Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103013519/dn1020sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103013519/dn1020Isup2.hkl |
CCDC reference: 219554
The title compound was obtained by dissolving proguanil hydrochloride in DMF to a concentration of 0.2 mol L−1, (4 × 10−4 mol) and adding nickel chloride hexahydrate in DMF to a concentration of 0.1 mol L−1, (2 × 10−4 mol). This hydrochloric mixture was neutralized by a sodium hydroxide solution (4 × 10−4 mol). After mixing and heating (50°) for a period of 2 h and slow evaporation, yellow crystals were obtained under ambient pressure.
All H atoms were placed at their idealized positions as riding atoms (C—Haromatic=0.93 Å, C—Hmethine= 0.93 Å, C—Hmethyl=0.96 Å and N—H=0.86 Å). A disordered model for the DMF solvate based on a 60:40 distribution of the N(Me)2 over two sites related by a pseudo twofold axis was applied.
Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Ni(C11H16ClN5)2]Cl2·C3H7NO | F(000) = 1480 |
Mr = 710.18 | Dx = 1.377 Mg m−3 Dm = 1.38 Mg m−3 Dm measured by flotation (CHCl3 / CH2Cl2) |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71069 Å |
a = 10.824 (5) Å | Cell parameters from 25 reflections |
b = 24.12 (1) Å | θ = 7.0–11.1° |
c = 13.180 (3) Å | µ = 0.92 mm−1 |
β = 95.42 (3)° | T = 293 K |
V = 3426 (2) Å3 | Parallelepipedic, orange |
Z = 4 | 0.45 × 0.37 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 3270 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.061 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
ω – 2θ scans | h = −12→12 |
Absorption correction: empirical (using intensity measurements) 'multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995)' | k = 0→28 |
Tmin = 0.648, Tmax = 0.883 | l = −15→15 |
11970 measured reflections | 3 standard reflections every 60 min |
6000 independent reflections | intensity decay: 2% |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0724P)2] where P = (Fo2 + 2Fc2)/3 |
6000 reflections | (Δ/σ)max = 0.001 |
417 parameters | Δρmax = 0.37 e Å−3 |
31 restraints | Δρmin = −0.69 e Å−3 |
[Ni(C11H16ClN5)2]Cl2·C3H7NO | V = 3426 (2) Å3 |
Mr = 710.18 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 10.824 (5) Å | µ = 0.92 mm−1 |
b = 24.12 (1) Å | T = 293 K |
c = 13.180 (3) Å | 0.45 × 0.37 × 0.10 mm |
β = 95.42 (3)° |
Enraf–Nonius CAD-4 diffractometer | 3270 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) 'multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995)' | Rint = 0.061 |
Tmin = 0.648, Tmax = 0.883 | 3 standard reflections every 60 min |
11970 measured reflections | intensity decay: 2% |
6000 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 31 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.37 e Å−3 |
6000 reflections | Δρmin = −0.69 e Å−3 |
417 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni | 0.17718 (4) | 0.124941 (15) | 0.02731 (3) | 0.03747 (14) | |
N1 | 0.3256 (3) | −0.03075 (11) | 0.0936 (2) | 0.0480 (8) | |
H1 | 0.3134 | −0.0640 | 0.0714 | 0.058* | |
N2 | 0.2604 (3) | 0.06218 (10) | 0.0808 (2) | 0.0423 (7) | |
H2 | 0.3101 | 0.0679 | 0.1347 | 0.051* | |
