | 0.019 (2) | 0.012 (2) |
C14 | 0.069 (3) | 0.058 (3) | 0.057 (2) | 0.001 (2) | 0.0195 (19) | 0.0055 (19) |
C15 | 0.058 (2) | 0.080 (3) | 0.058 (2) | 0.005 (2) | 0.0168 (19) | −0.009 (2) |
C16 | 0.134 (5) | 0.057 (3) | 0.080 (3) | 0.015 (3) | 0.042 (3) | 0.007 (2) |
C17 | 0.050 (2) | 0.053 (2) | 0.055 (2) | 0.0036 (17) | 0.0169 (17) | 0.0043 (18) |
C18 | 0.079 (3) | 0.056 (2) | 0.076 (3) | −0.004 (2) | 0.039 (2) | 0.000 (2) |
C19 | 0.092 (3) | 0.068 (3) | 0.121 (4) | −0.011 (3) | 0.066 (3) | −0.001 (3) |
C20 | 0.097 (4) | 0.062 (3) | 0.131 (4) | −0.026 (3) | 0.056 (3) | −0.008 (3) |
C21 | 0.102 (4) | 0.048 (3) | 0.108 (3) | −0.011 (3) | 0.046 (3) | −0.016 (2) |
C22 | 0.072 (3) | 0.057 (2) | 0.074 (2) | 0.005 (2) | 0.035 (2) | −0.004 (2) |
C23 | 0.054 (2) | 0.046 (2) | 0.059 (2) | −0.0021 (18) | 0.0206 (19) | −0.0077 (18) |
C24 | 0.058 (2) | 0.072 (3) | 0.080 (3) | −0.002 (2) | 0.021 (2) | −0.024 (2) |
C25 | 0.087 (3) | 0.068 (3) | 0.099 (3) | −0.012 (3) | 0.042 (3) | −0.031 (3) |
C26 | 0.089 (3) | 0.049 (3) | 0.118 (4) | 0.006 (2) | 0.059 (3) | −0.006 (3) |
C27 | 0.072 (3) | 0.059 (3) | 0.100 (3) | 0.016 (2) | 0.025 (2) | −0.003 (2) |
C28 | 0.066 (3) | 0.055 (2) | 0.073 (2) | 0.000 (2) | 0.015 (2) | −0.008 (2) |
C29 | 0.051 (2) | 0.040 (2) | 0.060 (2) | 0.0013 (16) | 0.0196 (18) | −0.0042 (17) |
C30 | 0.047 (2) | 0.056 (2) | 0.071 (2) | 0.0061 (18) | 0.0144 (19) | 0.0035 (19) |
C31 | 0.058 (2) | 0.065 (3) | 0.106 (3) | 0.006 (2) | 0.043 (3) | 0.011 (3) |
C32 | 0.086 (3) | 0.071 (3) | 0.085 (3) | −0.001 (2) | 0.051 (3) | 0.003 (2) |
C33 | 0.076 (3) | 0.075 (3) | 0.068 (2) | −0.002 (2) | 0.024 (2) | −0.002 (2) |
C34 | 0.060 (2) | 0.069 (3) | 0.064 (2) | −0.006 (2) | 0.024 (2) | −0.005 (2) |
C35 | 0.064 (2) | 0.065 (3) | 0.050 (2) | 0.003 (2) | 0.0187 (18) | 0.0066 (19) |
C36 | 0.070 (3) | 0.078 (3) | 0.081 (3) | −0.004 (2) | 0.040 (2) | 0.006 (2) |
C37 | 0.099 (4) | 0.065 (3) | 0.098 (3) | −0.012 (3) | 0.046 (3) | 0.010 (3) |
C38 | 0.093 (3) | 0.061 (3) | 0.098 (3) | 0.006 (3) | 0.048 (3) | 0.019 (2) |
C39 | 0.075 (3) | 0.063 (3) | 0.075 (3) | 0.012 (2) | 0.034 (2) | 0.015 (2) |
C40 | 0.059 (2) | 0.067 (3) | 0.060 (2) | −0.004 (2) | 0.0176 (19) | 0.007 (2) |
