Poly[diaqua­bis­([mu]₃-2,2-dimethyl­propane­dioato)calcium(II)copper(II)]

The title complex, [CaCu(C₅H₆O₄)₂(H₂O)₂]_n, is the first heterobimetallic complex based on a substituted malonate dianion. The Cu^II cation and two independent 2,2-dimethyl­malonate (or 2,2-dimethyl­propane­dioate) dianions build up a robust dianionic [Cu(C₅H₆O₄)₂]^2- complex, which acts as a building block to coordinate to four Ca²⁺ cations. Each Cu^II centre is in a four-coordinate square plane of dimethyl­malonate O atoms, while each Ca^II atom is in an eight-coordinate distorted bicapped trigonal-prismatic environment of six O atoms from four different dimethyl­malonate groups and two water mol­ecules. This arrangement creates a two-dimensional layer connectivity of the structure. The dianionic [Cu(C₅H₆O₄)₂]^2- units are involved in different inter­mole­cular hydrogen-bonding inter­actions with water mol­ecules via the formation of hydrogen-bonded rings of graph sets R₁²(8) and R(6) within this layer. The crystal was nonmerohedrally twinned by rotation about [011] with a major twin volume fraction of 0.513 (3).

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Poly[diaquabis(µ₃-2,2-dimethylpropanedioato)calcium(II)copper(II)]

Crystal data

[CaCu(C5H6O4)2(H2O)2]	Z = 2
Mr = 399.85	F(000) = 410
Triclinic, P1	Dx = 1.773 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0113 (18) Å	Cell parameters from 3569 reflections
b = 9.6052 (19) Å	θ = 2.2–27.9°
c = 9.6248 (19) Å	µ = 1.85 mm^−1
α = 79.95 (3)°	T = 294 K
β = 72.14 (3)°	Plate, blue
γ = 71.40 (3)°	0.14 × 0.12 × 0.06 mm
V = 748.8 (3) Å^3

Data collection

Rigaku Saturn CCD area-detector diffractometer	2608 independent reflections
Radiation source: rotating anode	1622 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.000
Detector resolution: 27.892 pixels mm^-1	θmax = 25.0°, θmin = 2.2°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −10→11
Tmin = 0.783, Tmax = 0.887	l = −10→11
2608 measured reflections