N3 | 0.1791 (2) | −0.00413 (10) | −0.0336 (2) | 0.0406 (7) | |
H3 | 0.1851 | −0.0379 | −0.0536 | 0.049* | |
N4 | 0.0777 (3) | 0.07998 (10) | −0.0611 (2) | 0.0415 (7) | |
H4 | 0.0108 | 0.0953 | −0.0880 | 0.050* | |
N5 | 0.0332 (3) | 0.00371 (11) | −0.1680 (2) | 0.0482 (8) | |
H5 | 0.0350 | −0.0319 | −0.1701 | 0.058* | |
N21 | 0.3881 (3) | 0.25224 (12) | 0.1615 (3) | 0.0597 (9) | |
H21 | 0.3991 | 0.2865 | 0.1465 | 0.072* | |
N22 | 0.2813 (3) | 0.17040 (11) | 0.1114 (2) | 0.0468 (8) | |
H22 | 0.3194 | 0.1546 | 0.1638 | 0.056* | |
N23 | 0.2423 (3) | 0.25324 (11) | 0.0259 (2) | 0.0483 (8) | |
H23 | 0.2744 | 0.2846 | 0.0116 | 0.058* | |
N24 | 0.0939 (3) | 0.18774 (10) | −0.0268 (2) | 0.0412 (7) | |
H24 | 0.0193 | 0.1823 | −0.0535 | 0.049* | |
N25 | 0.0753 (3) | 0.28051 (11) | −0.0810 (2) | 0.0549 (9) | |
H25 | 0.1012 | 0.3136 | −0.0673 | 0.066* | |
Cl1 | 0.15706 (11) | −0.11925 (4) | −0.15644 (9) | 0.0699 (3) | |
Cl2 | 0.19344 (9) | −0.14532 (4) | 0.13548 (8) | 0.0559 (3) | |
Cl4 | 0.70335 (12) | 0.01491 (6) | 0.43410 (10) | 0.0930 (4) | |
Cl24 | 0.69527 (14) | 0.16978 (6) | 0.52408 (11) | 0.1046 (5) | |
C1 | 0.4180 (3) | −0.02108 (13) | 0.1745 (3) | 0.0427 (9) | |
C2 | 0.4077 (4) | −0.04429 (15) | 0.2688 (3) | 0.0531 (10) | |
H20 | 0.3409 | −0.0672 | 0.2789 | 0.064* | |
C3 | 0.4962 (4) | −0.03345 (18) | 0.3478 (3) | 0.0607 (11) | |
H30 | 0.4891 | −0.0488 | 0.4117 | 0.073* | |
C4 | 0.5942 (4) | −0.00027 (17) | 0.3327 (3) | 0.0561 (10) | |
C5 | 0.6085 (4) | 0.02173 (16) | 0.2390 (3) | 0.0561 (11) | |
H50 | 0.6773 | 0.0435 | 0.2292 | 0.067* | |
C6 | 0.5197 (3) | 0.01124 (15) | 0.1593 (3) | 0.0499 (9) | |
H60 | 0.5284 | 0.0260 | 0.0951 | 0.060* | |
C7 | 0.2551 (3) | 0.01135 (13) | 0.0494 (3) | 0.0382 (8) | |
C8 | 0.0939 (3) | 0.02861 (13) | −0.0885 (3) | 0.0380 (8) | |
C9 | −0.0366 (4) | 0.03274 (16) | −0.2522 (3) | 0.0522 (10) | |
H90 | −0.1014 | 0.0547 | −0.2240 | 0.063* | |
C10 | 0.0421 (5) | 0.0710 (2) | −0.3063 (4) | 0.0868 (15) | |
H101 | 0.0857 | 0.0956 | −0.2579 | 0.130* | |
H102 | −0.0092 | 0.0922 | −0.3553 | 0.130* | |
H103 | 0.1009 | 0.0499 | −0.3405 | 0.130* | |
C11 | −0.0990 (4) | −0.0106 (2) | −0.3212 (3) | 0.0817 (15) | |
H111 | −0.0372 | −0.0331 | −0.3488 | 0.123* | |
H112 | −0.1490 | 0.0072 | −0.3758 | 0.123* | |
H113 | −0.1506 | −0.0335 | −0.2831 | 0.123* | |
C21 | 0.4594 (3) | 0.22990 (14) | 0.2478 (3) | 0.0493 (10) | |
C22 | 0.5558 (4) | 0.19353 (15) | 0.2375 (3) | 0.0532 (10) | |
H220 | 0.5728 | 0.1819 | 0.1730 | 0.064* | |
C23 | 0.6273 (4) | 0.17427 (16) | 0.3224 (4) | 0.0611 (11) | |
H230 | 0.6915 | 0.1494 | 0.3152 | 0.073* | |
C24 | 0.6034 (4) | 0.19192 (18) | 0.4170 (3) | 0.0622 (11) | |
C25 | 0.5072 (4) | 0.22774 (18) | 0.4283 (3) | 0.0665 (12) | |
H250 | 0.4908 | 0.2392 | 0.4931 | 0.080* | |
C26 | 0.4352 (4) | 0.24668 (16) | 0.3442 (4) | 0.0616 (11) | |
H260 | 0.3699 | 0.2709 | 0.3521 | 0.074* | |
C27 | 0.3039 (3) | 0.22284 (13) | 0.1014 (3) | 0.0435 (9) | |
C28 | 0.1337 (3) | 0.23848 (13) | −0.0293 (3) | 0.0419 (9) | |
C29 | −0.0282 (4) | 0.27375 (16) | −0.1581 (3) | 0.0594 (11) | |
