Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805041322/cf6478sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805041322/cf6478Isup2.hkl |
CCDC reference: 296733
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.006 Å
- R factor = 0.031
- wR factor = 0.031
- Data-to-parameter ratio = 13.0
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for O2 - C2 .. 7.04 su
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ru1 - C2 .. 9.55 su PLAT431_ALERT_2_C Short Inter HL..A Contact Br12 .. O2 .. 3.36 Ang. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 14
Alert level G
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion
Ru3(CO)12 (200 mg, 0.31 mmol) was added to a solution of 4,4'-dibromoazobenzene (210 mg, 0.62 mmol) in n-octane (30 ml), and the mixture heated at reflux for 4 h. The resulting brown solution was taken to dryness on a rotary evaporator, and the residue dissolved in a minimum of CH2Cl2 (ca 3 ml) and applied to preparative thin-layer chromatography plates. Elution with CH2Cl2/petrol ether (1:9 v/v) gave four bands and a heavy baseline: band 1 was yellow (RF =)/4; band 2 was orange (RF = 0.52); band 3 was yellow (RF = 0.21); band 4 (RF = 0.10) was yellow. The contents of band 3 were identified as Ru(CO)2(C12H7Br2N2)2, (I) (10 mg, 4%). IR (CH2Cl2): ν(CO) 2039 s, 1991 s cm−1. Crystals were obtained by liquid diffusion of methanol into a dichloromethane solution.
H atoms were included at idealized positions and made to ride on their parent atoms, with C—H = 1.00 Å and Uiso(H) = 1.2Ueq(C).
Data collection: COLLECT (Nonius, 1997); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEPII (Johnson, 1976) in TEXSAN (Molecular Structure Corporation, 1997); software used to prepare material for publication: CRYSTALS.
Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. H atoms have been omitted for clarity. |
[Ru(C12H7Br2N2)2(CO)2] | Z = 2 |
Mr = 835.11 | F(000) = 796 |
Triclinic, P1 | Dx = 2.065 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.7137 (4) Å | Cell parameters from 28902 reflections |
b = 11.5618 (4) Å | θ = 3–27° |
c = 11.7896 (5) Å | µ = 6.57 mm−1 |
α = 78.7678 (19)° | T = 200 K |
β = 73.2924 (18)° | Block, red |
γ = 75.651 (2)° | 0.45 × 0.31 × 0.26 mm |
V = 1343.03 (9) Å3 |
Nonius KappaCCD diffractometer | 4348 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.05 |
ϕ and ω scans | θmax = 27.5°, θmin = 3.4° |
Absorption correction: integration Gaussian (Coppens, 1970) implemented in maXus (Mackay et al., 2000) | h = −13→13 |
