(Croconato-κ²O,O′)bis­(1,10-phenanthroline-κ²N,N′)cobalt(II), and the nickel(II) and copper(II) analogues

The title complexes, [M(C₅O₅)(C₁₂H₈N₂)₂], with M = Co^II, Ni^II and Cu^II, all lie across twofold rotation axes, around which two 1,10-phenanthroline ligands are arranged in a chiral propeller manner. The Co^II and Ni^II complexes are isostructural, with octa­hedral coordination geometry, while the local geometry of the Cu^II complex is severely distorted from octa­hedral.

Computing details

For all compounds, data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

(I) (Croconato-κ²O,O')bis(1,10-phenanthroline-κ²N,N')cobalt(II)

Crystal data

[Co(C5O5)(C12H8N2)2]	F(000) = 1140
Mr = 559.39	Dx = 1.601 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 46 reflections
a = 12.2197 (10) Å	θ = 4.7–12.5°
b = 11.0048 (11) Å	µ = 0.79 mm^−1
c = 17.2631 (14) Å	T = 293 K
V = 2321.5 (4) Å^3	Prism, dark-red
Z = 4	0.24 × 0.20 × 0.18 mm

Data collection

Bruker P4 diffractometer	1413 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 26.0°, θmin = 2.4°
ω scans	h = −15→1
Absorption correction: ψ scan (XSCANS; Bruker, 1996)	k = −1→13
Tmin = 0.779, Tmax = 0.869	l = −21→1
2953 measured reflections	3 standard reflections every 97 reflections
2283 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.091	w = 1/[σ^2(Fo^2) + (0.0356P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.001
2283 reflections	Δρmax = 0.27 e Å^−3
179 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0046 (4)

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
C1	0.6451 (3)	0.4089 (3)	0.66772 (17)	0.0377 (8)
H1	0.6970	0.4255	0.7056	0.045*
C2	0.6707 (3)	0.3228 (3)	0.61219 (17)	0.0454 (8)
H2	0.7376	0.2825	0.6134	0.054*
C3	0.5961 (3)	0.2981 (3)	0.55561 (17)	0.0443 (8)
H3	0.6118	0.2403	0.5179	0.053*
C4	0.4960 (3)	0.3597 (2)	0.55426 (15)	0.0340 (7)
C5	0.4773 (2)	0.4439 (3)	0.61386 (15)	0.0300 (7)
C6	0.3752 (2)	0.5087 (3)	0.61678 (15)	0.0313 (7)
C7	0.2966 (3)	0.4891 (3)	0.55895 (17)	0.0374 (8)
C8	0.3203 (3)	0.4072 (3)	0.49745 (17)	0.0441 (8)
H8	0.2694	0.3969	0.4580	0.053*
C9	0.4151 (3)	0.3441 (3)	0.49500 (17)	0.0420 (8)
H9	0.4280	0.2901	0.4546	0.050*
C10	0.1982 (3)	0.5557 (3)	0.56437 (19)	0.0519 (10)