C41 | 0.056 (2) | 0.072 (3) | 0.058 (2) | −0.001 (2) | 0.0185 (18) | −0.0052 (19) |
C42 | 0.095 (4) | 0.068 (3) | 0.101 (3) | 0.019 (3) | 0.045 (3) | 0.031 (2) |
C43 | 0.055 (2) | 0.051 (2) | 0.056 (2) | −0.0016 (18) | 0.0136 (18) | −0.0009 (18) |
C44 | 0.062 (2) | 0.056 (2) | 0.077 (3) | −0.005 (2) | 0.026 (2) | −0.001 (2) |
C45 | 0.065 (3) | 0.064 (3) | 0.106 (3) | −0.013 (2) | 0.028 (2) | 0.002 (3) |
C46 | 0.083 (3) | 0.063 (3) | 0.090 (3) | −0.022 (3) | 0.013 (3) | 0.005 (2) |
C47 | 0.108 (4) | 0.052 (3) | 0.075 (3) | −0.005 (3) | 0.021 (3) | −0.009 (2) |
C48 | 0.077 (3) | 0.056 (2) | 0.070 (2) | 0.001 (2) | 0.027 (2) | −0.007 (2) |
C49 | 0.057 (2) | 0.049 (2) | 0.073 (2) | −0.0080 (19) | 0.029 (2) | −0.010 (2) |
C50 | 0.076 (3) | 0.070 (3) | 0.091 (3) | −0.002 (2) | 0.031 (2) | −0.025 (2) |
C51 | 0.112 (4) | 0.070 (3) | 0.132 (5) | −0.007 (3) | 0.067 (4) | −0.032 (3) |
C52 | 0.112 (4) | 0.050 (3) | 0.159 (5) | 0.006 (3) | 0.088 (4) | −0.001 (3) |
C53 | 0.085 (3) | 0.068 (3) | 0.125 (4) | 0.017 (3) | 0.040 (3) | 0.012 (3) |
C54 | 0.083 (3) | 0.059 (3) | 0.089 (3) | 0.006 (2) | 0.028 (3) | −0.003 (2) |
C55 | 0.053 (2) | 0.047 (2) | 0.061 (2) | 0.0034 (18) | 0.0197 (19) | −0.0019 (18) |
C56 | 0.061 (2) | 0.052 (2) | 0.065 (2) | 0.0040 (19) | 0.017 (2) | 0.0067 (19) |
C57 | 0.062 (3) | 0.065 (3) | 0.093 (3) | 0.002 (2) | 0.031 (2) | 0.010 (2) |
C58 | 0.078 (3) | 0.059 (3) | 0.118 (4) | 0.006 (2) | 0.060 (3) | 0.012 (3) |
C59 | 0.104 (4) | 0.069 (3) | 0.075 (3) | 0.006 (3) | 0.050 (3) | 0.004 (2) |
C60 | 0.074 (3) | 0.060 (3) | 0.065 (2) | 0.000 (2) | 0.024 (2) | −0.001 (2) |
N1 | 0.095 (3) | 0.079 (3) | 0.090 (3) | 0.008 (2) | 0.032 (2) | 0.023 (2) |
N2 | 0.107 (3) | 0.089 (3) | 0.117 (3) | 0.029 (3) | 0.056 (3) | 0.002 (2) |
N3 | 0.104 (3) | 0.066 (2) | 0.099 (3) | 0.012 (2) | 0.045 (2) | 0.013 (2) |
N4 | 0.082 (3) | 0.097 (3) | 0.102 (3) | 0.032 (2) | 0.031 (2) | 0.006 (2) |
N5 | 0.211 (6) | 0.083 (3) | 0.142 (4) | 0.051 (3) | 0.106 (4) | 0.015 (3) |
N6 | 0.104 (3) | 0.093 (3) | 0.147 (4) | 0.027 (3) | 0.068 (3) | 0.046 (3) |
P1 | 0.0482 (5) | 0.0511 (6) | 0.0556 (5) | 0.0023 (4) | 0.0166 (4) | −0.0061 (5) |
P2 | 0.0509 (6) | 0.0529 (6) | 0.0574 (5) | −0.0007 (5) | 0.0182 (4) | −0.0080 (5) |