Tmin = 0.171, Tmax = 0.295 | k = −14→14 |
28902 measured reflections | l = −15→15 |
6138 independent reflections |
Refinement on F | 0 restraints |
R[F2 > 2σ(F2)] = 0.031 | w = [1-(Fo-Fc)2/36σ2(F)]2/[3.3T0(x)-2.25T1(x) + 2.27T2(x)]
where Ti are Chebychev polynomials and x = Fc/Fmax (Prince, 1982; Watkin, 1994) |
wR(F2) = 0.031 | (Δ/σ)max = 0.001 |
S = 1.16 | Δρmax = 0.58 e Å−3 |
4348 reflections | Δρmin = −1.19 e Å−3 |
334 parameters |
[Ru(C12H7Br2N2)2(CO)2] | γ = 75.651 (2)° |
Mr = 835.11 | V = 1343.03 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.7137 (4) Å | Mo Kα radiation |
b = 11.5618 (4) Å | µ = 6.57 mm−1 |
c = 11.7896 (5) Å | T = 200 K |
α = 78.7678 (19)° | 0.45 × 0.31 × 0.26 mm |
β = 73.2924 (18)° |
Nonius KappaCCD diffractometer | 6138 independent reflections |
Absorption correction: integration Gaussian (Coppens, 1970) implemented in maXus (Mackay et al., 2000) | 4348 reflections with I > 3σ(I) |
Tmin = 0.171, Tmax = 0.295 | Rint = 0.05 |
28902 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 334 parameters |
wR(F2) = 0.031 | 0 restraints |
S = 1.16 | Δρmax = 0.58 e Å−3 |
4348 reflections | Δρmin = −1.19 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Ru1 | 0.67742 (3) | 0.31200 (3) | 0.68806 (2) | 0.0307 | |
Br11 | 0.94256 (4) | −0.17701 (4) | 0.89028 (4) | 0.0468 | |
Br12 | 0.84081 (6) | 0.93605 (4) | 0.49733 (4) | 0.0637 | |
Br21 | 0.41773 (6) | −0.08671 (5) | 0.67631 (4) | 0.0687 | |
Br22 | 0.83628 (5) | 0.57873 (4) | 1.14751 (5) | 0.0588 | |
O1 | 0.4507 (3) | 0.5171 (3) | 0.6302 (3) | 0.0635 | |
O2 | 0.7609 (3) | 0.2375 (3) | 0.4407 (2) | 0.0501 | |
N11 | 0.8393 (3) | 0.4043 (3) | 0.6639 (2) | 0.0337 | |
N12 | 0.9397 (3) | 0.3465 (3) | 0.7044 (3) | 0.0359 | |
N21 | 0.6066 (3) | 0.3237 (3) | 0.8751 (2) | 0.0323 | |
N22 | 0.5288 (3) | 0.2561 (3) | 0.9385 (3) | 0.0351 | |
C1 | 0.5371 (4) | 0.4433 (4) | 0.6502 (3) | 0.0405 | |
C2 | 0.7322 (4) | 0.2680 (3) | 0.5334 (3) | 0.0373 | |
C111 | 0.9338 (3) | 0.2256 (3) | 0.7496 (3) | 0.0338 | |
C112 | 0.8273 (3) | 0.1779 (3) | 0.7438 (3) | 0.0315 | |
C113 | 0.8321 (3) | 0.0557 (3) | 0.7856 (3) | 0.0350 | |
C114 | 0.9377 (4) | −0.0108 (3) | 0.8316 (3) | 0.0358 | |
C115 | 1.0397 (4) | 0.0377 (4) | 0.8395 (3) | 0.0399 | |
C116 | 1.0391 (4) | 0.1576 (4) | 0.7969 (3) | 0.0403 | |
C121 | 0.8457 (4) | 0.5282 (3) | 0.6187 (3) | 0.0342 | |
C122 | 0.7731 (4) | 0.5905 (4) | 0.5378 (3) | 0.0412 | |
C123 | 0.7720 (4) | 0.7121 (4) | 0.4991 (4) | 0.0475 | |
C124 | 0.8441 (4) | 0.7693 (4) | 0.5424 (4) | 0.0462 | |