H290 | −0.0862 | 0.2470 | −0.1326 | 0.071* | |
C30 | 0.0129 (5) | 0.2517 (2) | −0.2553 (4) | 0.0996 (18) | |
H301 | 0.0692 | 0.2775 | −0.2819 | 0.149* | |
H302 | −0.0581 | 0.2467 | −0.3039 | 0.149* | |
H303 | 0.0539 | 0.2168 | −0.2426 | 0.149* | |
C31 | −0.0942 (4) | 0.32978 (18) | −0.1709 (4) | 0.0894 (16) | |
H311 | −0.1124 | 0.3433 | −0.1054 | 0.134* | |
H312 | −0.1701 | 0.3254 | −0.2141 | 0.134* | |
H313 | −0.0415 | 0.3558 | −0.2012 | 0.134* | |
C51 | 0.3507 (4) | 0.10755 (15) | 0.3792 (4) | 0.0579 (11) | |
H51 | 0.4171 | 0.0972 | 0.4252 | 0.070* | |
O50 | 0.3558 (3) | 0.09921 (11) | 0.2894 (2) | 0.0673 (8) | |
N50 | 0.2534 (18) | 0.1309 (14) | 0.4132 (11) | 0.063 (5) | 0.61 |
C52 | 0.1569 (12) | 0.1532 (7) | 0.3434 (10) | 0.081 (4) | 0.61 |
H52A | 0.1691 | 0.1924 | 0.3365 | 0.122* | 0.61 |
H52B | 0.0779 | 0.1465 | 0.3686 | 0.122* | 0.61 |
H52C | 0.1589 | 0.1357 | 0.2781 | 0.122* | 0.61 |
C53 | 0.2452 (16) | 0.1461 (9) | 0.5186 (10) | 0.114 (7) | 0.61 |
H53A | 0.3110 | 0.1284 | 0.5607 | 0.171* | 0.61 |
H53B | 0.1667 | 0.1343 | 0.5393 | 0.171* | 0.61 |
H53C | 0.2526 | 0.1856 | 0.5258 | 0.171* | 0.61 |
N50A | 0.278 (3) | 0.135 (2) | 0.4333 (17) | 0.080 (9) | 0.39 |
C52A | 0.157 (2) | 0.1524 (14) | 0.3977 (19) | 0.140 (13) | 0.39 |
H52D | 0.1434 | 0.1895 | 0.4207 | 0.210* | 0.39 |
H52E | 0.0973 | 0.1279 | 0.4238 | 0.210* | 0.39 |
H52F | 0.1472 | 0.1515 | 0.3246 | 0.210* | 0.39 |
C53A | 0.305 (2) | 0.1432 (11) | 0.5430 (13) | 0.084 (7) | 0.39 |
H53D | 0.3815 | 0.1250 | 0.5659 | 0.126* | 0.39 |
H53E | 0.2388 | 0.1277 | 0.5776 | 0.126* | 0.39 |
H53F | 0.3119 | 0.1821 | 0.5575 | 0.126* | 0.39 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0510 (3) | 0.01572 (19) | 0.0442 (3) | −0.0026 (2) | −0.00305 (19) | 0.0002 (2) |
N1 | 0.0585 (19) | 0.0178 (13) | 0.064 (2) | 0.0007 (13) | −0.0127 (16) | 0.0001 (13) |
N2 | 0.0545 (18) | 0.0202 (13) | 0.0488 (18) | −0.0033 (13) | −0.0127 (14) | 0.0003 (12) |
N3 | 0.0498 (18) | 0.0186 (13) | 0.0510 (18) | 0.0001 (12) | −0.0078 (14) | −0.0069 (12) |
N4 | 0.0415 (17) | 0.0236 (14) | 0.0571 (18) | 0.0036 (12) | −0.0072 (14) | −0.0056 (13) |
N5 | 0.0580 (19) | 0.0268 (15) | 0.056 (2) | −0.0011 (14) | −0.0136 (15) | −0.0085 (14) |
N21 | 0.072 (2) | 0.0232 (15) | 0.079 (2) | −0.0127 (15) | −0.0141 (19) | −0.0047 (15) |
N22 | 0.065 (2) | 0.0224 (14) | 0.0499 (18) | −0.0073 (14) | −0.0109 (15) | 0.0027 (13) |
N23 | 0.057 (2) | 0.0194 (14) | 0.067 (2) | −0.0071 (13) | 0.0008 (16) | 0.0072 (14) |
N24 | 0.0473 (18) | 0.0196 (14) | 0.0554 (19) | −0.0028 (12) | −0.0020 (14) | 0.0046 (12) |
N25 | 0.067 (2) | 0.0222 (15) | 0.074 (2) | −0.0010 (14) | −0.0028 (18) | 0.0134 (15) |
Cl1 | 0.0910 (8) | 0.0285 (5) | 0.0928 (8) | −0.0013 (5) | 0.0222 (6) | −0.0127 (5) |
Cl2 | 0.0487 (6) | 0.0274 (4) | 0.0909 (8) | 0.0015 (4) | 0.0032 (5) | −0.0015 (5) |
Cl4 | 0.0815 (8) | 0.1200 (11) | 0.0710 (8) | 0.0028 (8) | −0.0260 (7) | −0.0133 (7) |
Cl24 | 0.1243 (12) | 0.0970 (10) | 0.0857 (9) | 0.0176 (9) | −0.0265 (8) | 0.0027 (8) |
C1 | 0.044 (2) | 0.0326 (19) | 0.050 (2) | 0.0073 (16) | −0.0045 (17) | 0.0023 (16) |
