Tetra-μ-methacrylato-κO:O'-bis-[(pyri-din-2-amine-κN)copper(II)].

In the title carboxyl-ate-bridged binuclear copper complex, [Cu(2)(C(4)H(5)O(2))(4)(C(5)H(6)N(2))(2)], each Cu(II) ion has a distorted square-based pyramidal environment formed by one N and four O atoms. The asymmetric unit contains two halves of two centrosymmetric mol-ecules, with Cu⋯Cu separations of 2.6498 (8) and 2.6528 (8) Å.

Related literature

For the crystal structures of related binuclear complexes, see: Du et al. (2002 ▶); Wu & Wang (2004 ▶).

Experimental

Crystal data

[Cu2(C4H5O2)4(C5H6N2)2]

M = 655.64

Monoclinic,

a = 16.8591 (15) Å

b = 12.1185 (11) Å

c = 16.5980 (15) Å

β = 117.458 (2)°

V = 3009.1 (5) Å3

Z = 4

Mo Kα radiation

μ = 1.47 mm−1

T = 298 K

0.28 × 0.20 × 0.13 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.685, T max = 0.832

15356 measured reflections

5539 independent reflections

3542 reflections with I > 2σ(I)

R int = 0.099

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.084

S = 0.88

5539 reflections

365 parameters

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901352X/cv2539sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901352X/cv2539Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu2(C4H5O2)4(C5H6N2)2]	F(000) = 1352
Mr = 655.64	Dx = 1.447 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5539 reflections
a = 16.8591 (15) Å	θ = 2.2–25.4°
b = 12.1185 (11) Å	µ = 1.47 mm−1
c = 16.5980 (15) Å	T = 298 K
β = 117.458 (2)°	Block, blue
V = 3009.1 (5) Å3	0.28 × 0.20 × 0.13 mm
Z = 4

Bruker APEXII area-detector diffractometer	5539 independent reflections
Radiation source: fine-focus sealed tube	3542 reflections with I > 2σ(I)
graphite	Rint = 0.099
φ and ω scans	θmax = 25.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −20→20
Tmin = 0.685, Tmax = 0.832	k = −14→10
15356 measured reflections	l = −20→20

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H-atom parameters constrained
S = 0.88	w = 1/[σ2(Fo2) + (0.01P)2 + 0.272P] where P = (Fo2 + 2Fc2)/3
5539 reflections	(Δ/σ)max = 0.001
365 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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.