S1 | 0.0583 (6) | 0.0668 (6) | 0.0607 (6) | 0.0045 (5) | 0.0221 (5) | 0.0076 (5) |
S2 | 0.0835 (7) | 0.0727 (7) | 0.0708 (6) | 0.0205 (6) | 0.0397 (6) | 0.0171 (5) |
S3 | 0.0596 (6) | 0.0699 (7) | 0.0816 (7) | 0.0097 (5) | 0.0268 (5) | 0.0137 (6) |
S4 | 0.0561 (6) | 0.0621 (6) | 0.0705 (6) | 0.0069 (5) | 0.0215 (5) | 0.0061 (5) |
Ni1—S2i | 2.1661 (10) | C29—C30 | 1.392 (4) |
Ni1—S2 | 2.1661 (10) | C29—P1 | 1.795 (3) |
Ni1—S1 | 2.1709 (10) | C30—C31 | 1.370 (5) |
Ni1—S1i | 2.1709 (10) | C30—H30 | 0.9300 |
Ni2—S4ii | 2.1695 (10) | C31—C32 | 1.357 (5) |
Ni2—S4 | 2.1695 (10) | C31—H31 | 0.9300 |
Ni2—S3 | 2.1709 (10) | C32—C33 | 1.377 (5) |
Ni2—S3ii | 2.1709 (10) | C32—H32 | 0.9300 |
C1—C2 | 1.342 (4) | C33—C34 | 1.378 (5) |
C1—C4 | 1.416 (5) | C33—H33 | 0.9300 |
C1—S1 | 1.742 (4) | C34—H34 | 0.9300 |
C2—C3 | 1.434 (5) | C35—C40 | 1.379 (5) |
C2—S2 | 1.720 (4) | C35—C36 | 1.398 (5) |
C3—N1 | 1.143 (5) | C35—C41 | 1.510 (5) |
C4—N2 | 1.137 (5) | C36—C37 | 1.375 (5) |
C5—C6 | 1.341 (5) | C36—H36 | 0.9300 |
C5—C8 | 1.430 (5) | C37—C38 | 1.365 (6) |
C5—S3 | 1.735 (4) | C37—H37 | 0.9300 |
C6—C7 | 1.421 (5) | C38—C39 | 1.371 (5) |
C6—S4 | 1.735 (4) | C38—H38 | 0.9300 |
C7—N3 | 1.135 (4) | C39—C40 | 1.379 (5) |
C8—N4 | 1.145 (5) | C39—C42 | 1.437 (6) |
C9—C14 | 1.372 (5) | C40—H40 | 0.9300 |
C9—C10 | 1.397 (6) | C41—P2 | 1.816 (3) |
C9—C15 | 1.505 (5) | C41—H41A | 0.9700 |
C10—C11 | 1.375 (7) | C41—H41B | 0.9700 |
C10—H10 | 0.9300 | C42—N6 | 1.130 (5) |
C11—C12 | 1.357 (7) | C43—C48 | 1.376 (5) |
C11—H11 | 0.9300 | C43—C44 | 1.386 (5) |
C12—C13 | 1.370 (6) | C43—P2 | 1.784 (4) |
C12—H12 | 0.9300 | C44—C45 | 1.367 (5) |
C13—C14 | 1.387 (5) | C44—H44 | 0.9300 |
C13—C16 | 1.445 (6) | C45—C46 | 1.365 (5) |
C14—H14 | 0.9300 | C45—H45 | 0.9300 |
C15—P1 | 1.821 (3) | C46—C47 | 1.371 (6) |
C15—H15A | 0.9700 | C46—H46 | 0.9300 |
C15—H15B | 0.9700 | C47—C48 | 1.381 (5) |
C16—N5 | 1.128 (6) | C47—H47 | 0.9300 |
C17—C22 | 1.378 (5) | C48—H48 | 0.9300 |
C17—C18 | 1.392 (5) | C49—C50 | 1.366 (5) |
C17—P1 | 1.781 (3) | C49—C54 | 1.383 (5) |
C18—C19 | 1.357 (5) | C49—P2 | 1.788 (4) |
C18—H18 | 0.9300 | C50—C51 | 1.367 (6) |
C19—C20 | 1.363 (6) | C50—H50 | 0.9300 |
C19—H19 | 0.9300 | C51—C52 | 1.344 (7) |