C125 | 0.9193 (4) | 0.7076 (4) | 0.6209 (4) | 0.0458 | |
C126 | 0.9204 (4) | 0.5865 (4) | 0.6599 (3) | 0.0426 | |
C211 | 0.4933 (3) | 0.1876 (3) | 0.8720 (3) | 0.0333 | |
C212 | 0.5495 (3) | 0.1959 (3) | 0.7471 (3) | 0.0341 | |
C213 | 0.5191 (4) | 0.1146 (4) | 0.6888 (3) | 0.0401 | |
C214 | 0.4400 (4) | 0.0328 (4) | 0.7542 (4) | 0.0428 | |
C215 | 0.3811 (4) | 0.0311 (4) | 0.8764 (4) | 0.0435 | |
C216 | 0.4087 (4) | 0.1102 (4) | 0.9350 (3) | 0.0394 | |
C221 | 0.6547 (3) | 0.3861 (3) | 0.9430 (3) | 0.0331 | |
C222 | 0.6753 (4) | 0.5018 (3) | 0.8983 (3) | 0.0361 | |
C223 | 0.7273 (4) | 0.5607 (3) | 0.9595 (3) | 0.0386 | |
C224 | 0.7586 (4) | 0.5019 (3) | 1.0650 (3) | 0.0400 | |
C225 | 0.7350 (4) | 0.3873 (4) | 1.1122 (4) | 0.0423 | |
C226 | 0.6832 (4) | 0.3289 (3) | 1.0502 (3) | 0.0393 | |
H1131 | 0.7601 | 0.0164 | 0.7824 | 0.0423* | |
H1151 | 1.1127 | −0.0130 | 0.8754 | 0.0487* | |
H1161 | 1.1125 | 0.1952 | 0.7998 | 0.0500* | |
H1221 | 0.7214 | 0.5479 | 0.5071 | 0.0493* | |
H1231 | 0.7197 | 0.7576 | 0.4407 | 0.0562* | |
H1251 | 0.9728 | 0.7501 | 0.6496 | 0.0561* | |
H1261 | 0.9743 | 0.5411 | 0.7171 | 0.0522* | |
H2131 | 0.5543 | 0.1158 | 0.6004 | 0.0500* | |
H2151 | 0.3209 | −0.0258 | 0.9200 | 0.0535* | |
H2161 | 0.3679 | 0.1118 | 1.0225 | 0.0476* | |
H2221 | 0.6525 | 0.5426 | 0.8217 | 0.0424* | |
H2231 | 0.7421 | 0.6444 | 0.9283 | 0.0461* | |
H2251 | 0.7551 | 0.3475 | 1.1900 | 0.0525* | |
H2261 | 0.6664 | 0.2460 | 1.0824 | 0.0479* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.03043 (14) | 0.03521 (15) | 0.02729 (13) | −0.00611 (11) | −0.00828 (10) | −0.00553 (10) |
Br11 | 0.0491 (2) | 0.0380 (2) | 0.0526 (2) | −0.00548 (17) | −0.01661 (18) | −0.00276 (17) |
Br12 | 0.0886 (4) | 0.0387 (2) | 0.0557 (3) | −0.0156 (2) | −0.0047 (2) | −0.00408 (19) |
Br21 | 0.0888 (4) | 0.0820 (3) | 0.0547 (3) | −0.0485 (3) | −0.0186 (3) | −0.0141 (2) |
Br22 | 0.0705 (3) | 0.0554 (3) | 0.0684 (3) | −0.0179 (2) | −0.0367 (2) | −0.0146 (2) |
O1 | 0.0559 (19) | 0.071 (2) | 0.0485 (17) | 0.0155 (17) | −0.0164 (15) | −0.0036 (15) |
O2 | 0.0621 (18) | 0.0567 (17) | 0.0339 (14) | −0.0135 (14) | −0.0075 (13) | −0.0166 (13) |
N11 | 0.0353 (15) | 0.0363 (15) | 0.0296 (14) | −0.0070 (12) | −0.0062 (12) | −0.0075 (12) |
N12 | 0.0339 (15) | 0.0395 (16) | 0.0355 (15) | −0.0078 (12) | −0.0079 (12) | −0.0083 (12) |
N21 | 0.0311 (14) | 0.0351 (15) | 0.0307 (14) | −0.0036 (12) | −0.0082 (11) | −0.0080 (12) |
N22 | 0.0328 (15) | 0.0390 (16) | 0.0329 (15) | −0.0055 (12) | −0.0066 (12) | −0.0082 (12) |
C1 | 0.043 (2) | 0.047 (2) | 0.0299 (17) | −0.0056 (17) | −0.0098 (15) | −0.0053 (15) |