C2 | 0.054 (2) | 0.040 (2) | 0.066 (3) | 0.0043 (18) | 0.005 (2) | 0.0081 (19) |
C3 | 0.063 (3) | 0.063 (3) | 0.055 (3) | 0.013 (2) | −0.003 (2) | 0.015 (2) |
C4 | 0.052 (3) | 0.058 (3) | 0.057 (3) | 0.008 (2) | −0.003 (2) | −0.003 (2) |
C5 | 0.048 (2) | 0.053 (2) | 0.067 (3) | −0.0045 (19) | 0.004 (2) | −0.001 (2) |
C6 | 0.052 (2) | 0.046 (2) | 0.051 (2) | −0.0018 (18) | 0.0010 (19) | 0.0013 (18) |
C7 | 0.046 (2) | 0.0227 (16) | 0.045 (2) | −0.0014 (15) | −0.0001 (17) | 0.0034 (15) |
C8 | 0.041 (2) | 0.0256 (17) | 0.047 (2) | −0.0013 (15) | 0.0015 (16) | −0.0024 (15) |
C9 | 0.055 (2) | 0.052 (2) | 0.048 (2) | 0.0108 (19) | −0.0044 (19) | −0.0060 (18) |
C10 | 0.113 (4) | 0.073 (3) | 0.075 (3) | −0.001 (3) | 0.011 (3) | 0.008 (3) |
C11 | 0.084 (3) | 0.089 (4) | 0.067 (3) | −0.001 (3) | −0.022 (3) | −0.028 (3) |
C21 | 0.051 (2) | 0.0314 (19) | 0.064 (3) | −0.0102 (17) | −0.001 (2) | −0.0069 (18) |
C22 | 0.056 (3) | 0.041 (2) | 0.062 (3) | −0.0069 (19) | 0.002 (2) | −0.0155 (19) |
C23 | 0.053 (3) | 0.044 (2) | 0.086 (3) | −0.0009 (19) | 0.002 (2) | −0.010 (2) |
C24 | 0.059 (3) | 0.058 (3) | 0.068 (3) | −0.002 (2) | −0.003 (2) | 0.000 (2) |
C25 | 0.072 (3) | 0.063 (3) | 0.064 (3) | −0.004 (2) | 0.006 (2) | −0.015 (2) |
C26 | 0.054 (3) | 0.047 (2) | 0.083 (3) | −0.0017 (19) | 0.005 (2) | −0.019 (2) |
C27 | 0.058 (2) | 0.0196 (16) | 0.052 (2) | −0.0057 (16) | 0.0008 (18) | −0.0046 (16) |
C28 | 0.051 (2) | 0.0263 (18) | 0.048 (2) | 0.0024 (16) | 0.0053 (18) | 0.0054 (15) |
C29 | 0.060 (3) | 0.042 (2) | 0.075 (3) | −0.003 (2) | 0.003 (2) | 0.025 (2) |
C30 | 0.125 (5) | 0.094 (4) | 0.077 (4) | −0.005 (4) | −0.001 (3) | 0.015 (3) |
C31 | 0.080 (3) | 0.056 (3) | 0.129 (5) | 0.010 (3) | −0.004 (3) | 0.041 (3) |
C51 | 0.073 (3) | 0.038 (2) | 0.061 (3) | −0.003 (2) | −0.009 (2) | 0.008 (2) |
O50 | 0.096 (2) | 0.0474 (16) | 0.0554 (19) | −0.0021 (15) | −0.0098 (16) | 0.0012 (14) |
N50 | 0.069 (6) | 0.047 (11) | 0.075 (6) | 0.003 (8) | 0.017 (6) | 0.000 (6) |
C52 | 0.066 (6) | 0.067 (7) | 0.114 (10) | 0.027 (5) | 0.025 (6) | 0.023 (8) |
C53 | 0.132 (15) | 0.119 (11) | 0.092 (11) | 0.000 (12) | 0.025 (10) | 0.017 (9) |
N50A | 0.12 (2) | 0.033 (9) | 0.091 (15) | −0.015 (14) | 0.026 (12) | −0.017 (12) |
C52A | 0.127 (19) | 0.098 (19) | 0.20 (3) | 0.010 (15) | 0.04 (2) | −0.07 (2) |
C53A | 0.13 (2) | 0.059 (10) | 0.067 (11) | −0.007 (12) | 0.036 (12) | −0.019 (9) |
Ni—N4 | 1.859 (3) | C10—H101 | 0.9600 |
Ni—N22 | 1.861 (3) | C10—H102 | 0.9600 |
Ni—N2 | 1.866 (3) | C10—H103 | 0.9600 |
Ni—N24 | 1.869 (3) | C11—H111 | 0.9600 |
N1—C7 | 1.367 (4) | C11—H112 | 0.9600 |
N1—C1 | 1.411 (4) | C11—H113 | 0.9600 |
N1—H1 | 0.8600 | C21—C26 | 1.382 (5) |
N2—C7 | 1.293 (4) | C21—C22 | 1.380 (5) |
N2—H2 | 0.8600 | C22—C23 | 1.379 (5) |
N3—C7 | 1.357 (4) | C22—H220 | 0.9300 |
N3—C8 | 1.368 (4) | C23—C24 | 1.366 (6) |
N3—H3 | 0.8600 | C23—H230 | 0.9300 |
N4—C8 | 1.307 (4) | C24—C25 | 1.371 (6) |
N4—H4 | 0.8600 | C25—C26 | 1.372 (6) |
N5—C8 | 1.327 (4) | C25—H250 | 0.9300 |
N5—C9 | 1.460 (4) | C26—H260 | 0.9300 |
N5—H5 | 0.8600 | C29—C30 | 1.494 (6) |
N21—C27 | 1.351 (4) | C29—C31 | 1.530 (5) |