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.152	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0828P)^2] where P = (Fo^2 + 2Fc^2)/3
2608 reflections	(Δ/σ)max = 0.001
204 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.95 e Å^−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
Ca1	0.50139 (19)	0.74114 (16)	0.24000 (16)	0.0360 (3)
Cu1	0.68110 (10)	0.60676 (9)	0.79755 (9)	0.0398 (3)
O1	0.6532 (6)	0.8895 (6)	0.0625 (6)	0.0466 (14)
H1A	0.6460	0.9801	0.0618	0.056*
H1B	0.6837	0.8606	−0.0229	0.056*
O2	0.3540 (6)	0.6420 (6)	0.4678 (6)	0.0432 (14)
H2A	0.3555	0.5653	0.4353	0.052*
H2B	0.3677	0.6273	0.5536	0.052*
O3	0.6702 (7)	0.5950 (6)	1.0012 (6)	0.0457 (14)
O4	0.6846 (7)	0.4778 (6)	1.2163 (7)	0.0484 (17)
O5	0.6781 (7)	0.4040 (6)	0.8127 (6)	0.0437 (13)
O6	0.6657 (7)	0.1939 (7)	0.9324 (6)	0.0479 (17)
C1	0.7128 (9)	0.4766 (8)	1.0840 (8)	0.0369 (18)
C2	0.8101 (7)	0.3313 (7)	1.0119 (9)	0.0335 (14)
C3	0.7120 (9)	0.3066 (8)	0.9139 (9)	0.0376 (19)
C4	0.9751 (8)	0.3513 (9)	0.9130 (10)	0.061 (2)
H4A	1.0343	0.2659	0.8596	0.092*
H4B	1.0373	0.3635	0.9728	0.092*
H4C	0.9560	0.4369	0.8454	0.092*
C5	0.8364 (10)	0.2031 (9)	1.1247 (10)	0.064 (2)
H5A	0.7335	0.1982	1.1908	0.095*
H5B	0.9042	0.2158	1.1786	0.095*
H5C	0.8882	0.1135	1.0769	0.095*
O7	0.6725 (8)	0.6245 (7)	0.6010 (6)	0.0529 (15)
O8	0.6612 (8)	0.7436 (7)	0.3870 (7)	0.0504 (16)
O9	0.6695 (9)	0.8098 (6)	0.7901 (6)	0.0591 (17)
O10	0.6731 (8)	1.0297 (7)	0.6765 (7)	0.0563 (18)
C6	0.6996 (10)	0.7290 (8)	0.4991 (8)	0.0391 (19)
C7	0.7890 (8)	0.8295 (8)	0.5258 (9)	0.0396 (15)
C8	0.7017 (10)	0.8968 (8)	0.6745 (9)	0.0393 (19)
C9	0.9617 (9)	0.7333 (11)	0.5366 (10)	0.069 (2)
H9A	1.0181	0.7938	0.5565	0.103*
H9B	1.0216	0.6904	0.4456	0.103*
H9C	0.9516	0.6563	0.6142	0.103*
C10	0.7977 (12)	0.9508 (10)	0.4016 (9)	0.073 (3)
H10A	0.6930	1.0222	0.4132	0.110*
H10B	0.8292	0.9090	0.3097	0.110*
H10C	0.8763	0.9979	0.4034	0.110*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0443 (7)	0.0318 (10)	0.0308 (10)	−0.0068 (7)	−0.0126 (7)	−0.0032 (5)
Cu1	0.0521 (5)	0.0354 (6)	0.0298 (6)	−0.0128 (4)	−0.0105 (4)	0.0029 (3)
O1	0.059 (3)	0.046 (3)	0.040 (3)	−0.022 (3)	−0.015 (3)	−0.002 (3)
O2	0.057 (3)	0.038 (3)	0.041 (3)	−0.018 (2)	−0.019 (3)	0.000 (3)
O3	0.063 (4)	0.036 (3)	0.031 (3)	−0.015 (3)	−0.001 (3)	−0.004 (2)
O4	0.060 (4)	0.041 (4)	0.040 (4)	0.008 (3)	−0.029 (3)	−0.007 (3)
O5	0.067 (4)	0.039 (3)	0.033 (3)	−0.017 (3)	−0.028 (3)	0.008 (2)
O6	0.071 (4)	0.051 (4)	0.042 (4)	−0.045 (3)	−0.024 (3)	0.013 (3)
C1	0.046 (5)	0.021 (4)	0.032 (4)	−0.003 (3)	−0.003 (4)	0.001 (3)
C2	0.037 (3)	0.018 (4)	0.046 (5)	−0.007 (3)	−0.010 (4)	−0.010 (3)
C3	0.043 (4)	0.024 (4)	0.046 (5)	−0.005 (3)	−0.011 (4)	−0.013 (4)
C4	0.049 (4)	0.060 (6)	0.063 (6)	0.007 (4)	−0.014 (4)	−0.021 (4)
C5	0.088 (6)	0.047 (5)	0.063 (6)	−0.016 (5)	−0.034 (5)	−0.005 (4)
O7	0.083 (4)	0.058 (4)	0.037 (3)	−0.045 (3)	−0.024 (3)	0.007 (3)
O8	0.067 (4)	0.054 (4)	0.050 (4)	−0.023 (3)	−0.045 (3)	0.009 (3)
O9	0.109 (5)	0.036 (3)	0.026 (3)	−0.018 (3)	−0.015 (3)	0.003 (3)
O10	0.077 (5)	0.043 (4)	0.039 (4)	−0.026 (3)	0.004 (3)	0.004 (3)
C6	0.051 (5)	0.033 (4)	0.029 (4)	−0.012 (4)	0.001 (4)	−0.008 (4)
C7	0.049 (4)	0.026 (4)	0.032 (5)	−0.004 (3)	−0.001 (4)	−0.003 (3)
C8	0.045 (4)	0.033 (4)	0.032 (5)	−0.005 (3)	−0.005 (4)	−0.002 (4)
C9	0.046 (4)	0.104 (8)	0.070 (7)	−0.024 (5)	−0.014 (4)	−0.037 (5)
C10	0.129 (8)	0.073 (7)	0.037 (5)	−0.070 (6)	−0.009 (5)	0.002 (4)