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 > 2sigma(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
Cu2	0.45444 (2)	0.09186 (3)	0.49285 (2)	0.04205 (13)
O6	0.57214 (14)	0.1643 (2)	0.55362 (14)	0.0594 (7)
O5	0.64848 (13)	0.0105 (2)	0.56541 (14)	0.0568 (6)
O7	0.46883 (14)	0.0508 (2)	0.61306 (13)	0.0559 (6)
O8	0.45651 (13)	0.1057 (2)	0.37567 (13)	0.0531 (6)
N1	0.37557 (15)	0.2416 (2)	0.47289 (15)	0.0420 (7)
N2	0.26243 (18)	0.1607 (3)	0.4918 (2)	0.0837 (11)
H2A	0.2881	0.0979	0.4969	0.100*
H2B	0.2133	0.1647	0.4955	0.100*
C1	0.4104 (2)	0.3339 (3)	0.45853 (19)	0.0498 (9)
H1	0.4633	0.3273	0.4542	0.060*
C2	0.3754 (2)	0.4363 (3)	0.4498 (2)	0.0637 (10)
H2	0.4029	0.4976	0.4397	0.076*
C3	0.2970 (3)	0.4456 (4)	0.4565 (2)	0.0739 (12)
H3	0.2711	0.5146	0.4520	0.089*
C4	0.2579 (2)	0.3550 (4)	0.4694 (2)	0.0671 (11)
H4	0.2043	0.3606	0.4725	0.081*
C5	0.2991 (2)	0.2524 (3)	0.4781 (2)	0.0511 (9)
C6	0.6433 (2)	0.1113 (3)	0.5791 (2)	0.0491 (9)
C7	0.7293 (2)	0.1718 (4)	0.6338 (2)	0.0638 (11)
C8	0.7244 (3)	0.2751 (4)	0.6645 (3)	0.123 (2)
H5	0.7764	0.3150	0.6986	0.148*
H6	0.6691	0.3054	0.6514	0.148*
C9	0.8112 (2)	0.1162 (4)	0.6499 (3)	0.0890 (14)
H7	0.8151	0.0472	0.6799	0.134*
H8	0.8614	0.1616	0.6875	0.134*
H9	0.8114	0.1029	0.5930	0.134*
C10	0.5107 (2)	−0.0342 (3)	0.6544 (2)	0.0459 (9)
C11	0.5223 (2)	−0.0509 (4)	0.7493 (2)	0.0596 (10)
C12	0.5509 (2)	−0.1495 (4)	0.7904 (2)	0.0842 (13)
H12A	0.5571	−0.1610	0.8484	0.101*
H12B	0.5645	−0.2058	0.7607	0.101*
C13	0.5006 (3)	0.0384 (5)	0.7901 (3)	0.1203 (19)
H13A	0.5050	0.0153	0.8474	0.180*
H13B	0.4407	0.0623	0.7511	0.180*
H13C	0.5413	0.0982	0.7997	0.180*
Cu1	0.95058 (2)	0.58684 (3)	0.95769 (2)	0.04257 (13)
O2	0.95450 (14)	0.6179 (2)	1.07602 (13)	0.0538 (6)
O1	1.03977 (14)	0.4737 (2)	1.14736 (13)	0.0557 (6)
O4	0.84923 (13)	0.4861 (2)	0.92871 (14)	0.0580 (6)
O3	1.06707 (14)	0.6594 (2)	1.00035 (15)	0.0581 (6)
N3	0.87554 (16)	0.7370 (2)	0.89766 (16)	0.0459 (7)
N4	0.7646 (2)	0.6533 (3)	0.7748 (2)	0.1019 (13)
H4A	0.7880	0.5907	0.7981	0.122*
H4B	0.7171	0.6557	0.7233	0.122*
C14	0.8020 (2)	0.7465 (4)	0.8181 (2)	0.0595 (10)
C15	0.7644 (3)	0.8481 (4)	0.7818 (3)	0.0766 (13)
H14	0.7130	0.8525	0.7264	0.092*
C16	0.8035 (3)	0.9387 (4)	0.8278 (3)	0.0878 (14)
H15	0.7798	1.0075	0.8040	0.105*
C17	0.8792 (3)	0.9320 (4)	0.9108 (3)	0.0791 (12)
H16	0.9065	0.9950	0.9440	0.095*
C18	0.9116 (2)	0.8313 (3)	0.9417 (2)	0.0580 (10)
H18	0.9626	0.8264	0.9974	0.070*
C19	0.9986 (2)	0.5606 (3)	1.1453 (2)	0.0438 (8)
C20	1.0036 (2)	0.6006 (3)	1.2327 (2)	0.0485 (9)
C21	0.9650 (2)	0.7007 (4)	1.2336 (2)	0.0756 (12)
H21A	0.9676	0.7271	1.2874	0.091*
H21B	0.9364	0.7417	1.1805	0.091*
C22	1.0486 (2)	0.5319 (4)	1.3096 (2)	0.0833 (13)
H22A	1.0584	0.5718	1.3634	0.125*
H22B	1.1051	0.5096	1.3139	0.125*
H22C	1.0129	0.4678	1.3037	0.125*
C23	0.8592 (2)	0.3867 (3)	0.9520 (2)	0.0484 (9)
C24	0.7760 (2)	0.3184 (3)	0.9224 (2)	0.0632 (10)
C25	0.6949 (3)	0.3669 (4)	0.8807 (3)	0.1101 (17)
H25A	0.6434	0.3249	0.8636	0.132*
H25B	0.6904	0.4423	0.8691	0.132*
C26	0.7873 (3)	0.2029 (4)	0.9421 (4)	0.1107 (17)
H26A	0.7305	0.1706	0.9287	0.166*
H26B	0.8280	0.1923	1.0052	0.166*
H26C	0.8108	0.1683	0.9057	0.166*

