Synthesis and mol­ecular structure of Cr(salen)(μ-N)RhCl(COD): the first example of a heterobimetallic nitride-bridged complex containing chromium

Five-coordinate Cr(N)(salen) {salen is 2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolate} reacts with [RhCl(COD)]₂ (COD is 1,5-cyclo­octa­diene) to yield the heterobimetallic nitride-bridged title compound, namely chlorido-2κCl-[2(η⁴)-1,5-cyclo­octa­diene]{2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato-1κ⁴O,N,N′,O′}-μ-nitrido-1:2κ²N:N-chromium(V)­rhodium(I), [CrRh(C₁₆H₁₄N₂O₂)ClN(C₈H₁₂)]. The Cr—N bond of 1.5936 (14) Å is elongated by only 0.035 Å compared to the terminal Cr—N bond in the precursor. The nitride bridge is close to being linear [173.03 (9)°] and the Rh—N bond of 1.9594 (14) Å is very short for a monodentate nitro­gen-donor ligand, indicating significant π-acceptor character of the Cr[triple bond]N group.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: COLLECT (Nonius, 1999); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

chlorido-2κCl-[2(η⁴)-1,5-cyclooctadiene]{2,2'-[ethane-1,2- diylbis(nitrilomethylidyne)]diphenolato- 1κ⁴O,N,N',O'}-µ-nitrido- 1:2κ²N:N-chromium(V)rhodium(I)

Crystal data

[CrRh(C16H14N2O2)ClN(C8H12)]	F(000) = 1172
Mr = 578.84	Dx = 1.667 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 34038 reflections
a = 12.6140 (13) Å	θ = 1.7–34.0°
b = 15.1085 (14) Å	µ = 1.33 mm^−1
c = 12.6704 (17) Å	T = 122 K
β = 107.259 (10)°	Prism, red
V = 2306.0 (4) Å^3	0.32 × 0.09 × 0.09 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	9382 independent reflections
Radiation source: fine-focus sealed tube	7611 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
ω and φ scans	θmax = 34.0°, θmin = 1.7°
Absorption correction: integration (Gaussian integration; Coppens, 1970)	h = −19→19
Tmin = 0.718, Tmax = 0.929	k = −23→23
77914 measured reflections	l = −19→19

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.067	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0224P)^2 + 2.474P] where P = (Fo^2 + 2Fc^2)/3
9382 reflections	(Δ/σ)max = 0.001
289 parameters	Δρmax = 0.92 e Å^−3
0 restraints	Δρmin = −0.98 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 6.1810 (0.0056) x + 13.0814 (0.0045) y + 0.6216 (0.0059) z = 1.8390 (0.0032)