C2 | 0.0350 (18) | 0.0347 (18) | 0.042 (2) | −0.0094 (14) | −0.0097 (15) | −0.0002 (15) |
C111 | 0.0330 (17) | 0.0371 (18) | 0.0312 (17) | −0.0064 (14) | −0.0065 (14) | −0.0074 (14) |
C112 | 0.0293 (16) | 0.0395 (18) | 0.0271 (16) | −0.0064 (14) | −0.0063 (13) | −0.0095 (14) |
C113 | 0.0358 (19) | 0.0382 (19) | 0.0317 (17) | −0.0069 (15) | −0.0092 (14) | −0.0060 (14) |
C114 | 0.0377 (19) | 0.0353 (18) | 0.0321 (17) | −0.0053 (15) | −0.0078 (14) | −0.0033 (14) |
C115 | 0.0340 (18) | 0.045 (2) | 0.042 (2) | −0.0051 (15) | −0.0140 (15) | −0.0074 (16) |
C116 | 0.0354 (19) | 0.045 (2) | 0.044 (2) | −0.0088 (16) | −0.0137 (16) | −0.0090 (16) |
C121 | 0.0375 (18) | 0.0340 (17) | 0.0305 (17) | −0.0090 (14) | −0.0048 (14) | −0.0063 (13) |
C122 | 0.045 (2) | 0.045 (2) | 0.0338 (18) | −0.0110 (17) | −0.0098 (16) | −0.0017 (16) |
C123 | 0.055 (2) | 0.045 (2) | 0.041 (2) | −0.0112 (18) | −0.0144 (18) | 0.0037 (17) |
C124 | 0.054 (2) | 0.041 (2) | 0.039 (2) | −0.0109 (18) | −0.0006 (17) | −0.0079 (16) |
C125 | 0.051 (2) | 0.044 (2) | 0.045 (2) | −0.0153 (18) | −0.0082 (18) | −0.0118 (17) |
C126 | 0.047 (2) | 0.044 (2) | 0.040 (2) | −0.0140 (17) | −0.0123 (17) | −0.0035 (16) |
C211 | 0.0283 (16) | 0.0382 (18) | 0.0338 (17) | −0.0047 (14) | −0.0094 (13) | −0.0059 (14) |
C212 | 0.0308 (17) | 0.0383 (18) | 0.0333 (17) | −0.0039 (14) | −0.0105 (14) | −0.0054 (14) |
C213 | 0.0370 (19) | 0.052 (2) | 0.0357 (18) | −0.0120 (17) | −0.0116 (15) | −0.0094 (16) |
C214 | 0.041 (2) | 0.054 (2) | 0.042 (2) | −0.0162 (17) | −0.0153 (16) | −0.0095 (17) |
C215 | 0.0370 (19) | 0.051 (2) | 0.045 (2) | −0.0167 (17) | −0.0128 (16) | −0.0007 (17) |
C216 | 0.0322 (18) | 0.051 (2) | 0.0357 (18) | −0.0101 (16) | −0.0079 (15) | −0.0067 (16) |
C221 | 0.0297 (16) | 0.0370 (18) | 0.0327 (17) | −0.0033 (14) | −0.0056 (14) | −0.0126 (14) |
C222 | 0.0368 (18) | 0.0374 (18) | 0.0319 (17) | −0.0027 (14) | −0.0078 (14) | −0.0069 (14) |
C223 | 0.0397 (19) | 0.0372 (19) | 0.0383 (19) | −0.0076 (15) | −0.0058 (15) | −0.0102 (15) |
C224 | 0.0375 (19) | 0.042 (2) | 0.044 (2) | −0.0056 (15) | −0.0123 (16) | −0.0141 (16) |
C225 | 0.048 (2) | 0.044 (2) | 0.0392 (19) | −0.0048 (17) | −0.0192 (17) | −0.0093 (16) |
C226 | 0.047 (2) | 0.0372 (18) | 0.0356 (18) | −0.0077 (16) | −0.0133 (16) | −0.0063 (15) |
Ru1—N11 | 2.178 (3) | C121—C126 | 1.397 (5) |
Ru1—N21 | 2.135 (3) | C122—C123 | 1.389 (6) |
Ru1—C1 | 1.938 (4) | C122—H1221 | 1.000 |
Ru1—C2 | 1.877 (4) | C123—C124 | 1.380 (6) |
Ru1—C112 | 2.096 (3) | C123—H1231 | 1.000 |