N21—C21 | 1.419 (5) | C29—H290 | 0.9800 |
N21—H21 | 0.8600 | C30—H301 | 0.9600 |
N22—C27 | 1.298 (4) | C30—H302 | 0.9600 |
N22—H22 | 0.8600 | C30—H303 | 0.9600 |
N23—C27 | 1.358 (4) | C31—H311 | 0.9600 |
N23—C28 | 1.370 (4) | C31—H312 | 0.9600 |
N23—H23 | 0.8600 | C31—H313 | 0.9600 |
N24—C28 | 1.299 (4) | C51—O50 | 1.207 (5) |
N24—H24 | 0.8600 | C51—N50A | 1.289 (13) |
N25—C28 | 1.345 (4) | C51—N50 | 1.309 (9) |
N25—C29 | 1.449 (5) | C51—H51 | 0.9300 |
N25—H25 | 0.8600 | N50—C52 | 1.430 (14) |
Cl4—C4 | 1.737 (4) | N50—C53 | 1.449 (12) |
Cl24—C24 | 1.732 (4) | C52—H52A | 0.9600 |
C1—C6 | 1.379 (5) | C52—H52B | 0.9600 |
C1—C2 | 1.377 (5) | C52—H52C | 0.9600 |
C2—C3 | 1.372 (5) | C53—H53A | 0.9600 |
C2—H20 | 0.9300 | C53—H53B | 0.9600 |
C3—C4 | 1.358 (5) | C53—H53C | 0.9600 |
C3—H30 | 0.9300 | N50A—C52A | 1.420 (17) |
C4—C5 | 1.366 (5) | N50A—C53A | 1.461 (16) |
C5—C6 | 1.379 (5) | C52A—H52D | 0.9600 |
C5—H50 | 0.9300 | C52A—H52E | 0.9600 |
C6—H60 | 0.9300 | C52A—H52F | 0.9600 |
C9—C10 | 1.483 (6) | C53A—H53D | 0.9600 |
C9—C11 | 1.503 (5) | C53A—H53E | 0.9600 |
C9—H90 | 0.9800 | C53A—H53F | 0.9600 |
N4—Ni—N22 | 177.55 (13) | C9—C11—H111 | 109.5 |
N4—Ni—N2 | 89.65 (12) | C9—C11—H112 | 109.5 |
N22—Ni—N2 | 90.53 (12) | H111—C11—H112 | 109.5 |
N4—Ni—N24 | 90.23 (12) | C9—C11—H113 | 109.5 |
N22—Ni—N24 | 89.58 (13) | H111—C11—H113 | 109.5 |
N2—Ni—N24 | 179.79 (13) | H112—C11—H113 | 109.5 |
C7—N1—C1 | 121.8 (3) | C26—C21—C22 | 119.1 (4) |
C7—N1—H1 | 119.1 | C26—C21—N21 | 119.4 (4) |
C1—N1—H1 | 119.1 | C22—C21—N21 | 121.5 (4) |
C7—N2—Ni | 130.0 (2) | C23—C22—C21 | 120.4 (4) |
C7—N2—H2 | 115.0 | C23—C22—H220 | 119.8 |
Ni—N2—H2 | 115.0 | C21—C22—H220 | 119.8 |
C7—N3—C8 | 126.5 (3) | C24—C23—C22 | 119.7 (4) |
C7—N3—H3 | 116.8 | C24—C23—H230 | 120.1 |
C8—N3—H3 | 116.8 | C22—C23—H230 | 120.1 |
C8—N4—Ni | 129.9 (2) | C23—C24—C25 | 120.4 (4) |
C8—N4—H4 | 115.0 | C23—C24—Cl24 | 120.3 (4) |
Ni—N4—H4 | 115.0 | C25—C24—Cl24 | 119.3 (4) |
C8—N5—C9 | 124.4 (3) | C24—C25—C26 | 120.1 (4) |
C8—N5—H5 | 117.8 | C24—C25—H250 | 120.0 |
C9—N5—H5 | 117.8 | C26—C25—H250 | 120.0 |
C27—N21—C21 | 123.8 (3) | C25—C26—C21 | 120.2 (4) |
C27—N21—H21 | 118.1 | C25—C26—H260 | 119.9 |
C21—N21—H21 | 118.1 | C21—C26—H260 | 119.9 |
C27—N22—Ni | 128.5 (3) | N22—C27—N21 | 125.1 (3) |
C27—N22—H22 | 115.7 | N22—C27—N23 | 121.1 (3) |
Ni—N22—H22 | 115.7 | N21—C27—N23 | 113.8 (3) |
C27—N23—C28 | 125.9 (3) | N24—C28—N25 | 125.6 (3) |
C27—N23—H23 | 117.1 | N24—C28—N23 | 120.1 (3) |
C28—N23—H23 | 117.1 | N25—C28—N23 | 114.3 (3) |
C28—N24—Ni | 128.6 (3) | N25—C29—C30 | 111.6 (4) |
C28—N24—H24 | 115.7 | N25—C29—C31 | 107.5 (4) |
Ni—N24—H24 | 115.7 | C30—C29—C31 | 113.1 (4) |
C28—N25—C29 | 124.4 (3) | N25—C29—H290 | 108.2 |
C28—N25—H25 | 117.8 | C30—C29—H290 | 108.2 |
C29—N25—H25 | 117.8 | C31—C29—H290 | 108.2 |
C6—C1—C2 | 119.7 (3) | C29—C30—H301 | 109.5 |
C6—C1—N1 | 120.2 (3) | C29—C30—H302 | 109.5 |
C2—C1—N1 | 120.2 (3) | H301—C30—H302 | 109.5 |
C3—C2—C1 | 119.8 (4) | C29—C30—H303 | 109.5 |
C3—C2—H20 | 120.1 | H301—C30—H303 | 109.5 |
C1—C2—H20 | 120.1 | H302—C30—H303 | 109.5 |