C20—C21 | 1.371 (5) | C51—H51 | 0.9300 |
C20—H20 | 0.9300 | C52—C53 | 1.370 (6) |
C21—C22 | 1.381 (5) | C52—H52 | 0.9300 |
C21—H21 | 0.9300 | C53—C54 | 1.374 (6) |
C22—H22 | 0.9300 | C53—H53 | 0.9300 |
C23—C24 | 1.377 (5) | C54—H54 | 0.9300 |
C23—C28 | 1.392 (5) | C55—C60 | 1.383 (5) |
C23—P1 | 1.790 (3) | C55—C56 | 1.378 (5) |
C24—C25 | 1.375 (5) | C55—P2 | 1.792 (3) |
C24—H24 | 0.9300 | C56—C57 | 1.377 (5) |
C25—C26 | 1.361 (6) | C56—H56 | 0.9300 |
C25—H25 | 0.9300 | C57—C58 | 1.355 (5) |
C26—C27 | 1.370 (6) | C57—H57 | 0.9300 |
C26—H26 | 0.9300 | C58—C59 | 1.369 (6) |
C27—C28 | 1.365 (5) | C58—H58 | 0.9300 |
C27—H27 | 0.9300 | C59—C60 | 1.381 (5) |
C28—H28 | 0.9300 | C59—H59 | 0.9300 |
C29—C34 | 1.380 (4) | C60—H60 | 0.9300 |
S2i—Ni1—S2 | 180.0 | C32—C33—C34 | 120.4 (4) |
S2i—Ni1—S1 | 87.41 (4) | C32—C33—H33 | 119.8 |
S2—Ni1—S1 | 92.59 (4) | C34—C33—H33 | 119.8 |
S2i—Ni1—S1i | 92.59 (4) | C29—C34—C33 | 119.9 (4) |
S2—Ni1—S1i | 87.41 (4) | C29—C34—H34 | 120.1 |
S1—Ni1—S1i | 180.000 (1) | C33—C34—H34 | 120.1 |
S4ii—Ni2—S4 | 180.0 | C40—C35—C36 | 117.9 (4) |
S4ii—Ni2—S3 | 87.69 (4) | C40—C35—C41 | 121.5 (4) |
S4—Ni2—S3 | 92.31 (4) | C36—C35—C41 | 120.6 (4) |
S4ii—Ni2—S3ii | 92.31 (4) | C37—C36—C35 | 120.4 (4) |
S4—Ni2—S3ii | 87.69 (4) | C37—C36—H36 | 119.8 |
S3—Ni2—S3ii | 180.00 (5) | C35—C36—H36 | 119.8 |
C2—C1—C4 | 121.2 (3) | C38—C37—C36 | 121.4 (4) |
C2—C1—S1 | 120.8 (3) | C38—C37—H37 | 119.3 |
C4—C1—S1 | 118.0 (3) | C36—C37—H37 | 119.3 |
C1—C2—C3 | 118.9 (3) | C37—C38—C39 | 118.4 (4) |
C1—C2—S2 | 121.6 (3) | C37—C38—H38 | 120.8 |
C3—C2—S2 | 119.4 (3) | C39—C38—H38 | 120.8 |
N1—C3—C2 | 177.7 (4) | C40—C39—C38 | 121.4 (4) |
N2—C4—C1 | 179.4 (5) | C40—C39—C42 | 118.1 (4) |
C6—C5—C8 | 121.1 (3) | C38—C39—C42 | 120.5 (4) |
C6—C5—S3 | 121.6 (3) | C39—C40—C35 | 120.5 (4) |
C8—C5—S3 | 117.2 (3) | C39—C40—H40 | 119.7 |
C5—C6—C7 | 120.9 (3) | C35—C40—H40 | 119.7 |
C5—C6—S4 | 120.4 (3) | C35—C41—P2 | 111.6 (2) |
C7—C6—S4 | 118.5 (3) | C35—C41—H41A | 109.3 |
N3—C7—C6 | 178.7 (5) | P2—C41—H41A | 109.3 |
N4—C8—C5 | 179.0 (5) | C35—C41—H41B | 109.3 |
C14—C9—C10 | 118.0 (4) | P2—C41—H41B | 109.3 |
C14—C9—C15 | 121.8 (4) | H41A—C41—H41B | 108.0 |
C10—C9—C15 | 120.2 (4) | N6—C42—C39 | 177.6 (5) |