Ru1—C212 | 2.040 (4) | C124—C125 | 1.380 (6) |
Br11—C114 | 1.905 (4) | C125—C126 | 1.384 (6) |
Br12—C124 | 1.892 (4) | C125—H1251 | 1.000 |
Br21—C214 | 1.896 (4) | C126—H1261 | 1.000 |
Br22—C224 | 1.897 (4) | C211—C212 | 1.416 (5) |
O1—C1 | 1.138 (5) | C211—C216 | 1.390 (5) |
O2—C2 | 1.148 (5) | C212—C213 | 1.412 (5) |
N11—N12 | 1.283 (4) | C213—C214 | 1.394 (5) |
N11—C121 | 1.439 (5) | C213—H2131 | 1.000 |
N12—C111 | 1.406 (5) | C214—C215 | 1.395 (6) |
N21—N22 | 1.265 (4) | C215—C216 | 1.378 (5) |
N21—C221 | 1.440 (4) | C215—H2151 | 1.000 |
N22—C211 | 1.396 (5) | C216—H2161 | 1.000 |
C111—C112 | 1.408 (5) | C221—C222 | 1.386 (5) |
C111—C116 | 1.397 (5) | C221—C226 | 1.388 (5) |
C112—C113 | 1.396 (5) | C222—C223 | 1.382 (5) |
C113—C114 | 1.387 (5) | C222—H2221 | 1.000 |
C113—H1131 | 1.000 | C223—C224 | 1.384 (5) |
C114—C115 | 1.379 (5) | C223—H2231 | 1.000 |
C115—C116 | 1.378 (6) | C224—C225 | 1.388 (6) |
C115—H1151 | 1.000 | C225—C226 | 1.381 (5) |
C116—H1161 | 1.000 | C225—H2251 | 1.000 |
C121—C122 | 1.384 (5) | C226—H2261 | 1.000 |
Br12···O2i | 3.357 (3) | N12···C123v | 3.330 (5) |
Br21···O2ii | 3.566 (4) | N12···C124v | 3.425 (5) |
O1···O1iii | 3.016 (7) | N22···C223iv | 3.111 (4) |
O1···C1iii | 3.217 (5) | C111···C124v | 3.577 (5) |
O1···O2iii | 3.296 (4) | C215···C216vi | 3.511 (6) |
O1···C225iv | 3.339 (5) | C216···C216vi | 3.225 (8) |
O1···C2iii | 3.410 (5) | C221···C222iv | 3.543 (4) |
O2···C125v | 3.484 (6) | ||
N11—Ru1—N21 | 94.09 (11) | C122—C123—C124 | 119.1 (4) |
N11—Ru1—C1 | 102.07 (14) | C122—C123—H1231 | 120.427 |
N21—Ru1—C1 | 92.61 (13) | C124—C123—H1231 | 120.426 |
N11—Ru1—C2 | 95.27 (13) | Br12—C124—C123 | 120.9 (3) |
N21—Ru1—C2 | 167.61 (13) | Br12—C124—C125 | 117.8 (3) |
C1—Ru1—C2 | 93.36 (15) | C123—C124—C125 | 121.4 (4) |
N11—Ru1—C112 | 75.79 (12) | C124—C125—C126 | 119.7 (4) |
N21—Ru1—C112 | 82.40 (12) | C124—C125—H1251 | 120.156 |
C1—Ru1—C112 | 174.36 (14) | C126—C125—H1251 | 120.158 |
C2—Ru1—C112 | 92.04 (14) | C121—C126—C125 | 119.5 (4) |
N11—Ru1—C212 | 163.85 (12) | C121—C126—H1261 | 120.260 |
N21—Ru1—C212 | 76.44 (12) | C125—C126—H1261 | 120.259 |
C1—Ru1—C212 | 91.53 (15) | N22—C211—C212 | 119.1 (3) |
C2—Ru1—C212 | 92.55 (14) | N22—C211—C216 | 117.0 (3) |
C112—Ru1—C212 | 89.85 (13) | C212—C211—C216 | 123.9 (3) |
Ru1—N11—N12 | 117.7 (2) | C211—C212—Ru1 | 112.6 (2) |
Ru1—N11—C121 | 129.0 (2) | C211—C212—C213 | 115.3 (3) |
N12—N11—C121 | 113.0 (3) | Ru1—C212—C213 | 131.7 (3) |
N11—N12—C111 | 113.3 (3) | C212—C213—C214 | 120.2 (3) |