C4—C3—C2 | 120.0 (4) | C29—C31—H311 | 109.5 |
C4—C3—H30 | 120.0 | C29—C31—H312 | 109.5 |
C2—C3—H30 | 120.0 | H311—C31—H312 | 109.5 |
C3—C4—C5 | 121.2 (4) | C29—C31—H313 | 109.5 |
C3—C4—Cl4 | 119.7 (3) | H311—C31—H313 | 109.5 |
C5—C4—Cl4 | 119.1 (3) | H312—C31—H313 | 109.5 |
C4—C5—C6 | 119.1 (4) | O50—C51—N50A | 135.5 (12) |
C4—C5—H50 | 120.4 | O50—C51—N50 | 121.3 (8) |
C6—C5—H50 | 120.4 | N50A—C51—N50 | 17 (2) |
C1—C6—C5 | 120.1 (4) | O50—C51—H51 | 119.4 |
C1—C6—H60 | 120.0 | N50A—C51—H51 | 104.5 |
C5—C6—H60 | 120.0 | N50—C51—H51 | 119.4 |
N2—C7—N3 | 121.6 (3) | C51—N50—C52 | 120.3 (12) |
N2—C7—N1 | 124.2 (3) | C51—N50—C53 | 124.1 (12) |
N3—C7—N1 | 114.2 (3) | C52—N50—C53 | 114.5 (10) |
N4—C8—N5 | 125.3 (3) | C51—N50A—C52A | 124.2 (18) |
N4—C8—N3 | 120.1 (3) | C51—N50A—C53A | 122.9 (18) |
N5—C8—N3 | 114.5 (3) | C52A—N50A—C53A | 112.1 (15) |
N5—C9—C10 | 112.6 (3) | N50A—C52A—H52D | 109.5 |
N5—C9—C11 | 107.3 (3) | N50A—C52A—H52E | 109.5 |
C10—C9—C11 | 112.8 (4) | H52D—C52A—H52E | 109.5 |
N5—C9—H90 | 108.0 | N50A—C52A—H52F | 109.5 |
C10—C9—H90 | 108.0 | H52D—C52A—H52F | 109.5 |
C11—C9—H90 | 108.0 | H52E—C52A—H52F | 109.5 |
C9—C10—H101 | 109.5 | N50A—C53A—H53D | 109.5 |
C9—C10—H102 | 109.5 | N50A—C53A—H53E | 109.5 |
H101—C10—H102 | 109.5 | H53D—C53A—H53E | 109.5 |
C9—C10—H103 | 109.5 | N50A—C53A—H53F | 109.5 |
H101—C10—H103 | 109.5 | H53D—C53A—H53F | 109.5 |
H102—C10—H103 | 109.5 | H53E—C53A—H53F | 109.5 |
C1—N1—C7—N2 | −4.5 (5) | C21—N21—C27—N22 | −3.3 (6) |
C9—N5—C8—N4 | 16.9 (6) | C29—N25—C28—N24 | −13.0 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl2 | 0.86 | 2.54 | 3.184 (3) | 133 |
N2—H2···O50 | 0.86 | 2.19 | 2.981 (4) | 153 |
N3—H3···Cl1 | 0.86 | 2.39 | 3.212 (3) | 161 |
N4—H4···Cl2i | 0.86 | 2.54 | 3.394 (3) | 170 |
N5—H5···Cl1 | 0.86 | 2.48 | 3.253 (3) | 149 |
N21—H21···Cl1ii | 0.86 | 2.36 | 3.138 (3) | 151 |
N22—H22···O50 | 0.86 | 2.13 | 2.957 (4) | 160 |
N23—H23···Cl2ii | 0.86 | 2.62 | 3.358 (3) | 145 |
N24—H24···Cl2i | 0.86 | 2.61 | 3.454 (3) | 169 |
N25—H25···Cl2ii | 0.86 | 2.67 | 3.213 (3) | 123 |
N2—H2···O50 | 0.86 | 2.19 | 2.981 (4) | 153 |
N22—H22···O50 | 0.86 | 2.13 | 2.957 (4) | 160 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C11H16ClN5)2]Cl2·C3H7NO |
Mr | 710.18 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 293 |
a, b, c (Å) | 10.824 (5), 24.12 (1), 13.180 (3) |
β (°) | 95.42 (3) |
V (Å3) | 3426 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.92 |
Crystal size (mm) | 0.45 × 0.37 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) 'multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995)' |
Tmin, Tmax | 0.648, 0.883 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11970, 6000, 3270 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.110, 0.96 |
No. of reflections | 6000 |
No. of parameters | 417 |
No. of restraints | 31 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.69 |
Computer programs: CAD-4 EXPRESS (Enraf Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1996), WinGX (Farrugia, 1999).
Ni—N4 | 1.859 (3) | N4—C8 | 1.307 (4) |
Ni—N22 | 1.861 (3) | N5—C8 | 1.327 (4) |