Geometric parameters (Å, º)

Ca1—O4^i	2.546 (6)	C2—C4	1.551 (9)
Ca1—O6^ii	2.446 (6)	C2—C3	1.565 (12)
Ca1—O5^ii	2.647 (5)	C4—H4A	0.9600
Ca1—O8	2.315 (6)	C4—H4B	0.9600
Ca1—O10^iii	2.366 (7)	C4—H4C	0.9600
Ca1—O2	2.402 (5)	C5—H5A	0.9600
Ca1—O1	2.405 (5)	C5—H5B	0.9600
Ca1—O3^i	2.681 (5)	C5—H5C	0.9600
Cu1—O7	1.893 (5)	O7—C6	1.301 (10)
Cu1—O9	1.909 (5)	O8—C6	1.204 (10)
Cu1—O3	1.917 (5)	O9—C8	1.286 (10)
Cu1—O5	1.936 (5)	O10—C8	1.221 (9)
O1—H1A	0.8499	C6—C7	1.535 (13)
O1—H1B	0.8490	C7—C10	1.519 (9)
O2—H2A	0.8445	C7—C8	1.547 (11)
O2—H2B	0.8531	C7—C9	1.560 (10)
O3—C1	1.291 (9)	C9—H9A	0.9600
O4—C1	1.222 (9)	C9—H9B	0.9600
O5—C3	1.265 (9)	C9—H9C	0.9600
O6—C3	1.246 (9)	C10—H10A	0.9600
C1—C2	1.543 (10)	C10—H10B	0.9600
C2—C5	1.502 (9)	C10—H10C	0.9600
O8—Ca1—O10^iii	88.52 (18)	C1—O3—Cu1	126.6 (5)
O8—Ca1—O2	80.8 (2)	C1—O3—Ca1^iv	89.8 (4)
O10^iii—Ca1—O2	83.7 (2)	Cu1—O3—Ca1^iv	140.3 (3)
O8—Ca1—O1	85.5 (2)	C1—O4—Ca1^iv	97.9 (5)
O10^iii—Ca1—O1	84.3 (2)	C3—O5—Cu1	125.6 (5)
O2—Ca1—O1	162.03 (15)	C3—O5—Ca1^ii	90.4 (4)
O8—Ca1—O6^ii	164.9 (2)	Cu1—O5—Ca1^ii	137.4 (3)
O10^iii—Ca1—O6^ii	80.9 (2)	C3—O6—Ca1^ii	100.5 (5)
O2—Ca1—O6^ii	108.5 (2)	O4—C1—O3	121.9 (7)
O1—Ca1—O6^ii	82.71 (19)	O4—C1—C2	119.2 (7)
O8—Ca1—O4^i	81.84 (19)	O3—C1—C2	118.8 (6)
O10^iii—Ca1—O4^i	166.0 (2)	O4—C1—Ca1^iv	58.1 (4)
O2—Ca1—O4^i	84.7 (2)	O3—C1—Ca1^iv	64.4 (3)
O1—Ca1—O4^i	104.9 (2)	C2—C1—Ca1^iv	174.3 (5)
O6^ii—Ca1—O4^i	110.38 (15)	C5—C2—C1	111.5 (7)
O8—Ca1—O5^ii	144.8 (2)	C5—C2—C4	110.6 (6)
O10^iii—Ca1—O5^ii	107.8 (2)	C1—C2—C4	107.6 (7)
O2—Ca1—O5^ii	70.57 (18)	C5—C2—C3	110.4 (7)
O1—Ca1—O5^ii	126.12 (19)	C1—C2—C3	107.6 (5)
O6^ii—Ca1—O5^ii	50.00 (17)	C4—C2—C3	109.1 (7)
O4^i—Ca1—O5^ii	75.58 (18)	O6—C3—O5	118.7 (7)
O8—Ca1—O3^i	113.1 (2)	O6—C3—C2	122.1 (7)
O10^iii—Ca1—O3^i	144.3 (2)	O5—C3—C2	119.2 (6)
O2—Ca1—O3^i	126.02 (18)	O6—C3—Ca1^ii	54.9 (4)