Ru1—N21—N22 | 118.5 (2) | C212—C213—H2131 | 119.924 |
Ru1—N21—C221 | 126.7 (2) | C214—C213—H2131 | 119.924 |
N22—N21—C221 | 114.0 (3) | Br21—C214—C213 | 118.9 (3) |
N21—N22—C211 | 113.3 (3) | Br21—C214—C215 | 118.0 (3) |
Ru1—C1—O1 | 177.0 (4) | C213—C214—C215 | 122.9 (4) |
Ru1—C2—O2 | 176.5 (3) | C214—C215—C216 | 117.8 (4) |
N12—C111—C112 | 120.3 (3) | C214—C215—H2151 | 121.085 |
N12—C111—C116 | 116.5 (3) | C216—C215—H2151 | 121.085 |
C112—C111—C116 | 123.2 (3) | C211—C216—C215 | 119.7 (3) |
C111—C112—Ru1 | 111.9 (2) | C211—C216—H2161 | 120.144 |
C111—C112—C113 | 116.7 (3) | C215—C216—H2161 | 120.137 |
Ru1—C112—C113 | 131.1 (3) | N21—C221—C222 | 119.2 (3) |
C112—C113—C114 | 119.4 (3) | N21—C221—C226 | 119.9 (3) |
C112—C113—H1131 | 120.300 | C222—C221—C226 | 120.9 (3) |
C114—C113—H1131 | 120.299 | C221—C222—C223 | 119.9 (3) |
Br11—C114—C113 | 119.2 (3) | C221—C222—H2221 | 120.044 |
Br11—C114—C115 | 117.4 (3) | C223—C222—H2221 | 120.044 |
C113—C114—C115 | 123.4 (3) | C222—C223—C224 | 118.8 (3) |
C114—C115—C116 | 118.6 (3) | C222—C223—H2231 | 120.591 |
C114—C115—H1151 | 120.709 | C224—C223—H2231 | 120.596 |
C116—C115—H1151 | 120.711 | Br22—C224—C223 | 119.5 (3) |
C111—C116—C115 | 118.7 (3) | Br22—C224—C225 | 118.8 (3) |
C111—C116—H1161 | 120.634 | C223—C224—C225 | 121.7 (3) |
C115—C116—H1161 | 120.634 | C224—C225—C226 | 119.1 (4) |
N11—C121—C122 | 119.5 (3) | C224—C225—H2251 | 120.461 |
N11—C121—C126 | 120.2 (3) | C226—C225—H2251 | 120.455 |
C122—C121—C126 | 120.2 (3) | C221—C226—C225 | 119.5 (4) |
C121—C122—C123 | 120.1 (4) | C221—C226—H2261 | 120.225 |
C121—C122—H1221 | 119.974 | C225—C226—H2261 | 120.227 |
C123—C122—H1221 | 119.972 | ||
Ru1—N11—N12—C111 | 5.6 (4) | N22—N21—Ru1—C212 | 3.4 (2) |
Ru1—N11—C121—C122 | −28.5 (4) | N22—N21—C221—C222 | −145.0 (3) |
Ru1—N11—C121—C126 | 148.9 (3) | N22—N21—C221—C226 | 36.7 (4) |
Ru1—N21—N22—C211 | −4.2 (4) | N22—C211—C212—C213 | 173.7 (3) |
Ru1—N21—C221—C222 | 45.9 (4) | N22—C211—C216—C215 | −173.2 (3) |
Ru1—N21—C221—C226 | −132.3 (3) | C1—Ru1—N11—C121 | −6.2 (3) |
Ru1—C112—C111—N12 | −8.8 (4) | C1—Ru1—N21—C221 | −97.0 (3) |
Ru1—C112—C111—C116 | 172.6 (3) | C1—Ru1—C212—C211 | −94.0 (2) |
Ru1—C112—C113—C114 | −171.7 (3) | C1—Ru1—C212—C213 | 93.8 (3) |
Ru1—C212—C211—N22 | 0.2 (4) | C2—Ru1—N11—C121 | 88.4 (3) |
Ru1—C212—C211—C216 | −176.5 (3) | C2—Ru1—C112—C111 | 103.0 (3) |
Ru1—C212—C213—C214 | 171.3 (3) | C2—Ru1—C112—C113 | −83.9 (3) |
Br11—C114—C113—C112 | 179.2 (2) | C2—Ru1—C212—C211 | 172.6 (2) |
Br11—C114—C115—C116 | 179.5 (3) | C2—Ru1—C212—C213 | 0.4 (3) |