* -0.0620 (0.0006) O1 * 0.0621 (0.0006) O2 * 0.0628 (0.0006) N2 * -0.0628 (0.0006) N3 0.4827 (0.0007) Cr1

Rms deviation of fitted atoms = 0.0624

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
Rh1	0.210064 (10)	0.544803 (8)	0.061385 (10)	0.01420 (3)
Cr1	0.35702 (2)	0.341441 (16)	0.099525 (19)	0.01091 (5)
Cl1	0.14529 (4)	0.51896 (4)	−0.13119 (4)	0.03189 (11)
N1	0.29689 (11)	0.43536 (9)	0.07862 (11)	0.0156 (2)
N2	0.32628 (11)	0.30229 (9)	−0.05763 (10)	0.0140 (2)
N3	0.50408 (11)	0.37031 (9)	0.07654 (11)	0.0150 (2)
O1	0.25988 (10)	0.25289 (8)	0.12085 (9)	0.0161 (2)
O2	0.42958 (9)	0.33620 (8)	0.25453 (9)	0.0151 (2)
C1	0.07706 (15)	0.63726 (12)	0.06440 (18)	0.0269 (4)
H1	0.0062	0.6286	0.0037	0.032*
C2	0.06342 (17)	0.64628 (13)	0.1791 (2)	0.0305 (4)
H2A	−0.0165	0.6437	0.1734	0.037*
H2B	0.0920	0.7047	0.2102	0.037*
C3	0.12487 (16)	0.57354 (13)	0.25749 (17)	0.0254 (4)
H3A	0.1460	0.5964	0.3342	0.031*
H3B	0.0739	0.5229	0.2532	0.031*
C4	0.22799 (14)	0.54118 (11)	0.23201 (13)	0.0173 (3)
H4	0.2570	0.4836	0.2681	0.021*
C5	0.31043 (14)	0.59651 (11)	0.21307 (14)	0.0185 (3)
H5	0.3868	0.5707	0.2381	0.022*
C6	0.30788 (17)	0.69704 (13)	0.22029 (19)	0.0303 (4)
H6A	0.3851	0.7195	0.2438	0.036*
H6B	0.2728	0.7140	0.2776	0.036*
C7	0.24431 (17)	0.74162 (13)	0.1105 (2)	0.0335 (5)
H7A	0.2064	0.7950	0.1268	0.040*
H7B	0.2983	0.7612	0.0724	0.040*
C8	0.15901 (16)	0.68242 (13)	0.03333 (19)	0.0287 (4)
H8	0.1370	0.7011	−0.0459	0.034*
C11	0.18026 (13)	0.20873 (10)	0.04698 (12)	0.0134 (3)
C12	0.10077 (14)	0.16293 (12)	0.08405 (14)	0.0190 (3)
H12	0.1045	0.1649	0.1600	0.023*
C13	0.01718 (15)	0.11494 (12)	0.01064 (15)	0.0216 (3)
H13	−0.0365	0.0853	0.0368	0.026*
C14	0.01060 (14)	0.10941 (12)	−0.10137 (15)	0.0209 (3)
H14	−0.0470	0.0762	−0.1510	0.025*
C15	0.08845 (14)	0.15257 (11)	−0.13867 (13)	0.0173 (3)
H15	0.0848	0.1484	−0.2145	0.021*
C16	0.17386 (13)	0.20299 (10)	−0.06624 (12)	0.0130 (3)
C17	0.25104 (13)	0.24775 (10)	−0.11208 (12)	0.0143 (3)
H17	0.2462	0.2364	−0.1871	0.017*
C18	0.39613 (15)	0.34919 (11)	−0.11428 (13)	0.0198 (3)
H18A	0.3689	0.4104	−0.1328	0.024*
H18B	0.3949	0.3182	−0.1834	0.024*
C19	0.51269 (15)	0.35004 (12)	−0.03480 (14)	0.0212 (3)
H19A	0.5484	0.2917	−0.0346	0.025*
H19B	0.5582	0.3955	−0.0574	0.025*
C20	0.58805 (13)	0.40544 (10)	0.14935 (14)	0.0164 (3)
H20	0.6509	0.4211	0.1266	0.020*
C21	0.59273 (13)	0.42237 (10)	0.26236 (13)	0.0153 (3)
C22	0.68418 (14)	0.47114 (11)	0.32913 (15)	0.0200 (3)
H22	0.7370	0.4951	0.2969	0.024*
C23	0.69778 (15)	0.48432 (12)	0.43966 (15)	0.0226 (3)
H23	0.7588	0.5177	0.4835	0.027*