H10	0.1440	0.5466	0.5270	0.062*
C11	0.1836 (3)	0.6332 (3)	0.62483 (19)	0.0521 (10)
H11	0.1186	0.6765	0.6296	0.062*
C12	0.2665 (3)	0.6475 (3)	0.67963 (18)	0.0476 (9)
H12	0.2551	0.7014	0.7203	0.057*
C13	0.5318 (2)	0.8483 (3)	0.71506 (16)	0.0330 (7)
C14	0.5504 (3)	0.9727 (3)	0.68937 (19)	0.0409 (8)
C15	0.5000	1.0529 (4)	0.7500	0.0412 (11)
N1	0.5521 (2)	0.4689 (2)	0.67040 (13)	0.0305 (6)
N2	0.3607 (2)	0.5880 (2)	0.67660 (13)	0.0361 (6)
O1	0.56377 (19)	0.74960 (18)	0.68385 (11)	0.0419 (6)
O2	0.5982 (2)	1.0066 (2)	0.63037 (14)	0.0668 (8)
O3	0.5000	1.1647 (3)	0.7500	0.0600 (9)
Co1	0.5000	0.60353 (5)	0.7500	0.03232 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0381 (18)	0.0381 (18)	0.0369 (16)	0.0045 (16)	−0.0033 (14)	0.0010 (16)
C2	0.045 (2)	0.044 (2)	0.0473 (19)	0.0114 (18)	0.0072 (17)	−0.0037 (18)
C3	0.059 (2)	0.0325 (17)	0.0411 (18)	0.0027 (18)	0.0117 (18)	−0.0078 (16)
C4	0.0453 (17)	0.0270 (14)	0.0298 (14)	−0.0076 (18)	0.0059 (17)	−0.0002 (12)
C5	0.0349 (19)	0.0280 (14)	0.0270 (14)	−0.0027 (13)	0.0022 (13)	0.0025 (13)
C6	0.0338 (16)	0.0335 (17)	0.0267 (14)	−0.0070 (15)	0.0029 (14)	0.0056 (14)
C7	0.0374 (17)	0.0413 (19)	0.0336 (16)	−0.0104 (16)	−0.0029 (16)	0.0098 (15)
C8	0.053 (2)	0.046 (2)	0.0335 (16)	−0.0187 (19)	−0.0070 (16)	0.0048 (16)
C9	0.055 (2)	0.0398 (19)	0.0309 (16)	−0.0131 (18)	0.0020 (16)	−0.0042 (15)
C10	0.039 (2)	0.070 (3)	0.047 (2)	−0.006 (2)	−0.0107 (18)	0.020 (2)
C11	0.0374 (19)	0.068 (3)	0.0507 (19)	0.0155 (19)	−0.0006 (18)	0.023 (2)
C12	0.051 (2)	0.053 (2)	0.0389 (18)	0.0158 (19)	0.0062 (17)	0.0079 (18)
C13	0.0364 (18)	0.0330 (16)	0.0296 (15)	−0.0011 (14)	0.0006 (13)	0.0021 (14)
C14	0.0398 (18)	0.0366 (19)	0.0463 (18)	−0.0029 (16)	−0.0012 (17)	0.0087 (17)
C15	0.042 (3)	0.035 (2)	0.047 (3)	0.000	−0.015 (3)	0.000
N1	0.0328 (14)	0.0299 (14)	0.0289 (13)	0.0007 (12)	−0.0010 (11)	0.0001 (12)
N2	0.0404 (15)	0.0393 (15)	0.0287 (13)	0.0085 (13)	0.0024 (12)	0.0022 (12)
O1	0.0590 (15)	0.0335 (12)	0.0334 (11)	0.0006 (11)	0.0133 (11)	−0.0017 (10)
O2	0.0801 (19)	0.0515 (16)	0.0690 (16)	0.0017 (15)	0.0290 (17)	0.0218 (14)
O3	0.070 (2)	0.0344 (19)	0.076 (2)	0.000	−0.007 (2)	0.000
Co1	0.0406 (3)	0.0305 (3)	0.0259 (3)	0.000	0.0012 (3)	0.000