	U11	U22	U33	U12	U13	U23
Cu2	0.0353 (2)	0.0501 (3)	0.0383 (2)	0.00534 (19)	0.01493 (17)	0.0075 (2)
O6	0.0419 (13)	0.0637 (18)	0.0629 (14)	−0.0030 (13)	0.0160 (12)	0.0034 (14)
O5	0.0347 (13)	0.0625 (18)	0.0670 (15)	0.0007 (13)	0.0182 (11)	0.0027 (14)
O7	0.0655 (15)	0.0628 (17)	0.0452 (13)	0.0154 (14)	0.0304 (12)	0.0141 (12)
O8	0.0555 (14)	0.0648 (17)	0.0423 (12)	0.0132 (13)	0.0253 (11)	0.0124 (12)
N1	0.0351 (14)	0.0552 (19)	0.0365 (13)	0.0051 (14)	0.0171 (12)	0.0022 (13)
N2	0.064 (2)	0.088 (3)	0.126 (3)	0.013 (2)	0.067 (2)	0.023 (2)
C1	0.0408 (19)	0.061 (3)	0.0449 (19)	0.0041 (19)	0.0176 (16)	−0.0011 (19)
C2	0.067 (3)	0.050 (3)	0.068 (2)	0.003 (2)	0.027 (2)	0.000 (2)
C3	0.070 (3)	0.066 (3)	0.075 (3)	0.023 (2)	0.025 (2)	−0.007 (2)
C4	0.056 (2)	0.083 (3)	0.069 (3)	0.015 (2)	0.035 (2)	−0.005 (2)
C5	0.047 (2)	0.066 (3)	0.0431 (18)	0.007 (2)	0.0234 (16)	−0.0004 (19)
C6	0.041 (2)	0.064 (3)	0.0389 (19)	−0.007 (2)	0.0156 (17)	0.0116 (19)
C7	0.046 (2)	0.070 (3)	0.063 (2)	−0.010 (2)	0.0150 (19)	0.016 (2)
C8	0.078 (3)	0.084 (4)	0.159 (5)	−0.031 (3)	0.013 (3)	−0.038 (4)
C9	0.054 (2)	0.119 (4)	0.080 (3)	−0.017 (3)	0.019 (2)	0.014 (3)
C10	0.0346 (19)	0.061 (3)	0.0382 (18)	−0.0059 (18)	0.0136 (15)	0.0036 (18)
C11	0.060 (2)	0.081 (3)	0.0368 (19)	0.004 (2)	0.0221 (17)	0.007 (2)
C12	0.104 (3)	0.099 (4)	0.051 (2)	0.012 (3)	0.037 (2)	0.023 (2)
C13	0.181 (5)	0.128 (5)	0.063 (3)	0.028 (4)	0.066 (3)	0.001 (3)
Cu1	0.0397 (2)	0.0478 (3)	0.0397 (2)	0.0095 (2)	0.01785 (18)	0.00255 (19)
O2	0.0624 (14)	0.0598 (16)	0.0409 (12)	0.0190 (13)	0.0254 (11)	0.0052 (12)
O1	0.0651 (15)	0.0638 (18)	0.0424 (12)	0.0192 (14)	0.0283 (11)	0.0022 (12)
O4	0.0377 (13)	0.0662 (18)	0.0614 (14)	0.0051 (13)	0.0154 (11)	0.0078 (14)
O3	0.0415 (13)	0.0556 (17)	0.0765 (15)	0.0017 (12)	0.0267 (12)	0.0023 (14)
N3	0.0377 (15)	0.056 (2)	0.0390 (14)	0.0134 (15)	0.0136 (12)	0.0087 (14)
N4	0.090 (3)	0.105 (3)	0.057 (2)	0.010 (2)	−0.0116 (18)	0.002 (2)
C14	0.052 (2)	0.074 (3)	0.050 (2)	0.014 (2)	0.0207 (19)	0.010 (2)
C15	0.065 (3)	0.099 (4)	0.057 (2)	0.036 (3)	0.020 (2)	0.030 (3)
C16	0.098 (4)	0.079 (4)	0.091 (3)	0.042 (3)	0.047 (3)	0.036 (3)
C17	0.092 (3)	0.059 (3)	0.097 (3)	0.021 (3)	0.054 (3)	0.015 (3)
C18	0.060 (2)	0.054 (3)	0.062 (2)	0.012 (2)	0.0304 (19)	0.006 (2)
C19	0.0379 (18)	0.056 (2)	0.0425 (19)	−0.0068 (18)	0.0229 (16)	−0.0076 (18)
C20	0.0406 (19)	0.066 (3)	0.0394 (18)	−0.0094 (18)	0.0186 (15)	−0.0132 (18)
C21	0.092 (3)	0.084 (3)	0.056 (2)	0.011 (3)	0.038 (2)	−0.019 (2)
C22	0.091 (3)	0.106 (4)	0.052 (2)	0.001 (3)	0.032 (2)	−0.008 (3)
C23	0.047 (2)	0.054 (3)	0.047 (2)	−0.0013 (19)	0.0234 (17)	−0.0084 (18)
C24	0.052 (2)	0.065 (3)	0.071 (2)	−0.005 (2)	0.026 (2)	−0.015 (2)
C25	0.046 (2)	0.087 (4)	0.167 (5)	−0.001 (3)	0.023 (3)	−0.002 (4)
C26	0.083 (3)	0.067 (3)	0.174 (5)	−0.014 (3)	0.052 (3)	−0.008 (4)