C24	0.62023 (15)	0.44770 (12)	0.48682 (14)	0.0224 (3)
H24	0.6294	0.4564	0.5633	0.027*
C25	0.53063 (14)	0.39920 (11)	0.42404 (13)	0.0185 (3)
H25	0.4795	0.3748	0.4580	0.022*
C26	0.51429 (13)	0.38559 (10)	0.31042 (12)	0.0142 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.01302 (5)	0.01412 (5)	0.01470 (5)	0.00064 (4)	0.00295 (4)	0.00308 (4)
Cr1	0.01411 (10)	0.01046 (10)	0.00892 (9)	−0.00153 (8)	0.00456 (8)	−0.00158 (8)
Cl1	0.0227 (2)	0.0547 (3)	0.01440 (17)	−0.0086 (2)	−0.00046 (15)	0.00491 (19)
N1	0.0178 (6)	0.0172 (6)	0.0121 (5)	−0.0007 (5)	0.0049 (5)	−0.0030 (5)
N2	0.0203 (6)	0.0117 (5)	0.0114 (5)	−0.0018 (5)	0.0072 (5)	−0.0008 (4)
N3	0.0187 (6)	0.0135 (6)	0.0150 (6)	−0.0017 (5)	0.0083 (5)	−0.0007 (5)
O1	0.0199 (5)	0.0184 (5)	0.0101 (4)	−0.0079 (4)	0.0045 (4)	−0.0017 (4)
O2	0.0165 (5)	0.0171 (5)	0.0109 (5)	−0.0041 (4)	0.0026 (4)	−0.0005 (4)
C1	0.0186 (8)	0.0199 (8)	0.0427 (11)	0.0068 (6)	0.0099 (7)	0.0117 (8)
C2	0.0250 (9)	0.0207 (9)	0.0525 (13)	0.0043 (7)	0.0218 (9)	0.0030 (8)
C3	0.0242 (8)	0.0258 (9)	0.0321 (9)	−0.0011 (7)	0.0172 (7)	−0.0019 (7)
C4	0.0197 (7)	0.0172 (7)	0.0160 (6)	−0.0003 (6)	0.0067 (5)	−0.0022 (6)
C5	0.0177 (7)	0.0174 (7)	0.0205 (7)	−0.0015 (6)	0.0058 (6)	−0.0052 (6)
C6	0.0281 (9)	0.0194 (8)	0.0479 (12)	−0.0073 (7)	0.0184 (9)	−0.0125 (8)
C7	0.0270 (9)	0.0140 (8)	0.0661 (15)	0.0005 (7)	0.0236 (10)	0.0038 (9)
C8	0.0238 (9)	0.0194 (8)	0.0444 (11)	0.0071 (7)	0.0125 (8)	0.0152 (8)
C11	0.0154 (6)	0.0122 (6)	0.0122 (6)	−0.0014 (5)	0.0036 (5)	−0.0019 (5)
C12	0.0202 (7)	0.0206 (8)	0.0178 (7)	−0.0054 (6)	0.0080 (6)	−0.0032 (6)
C13	0.0191 (7)	0.0218 (8)	0.0251 (8)	−0.0060 (6)	0.0084 (6)	−0.0050 (7)
C14	0.0175 (7)	0.0202 (8)	0.0221 (8)	−0.0039 (6)	0.0014 (6)	−0.0070 (6)
C15	0.0183 (7)	0.0169 (7)	0.0140 (6)	0.0006 (6)	0.0005 (5)	−0.0028 (5)
C16	0.0157 (6)	0.0114 (6)	0.0108 (6)	0.0009 (5)	0.0022 (5)	−0.0013 (5)
C17	0.0203 (7)	0.0118 (6)	0.0104 (6)	0.0019 (5)	0.0039 (5)	−0.0001 (5)
C18	0.0315 (9)	0.0177 (7)	0.0139 (6)	−0.0071 (6)	0.0127 (6)	−0.0023 (6)
C19	0.0263 (8)	0.0232 (8)	0.0194 (7)	−0.0077 (7)	0.0149 (6)	−0.0064 (6)
C20	0.0168 (7)	0.0131 (6)	0.0204 (7)	−0.0013 (5)	0.0071 (6)	0.0009 (5)
C21	0.0157 (6)	0.0117 (6)	0.0170 (7)	−0.0009 (5)	0.0025 (5)	0.0006 (5)
C22	0.0184 (7)	0.0151 (7)	0.0236 (8)	−0.0025 (6)	0.0017 (6)	0.0005 (6)
C23	0.0218 (8)	0.0173 (7)	0.0229 (8)	−0.0027 (6)	−0.0022 (6)	−0.0046 (6)
C24	0.0243 (8)	0.0223 (8)	0.0161 (7)	0.0013 (7)	−0.0010 (6)	−0.0046 (6)
C25	0.0203 (7)	0.0193 (7)	0.0143 (7)	0.0012 (6)	0.0028 (6)	−0.0023 (6)
C26	0.0156 (6)	0.0118 (6)	0.0134 (6)	0.0014 (5)	0.0015 (5)	−0.0007 (5)

