[29H,31H-Tetra­benzo[b,g,l,q]porphinato(2–)-κ⁴N²¹,N²²,N²³,N²⁴]copper(II)

The mol­ecule of the title comound, [Cu(C₃₆H₂₀N₄)], is not entirely planar in the crystal structure (i.e. not D_4h), but is slightly deformed, with only C_i symmetry. The mol­ecules are stacked along the b axis in a herring-bone fashion.

Key indicators

• Single-crystal X-ray study
• T = 93 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.099
• wR factor = 0.266
• Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level A
RINTA01_ALERT_3_A  The value of Rint is greater than 0.20
            Rint given   0.206

Author Response: The single crystal used for the present analysis was extremely small (0.1x0.02x0.02 mm^3^). In addition, the crystallinity was found to be rather poor.

PLAT020_ALERT_3_A The value of Rint is greater than 0.10 .........       0.21

Author Response: The single crystal used for the present analysis was extremely small (0.1x0.02x0.02 mm^3^). In addition, the crystallinity was found to be rather poor.

Alert level C
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.266
PLAT084_ALERT_2_C High R2 Value ..................................       0.27
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.60
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8

   2 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2005); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: CrystalStructure.

[29H,31H-Tetrabenzo[b,g,l,q]porphinato(2-)- κ⁴N²¹,N²²,N²³,N²⁴]copper(II)

Crystal data

[Cu(C36H20N4)]	F(000) = 586.00
Mr = 572.11	Dx = 1.599 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2yn	Cell parameters from 7284 reflections
a = 12.339 (2) Å	θ = 3.0–68.2°
b = 6.5940 (12) Å	µ = 1.58 mm^−1
c = 14.908 (3) Å	T = 93 K
β = 101.537 (12)°	Needle, black
V = 1188.5 (4) Å^3	0.10 × 0.02 × 0.02 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID-F imaging-plate diffractometer	1347 reflections with F^2 > 2σ(F^2)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.206
ω scans	θmax = 68.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→14
Tmin = 0.860, Tmax = 0.969	k = −7→7
11140 measured reflections	l = −17→17
2161 independent reflections

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.099	w = 1/[σ^2(Fo^2) + (0.1369P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.266	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 1.43 e Å^−3
2161 reflections	Δρmin = −0.55 e Å^−3
188 parameters