Cu2—O7	1.960 (2)	Cu1—O3	1.962 (2)
Cu2—O8	1.968 (2)	Cu1—O1ii	1.966 (2)
Cu2—O6	1.970 (2)	Cu1—O4	1.971 (2)
Cu2—O5i	1.985 (2)	Cu1—O2	1.971 (2)
Cu2—N1	2.183 (3)	Cu1—N3	2.178 (3)
Cu2—Cu2i	2.6528 (8)	Cu1—Cu1ii	2.6498 (8)
O6—C6	1.250 (4)	O2—C19	1.253 (4)
O5—C6	1.252 (4)	O1—C19	1.253 (4)
O5—Cu2i	1.985 (2)	O1—Cu1ii	1.966 (2)
O7—C10	1.258 (4)	O4—C23	1.252 (4)
O8—C10i	1.249 (4)	O3—C23ii	1.256 (4)
N1—C1	1.335 (4)	N3—C14	1.336 (4)
N1—C5	1.338 (4)	N3—C18	1.341 (4)
N2—C5	1.340 (4)	N4—C14	1.332 (5)
N2—H2A	0.8600	N4—H4A	0.8600
N2—H2B	0.8600	N4—H4B	0.8600
C1—C2	1.352 (5)	C14—C15	1.388 (5)
C1—H1	0.9300	C15—C16	1.327 (6)
C2—C3	1.381 (5)	C15—H14	0.9300
C2—H2	0.9300	C16—C17	1.382 (5)
C3—C4	1.349 (5)	C16—H15	0.9300
C3—H3	0.9300	C17—C18	1.339 (5)
C4—C5	1.398 (5)	C17—H16	0.9300
C4—H4	0.9300	C18—H18	0.9300
C6—C7	1.501 (5)	C19—C20	1.495 (4)
C7—C8	1.368 (6)	C20—C21	1.380 (5)
C7—C9	1.445 (5)	C20—C22	1.416 (5)
C8—H5	0.9300	C21—H21A	0.9300
C8—H6	0.9300	C21—H21B	0.9300
C9—H7	0.9600	C22—H22A	0.9600
C9—H8	0.9600	C22—H22B	0.9600
C9—H9	0.9600	C22—H22C	0.9600
C10—O8i	1.249 (4)	C23—O3ii	1.256 (4)
C10—C11	1.508 (4)	C23—C24	1.502 (5)
C11—C12	1.350 (6)	C24—C25	1.351 (5)
C11—C13	1.412 (6)	C24—C26	1.429 (6)
C12—H12A	0.9300	C25—H25A	0.9300
C12—H12B	0.9300	C25—H25B	0.9300
C13—H13A	0.9600	C26—H26A	0.9600
C13—H13B	0.9600	C26—H26B	0.9600
C13—H13C	0.9600	C26—H26C	0.9600
O7—Cu2—O8	167.76 (9)	O3—Cu1—O1ii	90.51 (9)
O7—Cu2—O6	88.23 (9)	O3—Cu1—O4	167.62 (10)
O8—Cu2—O6	89.74 (9)	O1ii—Cu1—O4	88.24 (10)
O7—Cu2—O5i	90.42 (10)	O3—Cu1—O2	89.23 (9)
O8—Cu2—O5i	88.94 (9)	O1ii—Cu1—O2	167.56 (9)
O6—Cu2—O5i	167.47 (10)	O4—Cu1—O2	89.34 (9)
O7—Cu2—N1	98.41 (9)	O3—Cu1—N3	93.68 (10)
O8—Cu2—N1	93.81 (9)	O1ii—Cu1—N3	100.03 (10)
O6—Cu2—N1	96.13 (10)	O4—Cu1—N3	98.67 (10)
O5i—Cu2—N1	96.39 (10)	O2—Cu1—N3	92.39 (9)
O7—Cu2—Cu2i	84.33 (7)	O3—Cu1—Cu1ii	83.37 (7)
O8—Cu2—Cu2i	83.48 (7)	O1ii—Cu1—Cu1ii	83.38 (7)
O6—Cu2—Cu2i	85.58 (7)	O4—Cu1—Cu1ii	84.24 (7)
O5i—Cu2—Cu2i	81.89 (7)	O2—Cu1—Cu1ii	84.24 (7)
N1—Cu2—Cu2i	176.80 (6)	N3—Cu1—Cu1ii	175.54 (8)
C6—O6—Cu2	121.8 (2)	C19—O2—Cu1	122.8 (2)
C6—O5—Cu2i	125.4 (2)	C19—O1—Cu1ii	124.1 (2)
C10—O7—Cu2	122.5 (2)	C23—O4—Cu1	122.9 (2)
C10i—O8—Cu2	123.3 (2)	C23ii—O3—Cu1	124.3 (2)
C1—N1—C5	116.5 (3)	C14—N3—C18	116.5 (3)