Ni—N2 | 1.866 (3) | N21—C27 | 1.351 (4) |
Ni—N24 | 1.869 (3) | N23—C27 | 1.358 (4) |
N1—C7 | 1.367 (4) | N23—C28 | 1.370 (4) |
N2—C7 | 1.293 (4) | N24—C28 | 1.299 (4) |
N3—C7 | 1.357 (4) | N25—C28 | 1.345 (4) |
N3—C8 | 1.368 (4) | ||
N4—Ni—N22 | 177.55 (13) | N2—C7—N1 | 124.2 (3) |
N4—Ni—N2 | 89.65 (12) | N3—C7—N1 | 114.2 (3) |
N22—Ni—N2 | 90.53 (12) | N4—C8—N5 | 125.3 (3) |
N4—Ni—N24 | 90.23 (12) | N4—C8—N3 | 120.1 (3) |
N22—Ni—N24 | 89.58 (13) | N5—C8—N3 | 114.5 (3) |
N2—Ni—N24 | 179.79 (13) | N22—C27—N21 | 125.1 (3) |
C7—N2—Ni | 130.0 (2) | N22—C27—N23 | 121.1 (3) |
C7—N3—C8 | 126.5 (3) | N21—C27—N23 | 113.8 (3) |
C8—N4—Ni | 129.9 (2) | N24—C28—N25 | 125.6 (3) |
C27—N22—Ni | 128.5 (3) | N24—C28—N23 | 120.1 (3) |
C28—N24—Ni | 128.6 (3) | N25—C28—N23 | 114.3 (3) |
N2—C7—N3 | 121.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl2 | 0.86 | 2.54 | 3.184 (3) | 132.5 |
N2—H2···O50 | 0.86 | 2.19 | 2.981 (4) | 153.4 |
N3—H3···Cl1 | 0.86 | 2.39 | 3.212 (3) | 160.5 |
N4—H4···Cl2i | 0.86 | 2.54 | 3.394 (3) | 169.8 |
N5—H5···Cl1 | 0.86 | 2.48 | 3.253 (3) | 149.2 |
N21—H21···Cl1ii | 0.86 | 2.36 | 3.138 (3) | 150.5 |
N22—H22···O50 | 0.86 | 2.13 | 2.957 (4) | 160.1 |
N23—H23···Cl2ii | 0.86 | 2.62 | 3.358 (3) | 144.6 |
N24—H24···Cl2i | 0.86 | 2.61 | 3.454 (3) | 168.6 |
N25—H25···Cl2ii | 0.86 | 2.67 | 3.213 (3) | 122.7 |
N2—H2···O50 | 0.86 | 2.19 | 2.981 (4) | 153.4 |
N22—H22···O50 | 0.86 | 2.13 | 2.957 (4) | 160.1 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, y+1/2, −z. |
Proguanil, 1-(p-chlorophenyl)-5-isopropylbiguanide, an antimalarial drug used worldwide, is characterized by different tautomeric forms, one of which is stabilized upon complexation. This fact prompted us to synthesize new complexes of 3 d elements with a view to modulating the pharmacological properties of the free ligand. The asymmetric unit of the title compound, (I), consists of one nickel(II) atom, two proguanil ligands, two Cl−anions and one DMF solvent molecule. The NiII atom exhibits a square-planar coordination, built from two bidentate chelating proguanil ligands via atoms N2 and N4 in the first ligand (atoms N22 and N24 in the second ligand) from the biguanidyl moiety of each molecule. The same square-planar geometry was observed in [bis(2- guanidinobenzimidazole)nickel(II) dinitrate] (Barba-Behrens et al., 1996) and [bis(biguanidino)nickelate(II):(6,7-dimethoxy-2,4(1H, 3H)quinazolinedione](Bishop et al., 2002). The Ni—N bond lengths are all equivalent [within 2 s.u.; mean 1.864 (3) Å] and the angles at the Ni atom are in the range 89.6 (1)–90.5 (1) °. These values agree with those found in bis(N,N-dimethylbiguanide)nickel(II) salicylate (Lemoine et al., 1996) and bis(N,N-dimethylbiguanide)nickel(II)monohydroxide chloride (Lemoine et al., 1999). The Ni atom is 0.021 (2) Å out of the basal plane [P1; N2/N4/N22/N24]. The N2—C7—N3—C8—N4 and N22—C27—N23—C28—N24 sequences have nearly planar geometries (mean planes P2 and P3, respectively), allowing delocalization of the π electron system along them. The NiII atom is displaced 0.244 (4) and −0.459 (4) Å out of planes P2 