O1—Ca1—O3^i	70.31 (19)	O5—C3—Ca1^ii	64.2 (4)
O6^ii—Ca1—O3^i	71.6 (2)	C2—C3—Ca1^ii	173.6 (5)
O4^i—Ca1—O3^i	49.64 (18)	C2—C4—H4A	109.5
O5^ii—Ca1—O3^i	71.12 (14)	C2—C4—H4B	109.5
O8—Ca1—C3^ii	170.2 (2)	H4A—C4—H4B	109.5
O10^iii—Ca1—C3^ii	95.7 (2)	C2—C4—H4C	109.5
O2—Ca1—C3^ii	90.8 (2)	H4A—C4—H4C	109.5
O1—Ca1—C3^ii	103.7 (2)	H4B—C4—H4C	109.5
O6^ii—Ca1—C3^ii	24.6 (2)	C2—C5—H5A	109.5
O4^i—Ca1—C3^ii	92.37 (19)	C2—C5—H5B	109.5
O5^ii—Ca1—C3^ii	25.47 (19)	H5A—C5—H5B	109.5
O3^i—Ca1—C3^ii	67.85 (19)	C2—C5—H5C	109.5
O8—Ca1—C1^i	98.9 (2)	H5A—C5—H5C	109.5
O10^iii—Ca1—C1^i	170.0 (2)	H5B—C5—H5C	109.5
O2—Ca1—C1^i	104.1 (2)	C6—O7—Cu1	128.0 (5)
O1—Ca1—C1^i	89.5 (2)	C6—O8—Ca1	156.5 (6)
O6^ii—Ca1—C1^i	90.5 (2)	C8—O9—Cu1	126.9 (5)
O4^i—Ca1—C1^i	24.0 (2)	C8—O10—Ca1^iii	150.8 (6)
O5^ii—Ca1—C1^i	69.7 (2)	O8—C6—O7	121.7 (8)
O3^i—Ca1—C1^i	25.76 (19)	O8—C6—C7	121.3 (8)
C3^ii—Ca1—C1^i	78.09 (16)	O7—C6—C7	116.9 (7)
O8—Ca1—H2A	92.0	C10—C7—C6	109.2 (7)
O10^iii—Ca1—H2A	98.9	C10—C7—C8	110.3 (7)
O2—Ca1—H2A	18.6	C6—C7—C8	110.8 (5)
O1—Ca1—H2A	175.9	C10—C7—C9	111.7 (7)
O6^ii—Ca1—H2A	100.3	C6—C7—C9	108.3 (7)
O4^i—Ca1—H2A	71.5	C8—C7—C9	106.4 (7)
O5^ii—Ca1—H2A	55.4	O10—C8—O9	123.4 (8)
O3^i—Ca1—H2A	107.8	O10—C8—C7	118.0 (7)
C3^ii—Ca1—H2A	78.6	O9—C8—C7	118.5 (6)
C1^i—Ca1—H2A	87.7	C7—C9—H9A	109.5
O7—Cu1—O9	92.55 (18)	C7—C9—H9B	109.5
O7—Cu1—O3	175.2 (3)	H9A—C9—H9B	109.5
O9—Cu1—O3	86.9 (2)	C7—C9—H9C	109.5
O7—Cu1—O5	88.4 (2)	H9A—C9—H9C	109.5
O9—Cu1—O5	176.2 (3)	H9B—C9—H9C	109.5
O3—Cu1—O5	91.84 (17)	C7—C10—H10A	109.5
Ca1—O1—H1A	128.9	C7—C10—H10B	109.5
Ca1—O1—H1B	112.4	H10A—C10—H10B	109.5
H1A—O1—H1B	112.8	C7—C10—H10C	109.5
Ca1—O2—H2A	96.0	H10A—C10—H10C	109.5
Ca1—O2—H2B	131.6	H10B—C10—H10C	109.5
H2A—O2—H2B	113.6
O9—Cu1—O3—C1	−160.8 (7)	C4—C2—C3—O5	−58.4 (8)
O5—Cu1—O3—C1	22.7 (6)	O9—Cu1—O7—C6	17.3 (7)
O9—Cu1—O3—Ca1^iv	46.4 (4)	O5—Cu1—O7—C6	−166.4 (7)