Geometric parameters (Å, º)

C1—N1	1.315 (4)	C10—H10	0.9300
C1—C2	1.384 (4)	C11—C12	1.395 (4)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.363 (4)	C12—N2	1.324 (4)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.399 (4)	C13—O1	1.274 (3)
C3—H3	0.9300	C13—C13^i	1.435 (5)
C4—C5	1.403 (4)	C13—C14	1.457 (4)
C4—C9	1.433 (4)	C14—O2	1.232 (4)
C5—N1	1.366 (3)	C14—C15	1.501 (4)
C5—C6	1.437 (4)	C15—O3	1.230 (5)
C6—N2	1.364 (3)	C15—C14^i	1.501 (4)
C6—C7	1.403 (4)	N1—Co1	2.119 (2)
C7—C10	1.410 (4)	N2—Co1	2.129 (2)
C7—C8	1.423 (4)	O1—Co1	2.120 (2)
C8—C9	1.352 (4)	Co1—N1^i	2.119 (2)
C8—H8	0.9300	Co1—O1^i	2.120 (2)
C9—H9	0.9300	Co1—N2^i	2.129 (3)
C10—C11	1.360 (4)
N1—C1—C2	124.3 (3)	N2—C12—H12	118.4
N1—C1—H1	117.8	C11—C12—H12	118.4
C2—C1—H1	117.8	O1—C13—C13^i	121.44 (15)
C3—C2—C1	118.7 (3)	O1—C13—C14	128.7 (3)
C3—C2—H2	120.6	C13^i—C13—C14	109.90 (17)
C1—C2—H2	120.6	O2—C14—C13	127.6 (3)
C2—C3—C4	120.0 (3)	O2—C14—C15	126.4 (3)
C2—C3—H3	120.0	C13—C14—C15	106.0 (3)
C4—C3—H3	120.0	O3—C15—C14^i	126.00 (18)
C3—C4—C5	116.8 (3)	O3—C15—C14	126.00 (18)
C3—C4—C9	123.9 (3)	C14^i—C15—C14	108.0 (4)
C5—C4—C9	119.3 (3)	C1—N1—C5	116.9 (3)
N1—C5—C4	123.2 (3)	C1—N1—Co1	129.3 (2)
N1—C5—C6	117.1 (3)	C5—N1—Co1	113.77 (19)
C4—C5—C6	119.7 (3)	C12—N2—C6	117.4 (3)
N2—C6—C7	123.2 (3)	C12—N2—Co1	129.2 (2)
N2—C6—C5	117.2 (3)	C6—N2—Co1	113.4 (2)
C7—C6—C5	119.6 (3)	C13—O1—Co1	107.82 (17)
C6—C7—C10	117.2 (3)	N1^i—Co1—N1	91.27 (12)
C6—C7—C8	119.2 (3)	N1^i—Co1—O1^i	94.03 (8)
C10—C7—C8	123.5 (3)	N1—Co1—O1^i	171.88 (9)
C9—C8—C7	121.6 (3)	N1^i—Co1—O1	171.88 (9)
C9—C8—H8	119.2	N1—Co1—O1	94.03 (8)
C7—C8—H8	119.2	O1^i—Co1—O1	81.39 (11)
C8—C9—C4	120.5 (3)	N1^i—Co1—N2^i	78.37 (9)
C8—C9—H9	119.8	N1—Co1—N2^i	95.14 (9)
C4—C9—H9	119.8	O1^i—Co1—N2^i	91.96 (9)
C11—C10—C7	119.3 (3)	O1—Co1—N2^i	95.01 (10)
C11—C10—H10	120.4	N1^i—Co1—N2	95.14 (9)
C7—C10—H10	120.4	N1—Co1—N2	78.37 (9)
C10—C11—C12	119.7 (3)	O1^i—Co1—N2	95.01 (10)
C10—C11—H11	120.1	O1—Co1—N2	91.96 (9)
C12—C11—H11	120.1	N2^i—Co1—N2	170.81 (14)
N2—C12—C11	123.2 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

(II) (Croconato-κ²O,O')bis(1,10-phenanthroline-κ²N,N')nickel(II)

Crystal data

[Ni(C5O5)(C12H8N2)2]	F(000) = 1144
Mr = 559.17	Dx = 1.614 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 41 reflections
a = 12.2618 (16) Å	θ = 4.7–12.5°
b = 10.929 (2) Å	µ = 0.90 mm^−1
c = 17.171 (3) Å	T = 293 K
V = 2301.1 (7) Å^3	Prism, brown
Z = 4	0.38 × 0.34 × 0.18 mm

Data collection

Bruker P4 diffractometer	1457 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 26.0°, θmin = 2.5°
ω scans	h = −15→1
Absorption correction: ψ scan (XSCANS; Bruker, 1996)	k = −13→1
Tmin = 0.775, Tmax = 0.854	l = −1→21
2872 measured reflections	3 standard reflections every 97 reflections
2245 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.0387P)^2 + 3.6078P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2245 reflections	Δρmax = 0.30 e Å^−3
179 parameters	Δρmin = −0.41 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0061 (6)