C11—C10—C9 | 120.5 (5) | C48—C43—C44 | 119.8 (3) |
C11—C10—H10 | 119.7 | C48—C43—P2 | 121.5 (3) |
C9—C10—H10 | 119.7 | C44—C43—P2 | 118.0 (3) |
C12—C11—C10 | 121.1 (5) | C45—C44—C43 | 119.9 (4) |
C12—C11—H11 | 119.5 | C45—C44—H44 | 120.1 |
C10—C11—H11 | 119.5 | C43—C44—H44 | 120.0 |
C11—C12—C13 | 119.1 (5) | C44—C45—C46 | 120.1 (4) |
C11—C12—H12 | 120.5 | C44—C45—H45 | 120.0 |
C13—C12—H12 | 120.5 | C46—C45—H45 | 120.0 |
C14—C13—C12 | 120.7 (4) | C47—C46—C45 | 120.8 (4) |
C14—C13—C16 | 120.2 (4) | C47—C46—H46 | 119.6 |
C12—C13—C16 | 119.0 (4) | C45—C46—H46 | 119.6 |
C9—C14—C13 | 120.6 (4) | C46—C47—C48 | 119.5 (4) |
C9—C14—H14 | 119.7 | C46—C47—H47 | 120.2 |
C13—C14—H14 | 119.7 | C48—C47—H47 | 120.2 |
C9—C15—P1 | 113.0 (2) | C43—C48—C47 | 119.9 (4) |
C9—C15—H15A | 109.0 | C43—C48—H48 | 120.1 |
P1—C15—H15A | 109.0 | C47—C48—H48 | 120.1 |
C9—C15—H15B | 109.0 | C50—C49—C54 | 119.6 (4) |
P1—C15—H15B | 109.0 | C50—C49—P2 | 120.9 (3) |
H15A—C15—H15B | 107.8 | C54—C49—P2 | 119.5 (3) |
N5—C16—C13 | 179.0 (6) | C51—C50—C49 | 119.8 (5) |
C22—C17—C18 | 119.6 (3) | C51—C50—H50 | 120.1 |
C22—C17—P1 | 121.0 (3) | C49—C50—H50 | 120.1 |
C18—C17—P1 | 119.1 (3) | C52—C51—C50 | 121.2 (5) |
C19—C18—C17 | 119.7 (4) | C52—C51—H51 | 119.4 |
C19—C18—H18 | 120.1 | C50—C51—H51 | 119.4 |
C17—C18—H18 | 120.1 | C51—C52—C53 | 119.7 (5) |
C18—C19—C20 | 121.0 (4) | C51—C52—H52 | 120.1 |
C18—C19—H19 | 119.5 | C53—C52—H52 | 120.1 |
C20—C19—H19 | 119.5 | C54—C53—C52 | 120.2 (5) |
C19—C20—C21 | 120.0 (4) | C54—C53—H53 | 119.9 |
C19—C20—H20 | 120.0 | C52—C53—H53 | 119.9 |
C21—C20—H20 | 120.0 | C53—C54—C49 | 119.4 (4) |
C20—C21—C22 | 120.1 (4) | C53—C54—H54 | 120.3 |
C20—C21—H21 | 120.0 | C49—C54—H54 | 120.3 |
C22—C21—H21 | 120.0 | C60—C55—C56 | 119.8 (3) |
C17—C22—C21 | 119.6 (4) | C60—C55—P2 | 120.3 (3) |
C17—C22—H22 | 120.2 | C56—C55—P2 | 119.8 (3) |
C21—C22—H22 | 120.2 | C55—C56—C57 | 119.7 (4) |
C24—C23—C28 | 119.4 (3) | C55—C56—H56 | 120.2 |
C24—C23—P1 | 121.5 (3) | C57—C56—H56 | 120.2 |
C28—C23—P1 | 119.1 (3) | C58—C57—C56 | 120.3 (4) |
C25—C24—C23 | 119.3 (4) | C58—C57—H57 | 119.8 |
C25—C24—H24 | 120.3 | C56—C57—H57 | 119.8 |
C23—C24—H24 | 120.3 | C57—C58—C59 | 120.7 (4) |
C26—C25—C24 | 121.1 (4) | C57—C58—H58 | 119.7 |