O5—Cu1—O3—Ca1^iv	−130.0 (4)	O10^iii—Ca1—O8—C6	78.8 (15)
O7—Cu1—O5—C3	165.8 (7)	O2—Ca1—O8—C6	−5.0 (15)
O3—Cu1—O5—C3	−19.0 (6)	O1—Ca1—O8—C6	163.2 (15)
O7—Cu1—O5—Ca1^ii	−52.0 (4)	O6^ii—Ca1—O8—C6	124.2 (15)
O3—Cu1—O5—Ca1^ii	123.2 (4)	O4^i—Ca1—O8—C6	−91.0 (15)
Ca1^iv—O4—C1—O3	9.1 (9)	O5^ii—Ca1—O8—C6	−40.7 (16)
Ca1^iv—O4—C1—C2	−174.2 (6)	O3^i—Ca1—O8—C6	−130.4 (15)
Cu1—O3—C1—O4	−171.5 (6)	C1^i—Ca1—O8—C6	−108.0 (15)
Ca1^iv—O3—C1—O4	−8.5 (8)	O7—Cu1—O9—C8	−19.5 (7)
Cu1—O3—C1—C2	11.7 (10)	O3—Cu1—O9—C8	165.3 (8)
Ca1^iv—O3—C1—C2	174.7 (6)	Ca1—O8—C6—O7	36.3 (19)
Cu1—O3—C1—Ca1^iv	−163.0 (6)	Ca1—O8—C6—C7	−146.1 (11)
O4—C1—C2—C5	8.1 (11)	Cu1—O7—C6—O8	−165.7 (6)
O3—C1—C2—C5	−175.0 (7)	Cu1—O7—C6—C7	16.6 (10)
O4—C1—C2—C4	−113.3 (8)	O8—C6—C7—C10	6.6 (10)
O3—C1—C2—C4	63.6 (9)	O7—C6—C7—C10	−175.7 (7)
O4—C1—C2—C3	129.3 (8)	O8—C6—C7—C8	128.3 (8)
O3—C1—C2—C3	−53.8 (8)	O7—C6—C7—C8	−54.0 (8)
Ca1^ii—O6—C3—O5	−6.6 (8)	O8—C6—C7—C9	−115.3 (8)
Ca1^ii—O6—C3—C2	173.2 (5)	O7—C6—C7—C9	62.4 (9)
Cu1—O5—C3—O6	161.5 (5)	Ca1^iii—O10—C8—O9	−44.0 (18)
Ca1^ii—O5—C3—O6	6.0 (7)	Ca1^iii—O10—C8—C7	139.1 (10)
Cu1—O5—C3—C2	−18.4 (10)	Cu1—O9—C8—O10	170.8 (7)
Ca1^ii—O5—C3—C2	−173.8 (6)	Cu1—O9—C8—C7	−12.3 (12)
Cu1—O5—C3—Ca1^ii	155.5 (6)	C10—C7—C8—O10	−9.8 (11)
C5—C2—C3—O6	0.0 (10)	C6—C7—C8—O10	−130.8 (8)
C1—C2—C3—O6	−121.9 (8)	C9—C7—C8—O10	111.6 (8)
C4—C2—C3—O6	121.7 (8)	C10—C7—C8—O9	173.2 (8)
C5—C2—C3—O5	179.8 (7)	C6—C7—C8—O9	52.2 (9)
C1—C2—C3—O5	58.0 (8)	C9—C7—C8—O9	−65.4 (10)

Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+2, −z+1; (iv) x, y, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O6^v	0.85	2.24	2.996 (8)	149
O1—H1B···O9^i	0.85	2.00	2.806 (8)	159
O2—H2A···O7^ii	0.84	2.02	2.851 (7)	168
O2—H2B···O4^vi	0.85	2.24	3.012 (8)	150

Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+1, −z+1; (v) x, y+1, z−1; (vi) −x+1, −y+1, −z+2.