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
C1	0.6459 (3)	0.4090 (3)	0.6691 (2)	0.0385 (9)
H1	0.6981	0.4259	0.7069	0.046*
C2	0.6708 (3)	0.3221 (4)	0.6131 (2)	0.0469 (10)
H2	0.7375	0.2816	0.6139	0.056*
C3	0.5967 (3)	0.2974 (3)	0.5575 (2)	0.0429 (10)
H3	0.6119	0.2387	0.5199	0.052*
C4	0.4968 (3)	0.3595 (3)	0.5558 (2)	0.0333 (8)
C5	0.4784 (3)	0.4439 (3)	0.6157 (2)	0.0295 (8)
C6	0.3770 (3)	0.5093 (3)	0.6186 (2)	0.0312 (8)
C7	0.2981 (3)	0.4905 (4)	0.5607 (2)	0.0383 (9)
C8	0.3208 (3)	0.4082 (4)	0.4985 (2)	0.0435 (10)
H8	0.2699	0.3982	0.4588	0.052*
C9	0.4159 (3)	0.3440 (4)	0.4961 (2)	0.0430 (10)
H9	0.4286	0.2895	0.4555	0.052*
C10	0.2006 (3)	0.5581 (4)	0.5675 (3)	0.0516 (12)
H10	0.1457	0.5489	0.5305	0.062*
C11	0.1869 (3)	0.6363 (4)	0.6277 (3)	0.0531 (12)
H11	0.1224	0.6804	0.6327	0.064*
C12	0.2696 (3)	0.6503 (4)	0.6823 (2)	0.0457 (10)
H12	0.2590	0.7041	0.7235	0.055*
C13	0.5320 (3)	0.8456 (3)	0.7152 (2)	0.0354 (9)
C14	0.5501 (3)	0.9706 (3)	0.6894 (2)	0.0418 (10)
C15	0.5000	1.0511 (5)	0.7500	0.0402 (12)
N1	0.5529 (2)	0.4692 (2)	0.67213 (17)	0.0296 (7)
N2	0.3635 (2)	0.5896 (3)	0.67763 (18)	0.0363 (7)
O1	0.5633 (2)	0.7456 (2)	0.68342 (15)	0.0414 (7)
O2	0.5971 (3)	1.0041 (3)	0.62964 (19)	0.0665 (9)
O3	0.5000	1.1636 (3)	0.7500	0.0552 (11)
Ni1	0.5000	0.60120 (6)	0.7500	0.0305 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.037 (2)	0.036 (2)	0.042 (2)	0.0035 (18)	−0.0011 (17)	0.0010 (18)
C2	0.040 (2)	0.043 (2)	0.057 (3)	0.012 (2)	0.002 (2)	−0.001 (2)
C3	0.053 (2)	0.0300 (19)	0.045 (2)	−0.0002 (19)	0.013 (2)	−0.0070 (18)
C4	0.0434 (19)	0.0266 (15)	0.0299 (18)	−0.0115 (19)	0.0041 (18)	0.0005 (14)
C5	0.035 (2)	0.0258 (15)	0.0280 (18)	−0.0046 (14)	0.0021 (15)	0.0050 (14)
C6	0.0326 (18)	0.0307 (18)	0.0304 (19)	−0.0041 (16)	0.0020 (16)	0.0053 (16)
C7	0.0329 (18)	0.040 (2)	0.042 (2)	−0.0092 (18)	−0.0047 (18)	0.0122 (18)
C8	0.047 (2)	0.045 (2)	0.039 (2)	−0.018 (2)	−0.0106 (18)	0.0029 (19)
C9	0.056 (3)	0.035 (2)	0.037 (2)	−0.015 (2)	−0.003 (2)	−0.0049 (18)
C10	0.034 (2)	0.064 (3)	0.056 (3)	−0.005 (2)	−0.012 (2)	0.021 (2)
C11	0.037 (2)	0.069 (3)	0.053 (3)	0.018 (2)	0.002 (2)	0.020 (2)
C12	0.050 (3)	0.045 (2)	0.042 (2)	0.016 (2)	0.0066 (19)	0.007 (2)
C13	0.037 (2)	0.0330 (18)	0.036 (2)	0.0016 (16)	−0.0005 (16)	0.0030 (17)
C14	0.041 (2)	0.032 (2)	0.052 (3)	−0.0025 (18)	0.001 (2)	0.0104 (19)
C15	0.037 (3)	0.028 (2)	0.055 (3)	0.000	−0.012 (3)	0.000
N1	0.0311 (15)	0.0268 (14)	0.0310 (16)	0.0013 (13)	−0.0016 (13)	−0.0007 (13)
N2	0.0342 (16)	0.0339 (16)	0.0407 (18)	0.0079 (14)	0.0014 (14)	0.0063 (15)
O1	0.0532 (16)	0.0336 (13)	0.0373 (15)	0.0013 (13)	0.0119 (13)	0.0015 (12)
O2	0.080 (2)	0.0513 (18)	0.068 (2)	−0.0021 (18)	0.024 (2)	0.0215 (17)
O3	0.063 (3)	0.034 (2)	0.069 (3)	0.000	−0.012 (3)	0.000
Ni1	0.0356 (4)	0.0277 (3)	0.0281 (3)	0.000	0.0010 (3)	0.000

Geometric parameters (Å, º)