C26—C25—H25 | 119.4 | C59—C58—H58 | 119.7 |
C24—C25—H25 | 119.4 | C58—C59—C60 | 119.9 (4) |
C25—C26—C27 | 119.9 (4) | C58—C59—H59 | 120.1 |
C25—C26—H26 | 120.1 | C60—C59—H59 | 120.1 |
C27—C26—H26 | 120.1 | C55—C60—C59 | 119.5 (4) |
C28—C27—C26 | 120.1 (4) | C55—C60—H60 | 120.2 |
C28—C27—H27 | 119.9 | C59—C60—H60 | 120.2 |
C26—C27—H27 | 119.9 | C17—P1—C23 | 108.84 (16) |
C27—C28—C23 | 120.1 (4) | C17—P1—C29 | 110.34 (16) |
C27—C28—H28 | 119.9 | C23—P1—C29 | 109.18 (15) |
C23—C28—H28 | 119.9 | C17—P1—C15 | 108.13 (17) |
C34—C29—C30 | 119.4 (3) | C23—P1—C15 | 109.27 (16) |
C34—C29—P1 | 118.4 (3) | C29—P1—C15 | 111.05 (17) |
C30—C29—P1 | 121.9 (3) | C43—P2—C49 | 109.69 (17) |
C31—C30—C29 | 119.2 (3) | C43—P2—C55 | 111.52 (17) |
C31—C30—H30 | 120.4 | C49—P2—C55 | 109.65 (16) |
C29—C30—H30 | 120.4 | C43—P2—C41 | 105.81 (17) |
C32—C31—C30 | 121.7 (4) | C49—P2—C41 | 109.37 (17) |
C32—C31—H31 | 119.2 | C55—P2—C41 | 110.73 (16) |
C30—C31—H31 | 119.2 | C1—S1—Ni1 | 102.29 (13) |
C31—C32—C33 | 119.3 (4) | C2—S2—Ni1 | 102.74 (12) |
C31—C32—H32 | 120.3 | C5—S3—Ni2 | 102.43 (13) |
C33—C32—H32 | 120.3 | C6—S4—Ni2 | 102.97 (13) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+2, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···N4iii | 0.93 | 2.57 | 3.479 (7) | 165 |
C33—H33···N2iv | 0.93 | 2.62 | 3.452 (6) | 149 |
C36—H36···N2iii | 0.93 | 2.47 | 3.250 (6) | 141 |
Symmetry codes: (iii) x, y, z−1; (iv) x+1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | (C26H21NP)2[Ni(C4N2S2)2] |
Mr | 1095.89 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 19.158 (4), 14.956 (3), 19.598 (4) |
β (°) | 108.785 (4) |
V (Å3) | 5316.3 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.63 |
Crystal size (mm) | 0.34 × 0.22 × 0.15 |
Data collection | |
Diffractometer | Bruker Smart Apex CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.834, 0.912 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25624, 9356, 6235 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.139, 1.09 |
No. of reflections | 9356 |
No. of parameters | 661 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.83, −0.74 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Bruker, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···N4i | 0.930 | 2.570 | 3.479 (7) | 165.0 |