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using reflections with F² > 2 σ(F²). The weighted R-factor(wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.5000	0.5000	0.5000	0.0298 (5)
N1	0.6275 (4)	0.5827 (8)	0.4407 (3)	0.0321 (12)
N2	0.4170 (4)	0.7492 (7)	0.4497 (3)	0.0290 (12)
C1	0.7281 (5)	0.4816 (9)	0.4474 (4)	0.0287 (14)
C2	0.8008 (5)	0.5987 (10)	0.4021 (4)	0.0330 (14)
C3	0.9096 (5)	0.5686 (10)	0.3913 (4)	0.0355 (15)
C4	0.9576 (5)	0.7181 (9)	0.3470 (4)	0.0348 (15)
C5	0.9004 (5)	0.8934 (10)	0.3124 (4)	0.0344 (15)
C6	0.7908 (5)	0.9248 (10)	0.3230 (4)	0.0332 (14)
C7	0.7438 (4)	0.7743 (9)	0.3686 (3)	0.0279 (13)
C8	0.6347 (4)	0.7599 (9)	0.3938 (4)	0.0288 (13)
C9	0.5556 (4)	0.9077 (10)	0.3739 (3)	0.0285 (13)
C10	0.4538 (4)	0.9015 (9)	0.4005 (4)	0.0286 (13)
C11	0.3717 (4)	1.0609 (9)	0.3781 (4)	0.0279 (13)
C12	0.3714 (4)	1.2484 (9)	0.3331 (4)	0.0303 (14)
C13	0.2757 (5)	1.3617 (9)	0.3200 (4)	0.0311 (14)
C14	0.1827 (5)	1.2935 (9)	0.3520 (4)	0.0322 (14)
C15	0.1836 (4)	1.1166 (10)	0.3990 (4)	0.0338 (14)
C16	0.2808 (5)	0.9988 (8)	0.4134 (4)	0.0276 (13)
C17	0.3111 (4)	0.8060 (9)	0.4587 (4)	0.0277 (13)
C18	0.2448 (5)	0.6994 (9)	0.5068 (4)	0.0299 (13)
H3	0.9492	0.4494	0.4136	0.043*
H4	1.0319	0.7010	0.3398	0.042*
H5	0.9356	0.9919	0.2815	0.041*
H6	0.7507	1.0432	0.3001	0.040*
H9	0.5713	1.0218	0.3397	0.034*
H12	0.4350	1.2954	0.3125	0.036*
H13	0.2726	1.4878	0.2888	0.037*
H14	0.1172	1.3731	0.3406	0.039*
H15	0.1206	1.0736	0.4215	0.041*
H18	0.1744	0.7556	0.5085	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0183 (7)	0.0338 (8)	0.0383 (8)	−0.0001 (5)	0.0079 (5)	0.0005 (5)
N1	0.020 (2)	0.038 (3)	0.039 (2)	0.005 (2)	0.006 (2)	−0.000 (2)
N2	0.018 (2)	0.034 (3)	0.036 (2)	−0.003 (2)	0.007 (2)	−0.003 (2)
C1	0.017 (3)	0.038 (3)	0.031 (3)	−0.003 (2)	0.005 (2)	−0.002 (2)
C2	0.026 (3)	0.040 (3)	0.034 (3)	0.001 (2)	0.007 (2)	−0.001 (2)
C3	0.025 (3)	0.039 (3)	0.044 (3)	0.002 (2)	0.010 (2)	0.002 (3)
C4	0.019 (3)	0.045 (4)	0.040 (3)	0.000 (2)	0.005 (2)	0.000 (3)
C5	0.026 (3)	0.039 (3)	0.042 (3)	0.002 (2)	0.014 (2)	0.000 (3)
C6	0.022 (3)	0.040 (3)	0.038 (3)	0.005 (2)	0.005 (2)	−0.002 (2)
C7	0.015 (3)	0.035 (3)	0.033 (3)	−0.001 (2)	0.003 (2)	−0.004 (2)
C8	0.021 (3)	0.037 (3)	0.028 (3)	−0.003 (2)	0.003 (2)	−0.000 (2)
C9	0.019 (3)	0.040 (3)	0.027 (3)	−0.005 (2)	0.005 (2)	−0.002 (2)
C10	0.023 (3)	0.030 (3)	0.035 (3)	0.003 (2)	0.008 (2)	−0.000 (2)
C11	0.012 (2)	0.032 (3)	0.038 (3)	−0.001 (2)	0.001 (2)	−0.005 (2)
C12	0.019 (3)	0.030 (3)	0.043 (3)	−0.005 (2)	0.010 (2)	−0.001 (2)
C13	0.030 (3)	0.034 (3)	0.026 (3)	−0.001 (2)	−0.002 (2)	−0.001 (2)
C14	0.028 (3)	0.035 (3)	0.034 (3)	0.007 (2)	0.006 (2)	−0.002 (2)
C15	0.019 (3)	0.043 (3)	0.040 (3)	−0.003 (2)	0.008 (2)	−0.003 (3)
C16	0.017 (3)	0.032 (3)	0.032 (3)	−0.002 (2)	0.003 (2)	−0.004 (2)
C17	0.021 (3)	0.030 (3)	0.030 (3)	−0.002 (2)	−0.001 (2)	−0.003 (2)
C18	0.019 (3)	0.040 (3)	0.031 (3)	0.003 (2)	0.005 (2)	−0.006 (2)

Geometric parameters (Å, º)