Geometric parameters (Å, º)

Rh1—N1	1.9594 (14)	C7—C8	1.513 (3)
Rh1—Cl1	2.3644 (6)	C7—H7A	0.9900
Rh1—C1	2.1921 (18)	C7—H7B	0.9900
Rh1—C8	2.1744 (18)	C8—H8	1.0000
Rh1—C4	2.1065 (16)	C11—C12	1.409 (2)
Rh1—C5	2.1126 (17)	C11—C16	1.415 (2)
Cr1—N1	1.5936 (14)	C12—C13	1.386 (2)
Cr1—O1	1.8870 (11)	C12—H12	0.9500
Cr1—O2	1.9063 (11)	C13—C14	1.399 (3)
Cr1—N2	2.0017 (13)	C13—H13	0.9500
Cr1—N3	2.0091 (14)	C14—C15	1.374 (2)
N2—C17	1.291 (2)	C14—H14	0.9500
N2—C18	1.473 (2)	C15—C16	1.413 (2)
N3—C20	1.294 (2)	C15—H15	0.9500
N3—C19	1.479 (2)	C16—C17	1.441 (2)
O1—C11	1.3312 (18)	C17—H17	0.9500
O2—C26	1.3232 (18)	C18—C19	1.516 (3)
C1—C8	1.389 (3)	C18—H18A	0.9900
C1—C2	1.520 (3)	C18—H18B	0.9900
C1—H1	1.0000	C19—H19A	0.9900
C2—C3	1.529 (3)	C19—H19B	0.9900
C2—H2A	0.9900	C20—C21	1.438 (2)
C2—H2B	0.9900	C20—H20	0.9500
C3—C4	1.511 (2)	C21—C22	1.418 (2)
C3—H3A	0.9900	C21—C26	1.420 (2)
C3—H3B	0.9900	C22—C23	1.374 (3)
C4—C5	1.409 (2)	C22—H22	0.9500
C4—H4	1.0000	C23—C24	1.402 (3)
C5—C6	1.522 (3)	C23—H23	0.9500
C5—H5	1.0000	C24—C25	1.383 (2)
C6—C7	1.540 (3)	C24—H24	0.9500
C6—H6A	0.9900	C25—C26	1.407 (2)
C6—H6B	0.9900	C25—H25	0.9500
N1—Rh1—C4	88.71 (6)	C7—C6—H6B	108.9
N1—Rh1—C5	92.66 (6)	H6A—C6—H6B	107.7
C4—Rh1—C5	39.02 (6)	C8—C7—C6	113.90 (16)
N1—Rh1—C8	162.51 (7)	C8—C7—H7A	108.8
C4—Rh1—C8	97.41 (8)	C6—C7—H7A	108.8
C5—Rh1—C8	82.16 (8)	C8—C7—H7B	108.8
N1—Rh1—C1	160.25 (6)	C6—C7—H7B	108.8
C4—Rh1—C1	81.28 (7)	H7A—C7—H7B	107.7
C5—Rh1—C1	90.21 (7)	C1—C8—C7	123.6 (2)
C8—Rh1—C1	37.10 (7)	C1—C8—Rh1	72.14 (11)
N1—Rh1—Cl1	89.21 (4)	C7—C8—Rh1	109.89 (13)
C4—Rh1—Cl1	162.51 (5)	C1—C8—H8	114.5
C5—Rh1—Cl1	158.47 (5)	C7—C8—H8	114.5
C8—Rh1—Cl1	89.67 (6)	Rh1—C8—H8	114.5
C1—Rh1—Cl1	95.24 (6)	O1—C11—C12	118.36 (14)
N1—Cr1—O1	110.97 (6)	O1—C11—C16	123.20 (14)
N1—Cr1—O2	105.52 (6)	C12—C11—C16	118.41 (14)
O1—Cr1—O2	87.52 (5)	C13—C12—C11	120.55 (15)
N1—Cr1—N2	98.95 (6)	C13—C12—H12	119.7
O1—Cr1—N2	89.46 (5)	C11—C12—H12	119.7