and P3 and the dihedral angle between these two planes is 32.05 (1)°. The Ni/N2/C7/N3/C8/N4 metalloring may be regarded as having a boat shape, with atoms Ni and N3 on the same side of the N2/C7/C8/N4 (P4) plane [0.234 (5) and 0.018 (5) Å, respectively]. The geometry is the same for the Ni/N22/C27/N23/C28/N24 ring, with atoms Ni and N23 being −0.380 (5) and −0.145 (5) Å, respectively, from plane P5 (N22/C27/C28/N24). These configurations are similar to those described for [bis(2- guanidinobenzimidazole)nickel(II) dinitrate] (Barba-Behrens et al., 1996) The dihedral angle between plane P2 and its attached phenyl ring (C1–C6) is 70.0 (1) ° [the corresponding dihedral angle for P3 and C21–C26 is 76.3 (1)°]. The two halves of each biguanide group are planar, with atom C7 0.011 (4)° out of plane P6 (N1/N2/N3) and atom C8 0.001 (4) Å out of plane P7 (N3/N4/N5) [the corresponding out of plane distance values are 0.002 (4) Å for atom C27 and plane P8 (N21/N22/N23) and 0.011 (4) Å for atom C28 and plane P9 (N23/N24/N25)]. The dihedral angle between planes P6 and P7 is 5.9 (3)° and between planes P8 and P9 is 15.0 (3)°. Thus, the biguanide moiety in each proguanil bidentate chelating agent is almost planar. In contrast, the corresponding dihedral angle between the homologous Ni atoms in the crystal structure of 1-(p-chlorophenyl)-5-isopropylbiguanide hydrochloride (Brown., 1967) is 58.9 °, a value which is characteristic of a non-planar molecule. In the title compound, the corresponding distances in the two proguanil ligands are all equivalent (within 3 s.u.) except for the C9—C11 [1.503 (5) Å] and C29—C31 [1.530 (5) Å] distances in the terminal methyl groups. The C1—N1—C7—N2 [−4.5 (5) °] and C9—N5—C8—N4 [17.0 (6) °] torsion angles in the first ligand, and C21—N21—C27—N22 [−3.3 (7) °] and C29—N25—C28—N24 [−13.0 (6)°] torsion angles in the second proguanil ligand, showed that this conformation remains synperiplanar upon metallation. The same conformation was found for the corresponding atomic set in PdCl2(proguanil) (Bentefrit et al., 2002) but differed from (proguanil) hydrochloride (Brown, 1967) where the conformation was antiperiplanar (the C—N—C—N torsion angles being 164.1 and 164.5°). The DMF solvent molecule exhibits some disorder in the terminal methyl groups, as shown by its Ueq values. The crystal packing is characterized by several intra- and intermolecular hydrogen bonds, which involve, in particular, the DMF solvate molecule with each ligand of the same complex (table), in contrast to hydrogen bonds observed in [bis(biguanidino)nickelate(II):(6,7-dimethoxy-2,4(1H,3H)quinazolinedione], in which the DMSO solvate acts as a bridging molecule between two neighbouring complexes (Bishop et al., 2002). In (I), atom Cl1 participates in three hydrogen bonds to two chelate entities, while atom Cl2 is involved in five hydrogen bonds belonging to three different complexes.
In addition, the crystalline cohesion is likewise ensured by many van der Waals contacts, the shortest being C26—C52iii = 3.41 (2) Å [symmetry code: (iii) 1/2 + x, 1/2 − y, z].