Br12—C124—C123—C122 | −177.6 (3) | C111—N12—N11—C121 | 179.5 (3) |
Br12—C124—C125—C126 | 177.5 (3) | C111—C112—Ru1—C212 | −164.4 (3) |
Br21—C214—C213—C212 | −173.0 (3) | C111—C112—C113—C114 | 1.1 (5) |
Br21—C214—C215—C216 | 173.5 (3) | C111—C116—C115—C114 | 1.2 (5) |
Br22—C224—C223—C222 | 177.7 (3) | C112—Ru1—N11—C121 | 179.2 (3) |
Br22—C224—C225—C226 | −177.5 (3) | C112—Ru1—N21—C221 | 80.3 (3) |
N11—Ru1—N21—N22 | −163.4 (3) | C112—Ru1—C212—C211 | 80.6 (2) |
N11—Ru1—N21—C221 | 5.3 (3) | C112—Ru1—C212—C213 | −91.6 (3) |
N11—Ru1—C112—C111 | 8.1 (2) | C112—C111—C116—C115 | 0.4 (5) |
N11—Ru1—C112—C113 | −178.9 (4) | C112—C113—C114—C115 | 0.5 (5) |
N11—N12—C111—C112 | 2.2 (5) | C113—C112—Ru1—C212 | 8.6 (3) |
N11—N12—C111—C116 | −179.1 (3) | C113—C112—C111—C116 | −1.5 (5) |
N11—C121—C122—C123 | 176.1 (3) | C113—C114—C115—C116 | −1.7 (5) |
N11—C121—C126—C125 | −176.2 (3) | C121—C122—C123—C124 | 0.0 (5) |
N12—N11—Ru1—N21 | 73.1 (3) | C121—C126—C125—C124 | 0.3 (5) |
N12—N11—Ru1—C1 | 166.7 (3) | C122—C121—C126—C125 | 1.2 (5) |
N12—N11—Ru1—C2 | −98.7 (3) | C122—C123—C124—C125 | 1.5 (6) |
N12—N11—Ru1—C112 | −7.9 (2) | C123—C122—C121—C126 | −1.4 (5) |
N12—N11—C121—C122 | 158.3 (3) | C123—C124—C125—C126 | −1.7 (6) |
N12—N11—C121—C126 | −24.3 (4) | C211—N22—N21—C221 | −174.2 (3) |
N12—C111—C112—C113 | 177.1 (3) | C211—C212—C213—C214 | −0.7 (5) |
N12—C111—C116—C115 | −178.3 (3) | C211—C216—C215—C214 | −0.3 (6) |
N21—Ru1—N11—C121 | −99.7 (3) | C212—Ru1—N21—C221 | 172.0 (3) |
N21—Ru1—C112—C111 | −88.1 (3) | C212—C211—C216—C215 | 3.5 (5) |
N21—Ru1—C112—C113 | 85.0 (3) | C212—C213—C214—C215 | 3.9 (6) |
N21—Ru1—C212—C211 | −1.6 (2) | C213—C212—C211—C216 | −3.0 (5) |
N21—Ru1—C212—C213 | −173.8 (3) | C213—C214—C215—C216 | −3.4 (6) |
N21—N22—C211—C212 | 2.7 (4) | C221—C222—C223—C224 | 0.3 (5) |
N21—N22—C211—C216 | 179.6 (3) | C221—C226—C225—C224 | −0.6 (5) |
N21—C221—C222—C223 | −176.9 (3) | C222—C221—C226—C225 | −1.1 (5) |
N21—C221—C226—C225 | 177.1 (3) | C222—C223—C224—C225 | −2.1 (5) |
N22—N21—Ru1—C1 | 94.3 (3) | C223—C222—C221—C226 | 1.3 (5) |
N22—N21—Ru1—C112 | −88.3 (3) | C223—C224—C225—C226 | 2.2 (5) |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z+2; (v) −x+2, −y+1, −z+1; (vi) −x+1, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Ru(C12H7Br2N2)2(CO)2] |
Mr | 835.11 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 200 |
a, b, c (Å) | 10.7137 (4), 11.5618 (4), 11.7896 (5) |
α, β, γ (°) | 78.7678 (19), 73.2924 (18), 75.651 (2) |
V (Å3) | 1343.03 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 6.57 |