O2—Cr1—N2	154.77 (6)	C12—C13—C14	121.08 (16)
N1—Cr1—N3	101.36 (6)	C12—C13—H13	119.5
O1—Cr1—N3	147.29 (6)	C14—C13—H13	119.5
O2—Cr1—N3	88.66 (5)	C15—C14—C13	119.15 (15)
N2—Cr1—N3	80.48 (6)	C15—C14—H14	120.4
Cr1—N1—Rh1	173.03 (9)	C13—C14—H14	120.4
C17—N2—C18	119.86 (13)	C14—C15—C16	121.16 (15)
C17—N2—Cr1	127.94 (11)	C14—C15—H15	119.4
C18—N2—Cr1	112.04 (10)	C16—C15—H15	119.4
C20—N3—C19	119.25 (14)	C15—C16—C11	119.64 (14)
C20—N3—Cr1	125.54 (11)	C15—C16—C17	117.85 (14)
C19—N3—Cr1	115.19 (10)	C11—C16—C17	122.51 (14)
C11—O1—Cr1	129.88 (10)	N2—C17—C16	124.15 (14)
C26—O2—Cr1	126.34 (10)	N2—C17—H17	117.9
C8—C1—C2	122.1 (2)	C16—C17—H17	117.9
C8—C1—Rh1	70.75 (11)	N2—C18—C19	106.43 (13)
C2—C1—Rh1	112.22 (12)	N2—C18—H18A	110.4
C8—C1—H1	114.7	C19—C18—H18A	110.4
C2—C1—H1	114.7	N2—C18—H18B	110.4
Rh1—C1—H1	114.7	C19—C18—H18B	110.4
C1—C2—C3	112.16 (15)	H18A—C18—H18B	108.6
C1—C2—H2A	109.2	N3—C19—C18	107.71 (13)
C3—C2—H2A	109.2	N3—C19—H19A	110.2
C1—C2—H2B	109.2	C18—C19—H19A	110.2
C3—C2—H2B	109.2	N3—C19—H19B	110.2
H2A—C2—H2B	107.9	C18—C19—H19B	110.2
C4—C3—C2	113.36 (15)	H19A—C19—H19B	108.5
C4—C3—H3A	108.9	N3—C20—C21	124.45 (15)
C2—C3—H3A	108.9	N3—C20—H20	117.8
C4—C3—H3B	108.9	C21—C20—H20	117.8
C2—C3—H3B	108.9	C22—C21—C26	119.65 (15)
H3A—C3—H3B	107.7	C22—C21—C20	118.17 (15)
C5—C4—C3	124.74 (16)	C26—C21—C20	121.96 (14)
C5—C4—Rh1	70.72 (9)	C23—C22—C21	121.12 (17)
C3—C4—Rh1	111.94 (12)	C23—C22—H22	119.4
C5—C4—H4	113.9	C21—C22—H22	119.4
C3—C4—H4	113.9	C22—C23—C24	119.03 (16)
Rh1—C4—H4	113.9	C22—C23—H23	120.5
C4—C5—C6	123.49 (16)	C24—C23—H23	120.5
C4—C5—Rh1	70.26 (9)	C25—C24—C23	121.20 (16)
C6—C5—Rh1	113.95 (13)	C25—C24—H24	119.4
C4—C5—H5	113.9	C23—C24—H24	119.4
C6—C5—H5	113.9	C24—C25—C26	120.82 (16)
Rh1—C5—H5	113.9	C24—C25—H25	119.6
C5—C6—C7	113.38 (17)	C26—C25—H25	119.6
C5—C6—H6A	108.9	O2—C26—C25	118.67 (15)
C7—C6—H6A	108.9	O2—C26—C21	123.10 (14)
C5—C6—H6B	108.9	C25—C26—C21	118.17 (14)