C1—N1	1.318 (4)	C10—H10	0.9300
C1—C2	1.386 (5)	C11—C12	1.389 (6)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.345 (6)	C12—N2	1.331 (5)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.401 (5)	C13—O1	1.280 (4)
C3—H3	0.9300	C13—C13^i	1.430 (7)
C4—C5	1.399 (5)	C13—C14	1.453 (5)
C4—C9	1.437 (5)	C14—O2	1.232 (5)
C5—N1	1.360 (4)	C14—C15	1.495 (5)
C5—C6	1.435 (5)	C15—O3	1.229 (6)
C6—N2	1.350 (5)	C15—C14^i	1.495 (5)
C6—C7	1.403 (5)	N1—Ni1	2.071 (3)
C7—C10	1.411 (5)	N2—Ni1	2.088 (3)
C7—C8	1.424 (5)	O1—Ni1	2.098 (3)
C8—C9	1.362 (6)	Ni1—N1^i	2.071 (3)
C8—H8	0.9300	Ni1—N2^i	2.088 (3)
C9—H9	0.9300	Ni1—O1^i	2.098 (3)
C10—C11	1.352 (6)
N1—C1—C2	124.0 (4)	N2—C12—H12	118.8
N1—C1—H1	118.0	C11—C12—H12	118.8
C2—C1—H1	118.0	O1—C13—C13^i	121.4 (2)
C3—C2—C1	118.8 (4)	O1—C13—C14	128.8 (3)
C3—C2—H2	120.6	C13^i—C13—C14	109.8 (2)
C1—C2—H2	120.6	O2—C14—C13	127.2 (4)
C2—C3—C4	120.5 (4)	O2—C14—C15	126.6 (3)
C2—C3—H3	119.7	C13—C14—C15	106.1 (3)
C4—C3—H3	119.7	O3—C15—C14^i	126.1 (2)
C5—C4—C3	116.5 (3)	O3—C15—C14	126.1 (2)
C5—C4—C9	119.4 (4)	C14^i—C15—C14	107.9 (4)
C3—C4—C9	124.1 (3)	C1—N1—C5	116.9 (3)
N1—C5—C4	123.3 (3)	C1—N1—Ni1	130.1 (3)
N1—C5—C6	117.1 (3)	C5—N1—Ni1	113.0 (2)
C4—C5—C6	119.6 (3)	C12—N2—C6	118.3 (3)
N2—C6—C7	122.9 (3)	C12—N2—Ni1	128.8 (3)
N2—C6—C5	117.1 (3)	C6—N2—Ni1	112.8 (2)
C7—C6—C5	120.0 (3)	C13—O1—Ni1	107.4 (2)
C6—C7—C10	116.7 (4)	N1^i—Ni1—N1	91.69 (16)
C6—C7—C8	119.3 (3)	N1^i—Ni1—N2^i	79.89 (12)
C10—C7—C8	124.0 (4)	N1—Ni1—N2^i	95.22 (11)
C9—C8—C7	121.0 (4)	N1^i—Ni1—N2	95.22 (11)
C9—C8—H8	119.5	N1—Ni1—N2	79.89 (12)
C7—C8—H8	119.5	N2^i—Ni1—N2	173.03 (17)
C8—C9—C4	120.6 (4)	N1^i—Ni1—O1^i	93.23 (10)
C8—C9—H9	119.7	N1—Ni1—O1^i	172.64 (11)
C4—C9—H9	119.7	N2^i—Ni1—O1^i	91.03 (11)
C11—C10—C7	119.9 (4)	N2—Ni1—O1^i	94.22 (11)
C11—C10—H10	120.0	N1^i—Ni1—O1	172.64 (11)
C7—C10—H10	120.0	N1—Ni1—O1	93.23 (10)
C10—C11—C12	119.7 (4)	N2^i—Ni1—O1	94.22 (12)
C10—C11—H11	120.2	N2—Ni1—O1	91.03 (11)
C12—C11—H11	120.2	O1^i—Ni1—O1	82.41 (14)
N2—C12—C11	122.5 (4)

Symmetry code: (i) −x+1, y, −z+3/2.

(III) (Croconato-κ²O,O')bis(1,10-phenanthroline-κ²N,N')copper(II)

Crystal data

[Cu(C5O5)(C12H8N2)2]	F(000) = 1148
Mr = 564.00	Dx = 1.604 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 38 reflections
a = 14.6737 (16) Å	θ = 5.2–12.5°
b = 10.5316 (13) Å	µ = 0.99 mm^−1
c = 15.7783 (17) Å	T = 293 K
β = 106.666 (9)°	Prism, black
V = 2335.9 (5) Å^3	0.30 × 0.28 × 0.22 mm
Z = 4