Crystal size (mm) | 0.45 × 0.31 × 0.26 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Integration Gaussian (Coppens, 1970) implemented in maXus (Mackay et al., 2000) |
Tmin, Tmax | 0.171, 0.295 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 28902, 6138, 4348 |
Rint | 0.05 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.031, 1.16 |
No. of reflections | 4348 |
No. of parameters | 334 |
Δρmax, Δρmin (e Å−3) | 0.58, −1.19 |
Computer programs: COLLECT (Nonius, 1997), DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), ORTEPII (Johnson, 1976) in TEXSAN (Molecular Structure Corporation, 1997), CRYSTALS.
Ru1—N11 | 2.178 (3) | Ru1—C2 | 1.877 (4) |
Ru1—N21 | 2.135 (3) | Ru1—C112 | 2.096 (3) |
Ru1—C1 | 1.938 (4) | Ru1—C212 | 2.040 (4) |
N11—Ru1—N21 | 94.09 (11) | C1—Ru1—C112 | 174.36 (14) |
N11—Ru1—C1 | 102.07 (14) | C2—Ru1—C112 | 92.04 (14) |
N21—Ru1—C1 | 92.61 (13) | N11—Ru1—C212 | 163.85 (12) |
N11—Ru1—C2 | 95.27 (13) | N21—Ru1—C212 | 76.44 (12) |
N21—Ru1—C2 | 167.61 (13) | C1—Ru1—C212 | 91.53 (15) |
C1—Ru1—C2 | 93.36 (15) | C2—Ru1—C212 | 92.55 (14) |
N11—Ru1—C112 | 75.79 (12) | C112—Ru1—C212 | 89.85 (13) |
N21—Ru1—C112 | 82.40 (12) |
The title compound, (I), has been prepared as a minor product of the reaction of Ru3(CO)12 and 4,4'-dibromoazobenzene in refluxing n-octane; the major product is the cluster complex Ru3(µ3-NC6H4Br)2(CO)9 (Willis et al., 2005). Two strong ν(CO) absorptions at 2039 and 1991 cm−1 in the IR spectrum of (I) are consistent with the presence of two mutually cis carbonyl groups. The crystal structure was investigated to ascertain the relative dispositions of the remaining C and N donor atoms of the two cyclometallated 4,4'-dibromoazobenzene ligands.
Complex (I) possesses a distorted octahedral coordination of the Ru atom and the X-ray study confirms the cis-disposed carbonyl ligands (Fig. 1). One N atom is trans to an aryl C, while the other N atom is trans to a carbonyl ligand, with the other aryl C trans to the remaining carbonyl ligand.
For ruthenium complexes of this type, i.e. with cis monodentate ligands and two N,C-cyclometallated ligands, three different arrangements of the cyclometallated donor atoms are possible. Compound (I) and the analogue containing azobenzene residues, Ru(C6H4N═NPh)2(CO)2 (II) (Bruce et al., 1987), adopt the same configuration; the only difference in Ru-containing bond lengths between the two structures is the Ru—N bond trans to the carbonyl ligand [2.135 (3) Å in (II) and 2.103 (6) Å in (I)].