C1—N1—Cu2	115.9 (2)	C14—N3—Cu1	127.1 (3)
C5—N1—Cu2	127.5 (3)	C18—N3—Cu1	116.2 (2)
C5—N2—H2A	120.0	C14—N4—H4A	120.0
C5—N2—H2B	120.0	C14—N4—H4B	120.0
H2A—N2—H2B	120.0	H4A—N4—H4B	120.0
N1—C1—C2	125.6 (3)	N4—C14—N3	116.9 (4)
N1—C1—H1	117.2	N4—C14—C15	120.7 (4)
C2—C1—H1	117.2	N3—C14—C15	122.4 (4)
C1—C2—C3	116.9 (4)	C16—C15—C14	118.6 (4)
C1—C2—H2	121.5	C16—C15—H14	120.7
C3—C2—H2	121.5	C14—C15—H14	120.7
C4—C3—C2	120.2 (4)	C15—C16—C17	120.7 (4)
C4—C3—H3	119.9	C15—C16—H15	119.7
C2—C3—H3	119.9	C17—C16—H15	119.7
C3—C4—C5	119.0 (3)	C18—C17—C16	117.5 (4)
C3—C4—H4	120.5	C18—C17—H16	121.3
C5—C4—H4	120.5	C16—C17—H16	121.3
N1—C5—N2	117.6 (3)	C17—C18—N3	124.5 (4)
N1—C5—C4	121.8 (4)	C17—C18—H18	117.8
N2—C5—C4	120.6 (3)	N3—C18—H18	117.8
O6—C6—O5	125.1 (3)	O2—C19—O1	125.3 (3)
O6—C6—C7	117.6 (4)	O2—C19—C20	117.1 (3)
O5—C6—C7	117.2 (3)	O1—C19—C20	117.6 (3)
C8—C7—C9	125.1 (4)	C21—C20—C22	124.5 (3)
C8—C7—C6	117.7 (4)	C21—C20—C19	118.7 (3)
C9—C7—C6	117.2 (4)	C22—C20—C19	116.8 (3)
C7—C8—H5	120.0	C20—C21—H21A	120.0
C7—C8—H6	120.0	C20—C21—H21B	120.0
H5—C8—H6	120.0	H21A—C21—H21B	120.0
C7—C9—H7	109.5	C20—C22—H22A	109.5
C7—C9—H8	109.5	C20—C22—H22B	109.5
H7—C9—H8	109.5	H22A—C22—H22B	109.5
C7—C9—H9	109.5	C20—C22—H22C	109.5
H7—C9—H9	109.5	H22A—C22—H22C	109.5
H8—C9—H9	109.5	H22B—C22—H22C	109.5
O8i—C10—O7	126.2 (3)	O4—C23—O3ii	125.1 (3)
O8i—C10—C11	117.1 (3)	O4—C23—C24	117.2 (3)
O7—C10—C11	116.7 (3)	O3ii—C23—C24	117.6 (3)
C12—C11—C13	123.1 (3)	C25—C24—C26	122.6 (4)
C12—C11—C10	119.4 (4)	C25—C24—C23	120.0 (4)
C13—C11—C10	117.4 (4)	C26—C24—C23	117.4 (4)
C11—C12—H12A	120.0	C24—C25—H25A	120.0
C11—C12—H12B	120.0	C24—C25—H25B	120.0
H12A—C12—H12B	120.0	H25A—C25—H25B	120.0
C11—C13—H13A	109.5	C24—C26—H26A	109.5
C11—C13—H13B	109.5	C24—C26—H26B	109.5
H13A—C13—H13B	109.5	H26A—C26—H26B	109.5
C11—C13—H13C	109.5	C24—C26—H26C	109.5
H13A—C13—H13C	109.5	H26A—C26—H26C	109.5
H13B—C13—H13C	109.5	H26B—C26—H26C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5i	0.86	2.23	2.963 (4)	144
N2—H2B···O2iii	0.86	2.58	3.334 (3)	148
N4—H4A···O4	0.86	2.30	3.051 (4)	145

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O5i	0.86	2.23	2.963 (4)	144
N4—H4A⋯O4	0.86	2.30	3.051 (4)	145

Symmetry code: (i) .