Data collection

Bruker P4 diffractometer	1906 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 27.0°, θmin = 2.4°
ω scans	h = −1→18
Absorption correction: ψ scan (XSCANS; Bruker, 1996)	k = −1→13
Tmin = 0.719, Tmax = 0.805	l = −20→19
3179 measured reflections	97 standard reflections every 3 reflections
2558 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0318P)^2 + 2.2378P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2558 reflections	Δρmax = 0.41 e Å^−3
179 parameters	Δρmin = −0.34 e Å^−3
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0046 (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
C1	0.2046 (2)	0.0910 (3)	0.3204 (2)	0.0501 (8)
H1	0.2084	0.0878	0.2626	0.060*
C2	0.2845 (2)	0.0565 (3)	0.3889 (2)	0.0574 (9)
H2	0.3407	0.0343	0.3765	0.069*
C3	0.2799 (2)	0.0555 (3)	0.4740 (2)	0.0509 (8)
H3	0.3326	0.0321	0.5200	0.061*
C4	0.19446 (19)	0.0902 (3)	0.49138 (18)	0.0402 (7)
C5	0.11904 (18)	0.1279 (3)	0.41863 (16)	0.0346 (6)
C6	0.03168 (17)	0.1695 (3)	0.43275 (16)	0.0330 (6)
C7	0.01969 (18)	0.1637 (3)	0.51777 (16)	0.0370 (6)
C8	0.0975 (2)	0.1216 (3)	0.59026 (17)	0.0461 (7)
H8	0.0901	0.1174	0.6468	0.055*
C9	0.1809 (2)	0.0881 (3)	0.57737 (17)	0.0470 (8)
H9	0.2308	0.0630	0.6255	0.056*
C10	−0.06974 (19)	0.2009 (3)	0.52609 (17)	0.0421 (7)
H10	−0.0819	0.1965	0.5807	0.051*
C11	−0.13819 (19)	0.2435 (3)	0.45359 (17)	0.0438 (7)
H11	−0.1974	0.2676	0.4585	0.053*
C12	−0.11910 (19)	0.2509 (3)	0.37191 (17)	0.0396 (7)
H12	−0.1657	0.2829	0.3235	0.047*
C13	0.05073 (18)	0.4944 (3)	0.27218 (16)	0.0377 (7)
C14	0.08380 (18)	0.6244 (3)	0.28540 (16)	0.0384 (6)
C15	0.0000	0.7081 (4)	0.2500	0.0377 (9)
N1	0.12381 (16)	0.1280 (2)	0.33378 (14)	0.0390 (5)
N2	−0.03688 (14)	0.2137 (2)	0.36118 (12)	0.0349 (5)
O1	0.09782 (15)	0.3941 (2)	0.29311 (13)	0.0541 (5)
O2	0.16619 (13)	0.6606 (2)	0.32058 (15)	0.0630 (7)
O3	0.0000	0.8248 (3)	0.2500	0.0516 (8)
Cu1	0.0000	0.22050 (5)	0.2500	0.03688 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0507 (18)	0.058 (2)	0.0479 (16)	0.0108 (16)	0.0241 (14)	0.0049 (15)
C2	0.0442 (17)	0.065 (2)	0.070 (2)	0.0157 (17)	0.0271 (16)	0.0094 (19)
C3	0.0364 (15)	0.056 (2)	0.0561 (18)	0.0116 (15)	0.0066 (14)	0.0064 (16)
C4	0.0346 (14)	0.0421 (17)	0.0407 (14)	0.0027 (13)	0.0058 (12)	0.0011 (13)
C5	0.0331 (14)	0.0385 (16)	0.0322 (13)	−0.0001 (12)	0.0094 (11)	−0.0019 (12)
C6	0.0317 (13)	0.0365 (15)	0.0292 (12)	−0.0017 (12)	0.0060 (10)	−0.0029 (11)
C7	0.0366 (14)	0.0419 (17)	0.0312 (13)	−0.0022 (13)	0.0077 (11)	−0.0059 (12)
C8	0.0493 (17)	0.061 (2)	0.0247 (12)	0.0050 (16)	0.0057 (12)	−0.0013 (13)
C9	0.0440 (17)	0.057 (2)	0.0329 (14)	0.0040 (15)	0.0000 (12)	0.0026 (14)
C10	0.0439 (15)	0.0529 (19)	0.0318 (13)	−0.0033 (15)	0.0145 (12)	−0.0075 (13)
C11	0.0329 (14)	0.059 (2)	0.0423 (14)	0.0023 (13)	0.0147 (12)	−0.0052 (14)
C12	0.0321 (13)	0.0489 (19)	0.0361 (13)	0.0043 (12)	0.0073 (11)	−0.0002 (12)
C13	0.0357 (15)	0.0495 (18)	0.0261 (12)	0.0061 (13)	0.0059 (11)	−0.0030 (12)
C14	0.0282 (14)	0.0539 (18)	0.0320 (13)	−0.0011 (13)	0.0070 (11)	−0.0081 (13)
C15	0.040 (2)	0.048 (3)	0.0285 (18)	0.000	0.0136 (16)	0.000
N1	0.0391 (13)	0.0446 (14)	0.0352 (11)	0.0052 (11)	0.0138 (10)	0.0011 (11)
N2	0.0302 (11)	0.0452 (14)	0.0284 (10)	0.0013 (11)	0.0068 (8)	−0.0014 (10)
O1	0.0510 (13)	0.0475 (12)	0.0534 (12)	0.0096 (9)	−0.0015 (10)	−0.0063 (10)
O2	0.0290 (11)	0.0836 (18)	0.0687 (14)	−0.0098 (11)	0.0015 (10)	−0.0174 (13)
O3	0.068 (2)	0.0471 (19)	0.0419 (16)	0.000	0.0199 (15)	0.000
Cu1	0.0306 (3)	0.0532 (3)	0.0263 (2)	0.000	0.00723 (17)	0.000