C33—H33···N2ii | 0.930 | 2.620 | 3.452 (6) | 149.0 |
C36—H36···N2i | 0.930 | 2.470 | 3.250 (6) | 141.0 |
Symmetry codes: (i) x, y, z−1; (ii) x+1/2, −y+1/2, z−1/2. |
Much effort has been devoted to the study of square planar M(dithiolene)2 complexes (Robertson & Cronin, 2002; Ni et al., 2004; Nishijo et al., 2003; Canadell, 1999). Recently, we have carried out a systematic investigation on the coordination chemistry of salts containing Ni(mnt)2 anion and substituted benzyltriphenylphosphonium cations and obtained some Ni(mnt)22--based molecular solids (Ni et al., 2005; Yang & Ni, 2006; Liu & Ni, 2006; Zhou et al., 2007). In this paper, we report the structure of the title compound, Fig. 1. There are two halves of non-equivalent Ni(mnt)22- anions and two (mCNBzTPP)+ cations in the asymmetric unit. For the two Ni(mnt)22- anions. The Ni1 and Ni2 atoms are each coordinated to four sulfur atoms and exhibit square planar coordination geometry with the Ni atoms lying on inversion centres. The N atoms of the four unique CN groups deviate from the C1/C2/Ni1/S1/S2 or C5/C6/Ni2/S3/S4 planes by 0.029 (3) Å for N1, -0.077 (3) Å for N2, -0.216 (2) Å for N3 and -0.242 (2) Å for N4 respectively.
The two (mCNBzTPP)+ cations adopt a conformation where four phenyl rings are twisted with respect to the plane including the P atom and the two C atoms linking it to the 3-cyanobenzyl ring. For the cation containing P1, the dihedral angles are 88.7 (3) for the C9/C10/C11/C12/C13/C14 ring, 84.0 (2) ° for the C17/C18/C19/C20/C21/C22 ring, 24.4 (2) ° for the C23/C24/C25/C26/C27/C28 ring, and 87.7 (2) ° for the C29/C30/C31/C32/C33/C34 ring. For the cation containing P2, the dihedral angles are 90.6 (3) for the C35/C36/C37/C38/C39/C40 ring, 93.2 (2) ° for the C43/C44/C45/C46/C47/C48 ring, 23.0 (2) ° for the C49/C50/C51/C52/C53/C54 ring, and 82.1 (2) ° for the C55/C56/C57/C58/C59/C60 ring. The deviations of the N5 and N6 atoms from the C9/C10/C11/C12/C13/C14 and C35/C36/C37/C38/C39/C40 phenyl ring planes are -0.052 (2)Å and 0.130 (2) Å respectively.
The crystal structure is stabilized by C10—H10···N4, C33—H33···N2 and C36—H36···N hydrogen bonds, Fig 2, Table 1.