Cu1—N1	2.027 (5)	C6—H6	0.950
Cu1—N1^i	2.027 (5)	C7—C8	1.471 (8)
Cu1—N2	2.001 (4)	C8—C9	1.369 (8)
Cu1—N2^i	2.001 (4)	C9—C10	1.392 (8)
N1—C1	1.395 (8)	C9—H9	0.950
N1—C8	1.373 (8)	C10—C11	1.451 (8)
N2—C10	1.374 (8)	C11—C12	1.407 (8)
N2—C17	1.391 (8)	C11—C16	1.392 (9)
C1—C2	1.449 (9)	C12—C13	1.378 (8)
C1—C18^i	1.383 (8)	C12—H12	0.950
C2—C3	1.397 (9)	C13—C14	1.402 (9)
C2—C7	1.395 (8)	C13—H13	0.950
C3—C4	1.385 (9)	C14—C15	1.360 (9)
C3—H3	0.950	C14—H14	0.950
C4—C5	1.398 (8)	C15—C16	1.409 (8)
C4—H4	0.950	C15—H15	0.950
C5—C6	1.408 (9)	C16—C17	1.452 (8)
C5—H5	0.950	C17—C18	1.383 (9)
C6—C7	1.393 (9)	C18—H18	0.950
C11···H13^ii	2.797	H5···H12^vii	2.662
H18···H4^iii	2.789	H12···H4^viii	2.466
H3···H3^iv	2.712	H12···H5^viii	2.662
H3···H14^v	2.577	H13···C11^ix	2.797
H4···H18^vi	2.789	H14···H3^x	2.577
H4···H12^vii	2.466	H14···H4^x	2.404
H4···H14^v	2.404
N1—Cu1—N1^i	180.0 (2)	N1—C8—C7	109.9 (5)
N1—Cu1—N2	90.0 (2)	N1—C8—C9	126.9 (5)
N1—Cu1—N2^i	90.0 (2)	C7—C8—C9	123.2 (5)
N1^i—Cu1—N2	90.0 (2)	C8—C9—C10	124.2 (6)
N1^i—Cu1—N2^i	90.0 (2)	C8—C9—H9	117.9
N2—Cu1—N2^i	180.0 (2)	C10—C9—H9	117.9
Cu1—N1—C1	126.7 (4)	N2—C10—C9	126.0 (5)
Cu1—N1—C8	125.9 (4)	N2—C10—C11	111.2 (5)
C1—N1—C8	107.2 (5)	C9—C10—C11	122.8 (5)
Cu1—N2—C10	126.9 (4)	C10—C11—C12	132.9 (5)
Cu1—N2—C17	127.3 (4)	C10—C11—C16	106.2 (5)
C10—N2—C17	105.8 (4)	C12—C11—C16	120.9 (5)
N1—C1—C2	109.7 (5)	C11—C12—C13	117.7 (5)
N1—C1—C18^i	124.9 (6)	C11—C12—H12	121.2
C2—C1—C18^i	125.4 (5)	C13—C12—H12	121.2
C1—C2—C3	132.6 (6)	C12—C13—C14	121.0 (5)
C1—C2—C7	107.1 (5)	C12—C13—H13	119.5
C3—C2—C7	120.3 (6)	C14—C13—H13	119.5
C2—C3—C4	117.8 (6)	C13—C14—C15	121.8 (5)
C2—C3—H3	121.1	C13—C14—H14	119.1
C4—C3—H3	121.1	C15—C14—H14	119.1
C3—C4—C5	122.1 (6)	C14—C15—C16	118.1 (6)
C3—C4—H4	118.9	C14—C15—H15	121.0
C5—C4—H4	118.9	C16—C15—H15	121.0
C4—C5—C6	120.4 (6)	C11—C16—C15	120.4 (5)
C4—C5—H5	119.8	C11—C16—C17	106.3 (5)
C6—C5—H5	119.8	C15—C16—C17	133.2 (6)
C5—C6—C7	116.9 (5)	N2—C17—C16	110.5 (5)
C5—C6—H6	121.5	N2—C17—C18	125.2 (5)
C7—C6—H6	121.5	C16—C17—C18	124.2 (5)
C2—C7—C6	122.5 (5)	C1^i—C18—C17	125.8 (5)
C2—C7—C8	106.1 (5)	C1^i—C18—H18	117.1
C6—C7—C8	131.5 (5)	C17—C18—H18	117.1

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x−1, y, z; (iv) −x+2, −y+1, −z+1; (v) x+1, y−1, z; (vi) x+1, y, z; (vii) −x+3/2, y−1/2, −z+1/2; (viii) −x+3/2, y+1/2, −z+1/2; (ix) −x+1/2, y+1/2, −z+1/2; (x) x−1, y+1, z.