Geometric parameters (Å, º)

C1—N1	1.322 (3)	C10—H10	0.9300
C1—C2	1.395 (4)	C11—C12	1.397 (4)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.363 (4)	C12—N2	1.325 (3)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.406 (4)	C13—O1	1.254 (3)
C3—H3	0.9300	C13—C14	1.447 (4)
C4—C5	1.404 (3)	C13—C13^i	1.452 (5)
C4—C9	1.427 (4)	C14—O2	1.237 (3)
C5—N1	1.361 (3)	C14—C15	1.485 (4)
C5—C6	1.431 (3)	C15—O3	1.229 (5)
C6—N2	1.361 (3)	C15—C14^i	1.485 (4)
C6—C7	1.403 (3)	Cu1—N2	1.9799 (19)
C7—C10	1.411 (4)	Cu1—N2^i	1.9799 (19)
C7—C8	1.435 (4)	Cu1—N1^i	2.149 (2)
C8—C9	1.344 (4)	Cu1—N1	2.149 (2)
C8—H8	0.9300	Cu1—O1	2.303 (2)
C9—H9	0.9300	Cu1—O1^i	2.303 (2)
C10—C11	1.364 (4)
N1—C1—C2	123.1 (3)	N2—C12—H12	118.9
N1—C1—H1	118.5	C11—C12—H12	118.9
C2—C1—H1	118.5	O1—C13—C14	128.5 (2)
C3—C2—C1	119.8 (3)	O1—C13—C13^i	122.57 (16)
C3—C2—H2	120.1	C14—C13—C13^i	108.94 (15)
C1—C2—H2	120.1	O2—C14—C13	126.9 (3)
C2—C3—C4	119.3 (3)	O2—C14—C15	125.7 (3)
C2—C3—H3	120.4	C13—C14—C15	107.4 (2)
C4—C3—H3	120.4	O3—C15—C14^i	126.38 (18)
C5—C4—C3	116.8 (3)	O3—C15—C14	126.38 (18)
C5—C4—C9	119.3 (2)	C14^i—C15—C14	107.2 (4)
C3—C4—C9	123.9 (3)	C1—N1—C5	117.3 (2)
N1—C5—C4	123.6 (2)	C1—N1—Cu1	132.40 (19)
N1—C5—C6	117.0 (2)	C5—N1—Cu1	109.43 (17)
C4—C5—C6	119.4 (2)	C12—N2—C6	118.6 (2)
N2—C6—C7	122.9 (2)	C12—N2—Cu1	126.37 (17)
N2—C6—C5	117.2 (2)	C6—N2—Cu1	115.00 (16)
C7—C6—C5	119.9 (2)	C13—O1—Cu1	109.96 (17)
C6—C7—C10	116.8 (2)	N2—Cu1—N2^i	175.88 (14)
C6—C7—C8	119.1 (2)	N2—Cu1—N1^i	97.53 (8)
C10—C7—C8	124.1 (2)	N2^i—Cu1—N1^i	80.58 (8)
C9—C8—C7	120.7 (2)	N2—Cu1—N1	80.58 (8)
C9—C8—H8	119.6	N2^i—Cu1—N1	97.53 (8)
C7—C8—H8	119.6	N1^i—Cu1—N1	126.11 (13)
C8—C9—C4	121.4 (3)	N2—Cu1—O1	94.15 (8)
C8—C9—H9	119.3	N2^i—Cu1—O1	89.12 (8)
C4—C9—H9	119.3	N1^i—Cu1—O1	152.44 (8)
C11—C10—C7	119.6 (2)	N1—Cu1—O1	80.37 (8)
C11—C10—H10	120.2	N2—Cu1—O1^i	89.12 (8)
C7—C10—H10	120.2	N2^i—Cu1—O1^i	94.15 (8)
C10—C11—C12	119.9 (2)	N1^i—Cu1—O1^i	80.37 (8)
C10—C11—H11	120.1	N1—Cu1—O1^i	152.44 (8)
C12—C11—H11	120.1	O1—Cu1—O1^i	74.93 (10)
N2—C12—C11	122.2 (2)
N1—C1—C2—C3	2.6 (5)	C4—C5—N1—C1	−0.4 (4)
C1—C2—C3—C4	−0.4 (5)	C6—C5—N1—C1	179.3 (3)
C2—C3—C4—C5	−1.9 (5)	C4—C5—N1—Cu1	−171.1 (2)
C2—C3—C4—C9	177.7 (3)	C6—C5—N1—Cu1	8.6 (3)
C3—C4—C5—N1	2.4 (4)	N2—Cu1—N1—C1	−176.6 (3)
C9—C4—C5—N1	−177.2 (3)	N2^i—Cu1—N1—C1	7.1 (3)
C3—C4—C5—C6	−177.3 (3)	N1^i—Cu1—N1—C1	90.9 (3)
C9—C4—C5—C6	3.1 (4)	O1—Cu1—N1—C1	−80.7 (3)
N1—C5—C6—N2	−4.3 (4)	O1^i—Cu1—N1—C1	−107.2 (3)
C4—C5—C6—N2	175.4 (2)	N2—Cu1—N1—C5	−7.77 (18)
N1—C5—C6—C7	175.7 (2)	N2^i—Cu1—N1—C5	175.93 (19)
C4—C5—C6—C7	−4.6 (4)	N1^i—Cu1—N1—C5	−100.26 (19)
N2—C6—C7—C10	2.8 (4)	O1—Cu1—N1—C5	88.11 (19)
C5—C6—C7—C10	−177.3 (3)	O1^i—Cu1—N1—C5	61.6 (3)
N2—C6—C7—C8	−176.9 (3)	C11—C12—N2—C6	−1.4 (4)
C5—C6—C7—C8	3.0 (4)	C11—C12—N2—Cu1	−179.3 (2)
C6—C7—C8—C9	0.0 (5)	C7—C6—N2—C12	−1.2 (4)
C10—C7—C8—C9	−179.7 (3)	C5—C6—N2—C12	178.9 (2)
C7—C8—C9—C4	−1.5 (5)	C7—C6—N2—Cu1	177.0 (2)
C5—C4—C9—C8	−0.1 (5)	C5—C6—N2—Cu1	−3.0 (3)
C3—C4—C9—C8	−179.6 (3)	N1^i—Cu1—N2—C12	−50.7 (2)
C6—C7—C10—C11	−1.8 (4)	N1—Cu1—N2—C12	−176.2 (2)
C8—C7—C10—C11	177.8 (3)	O1—Cu1—N2—C12	104.3 (2)
C7—C10—C11—C12	−0.5 (4)	O1^i—Cu1—N2—C12	29.5 (2)
C10—C11—C12—N2	2.3 (4)	N1^i—Cu1—N2—C6	131.3 (2)
O1—C13—C14—O2	−0.1 (5)	N1—Cu1—N2—C6	5.82 (19)
C13^i—C13—C14—O2	−179.5 (3)	O1—Cu1—N2—C6	−73.7 (2)
O1—C13—C14—C15	−179.3 (2)	O1^i—Cu1—N2—C6	−148.5 (2)
C13^i—C13—C14—C15	1.3 (3)	C14—C13—O1—Cu1	−179.0 (2)
O2—C14—C15—O3	0.3 (3)	C13^i—C13—O1—Cu1	0.4 (4)
C13—C14—C15—O3	179.51 (12)	N2—Cu1—O1—C13	−88.10 (19)
O2—C14—C15—C14^i	−179.7 (3)	N2^i—Cu1—O1—C13	94.41 (19)
C13—C14—C15—C14^i	−0.49 (12)	N1^i—Cu1—O1—C13	26.9 (3)
C2—C1—N1—C5	−2.1 (5)	N1—Cu1—O1—C13	−167.80 (19)
C2—C1—N1—Cu1	166.0 (2)	O1^i—Cu1—O1—C13	−0.13 (13)

Symmetry code: (i) −x, y, −z+1/2.