4-Chloro-N-[4-(8-chloro-5H-dibenzo­[b,e][1,4]­diazepin-11-yl)-1-methylpiperazinio]benzamidate di­chloro­methane solvate

The structure of the title compound, C₂₅H₂₃Cl₂N₅O·CH₂Cl₂, confirms the presence of the buckled nature of the dibenzodiazepine nucleus, with the central seven-membered heterocycle in a boat conformation, the dihedral angle between the planes of the aromatic rings being similar to that found for the parent compound, clozapine and related structures. The piperazine ring displays an almost perfect chair conformation, with the methyl and chloro­benz­imide groups assuming equatorial and axial orientations, respectively, at the cationic nitro­gen site. At the other piperazine N atom, the dibenzodiazepine nucleus assumes an axial orientation. The relative positions of the dibenzodiazepine and piperazine ring systems is controlled by the planarity of the piperazine N atom in the amidine moiety.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.053
• wR factor = 0.111
• Data-to-parameter ratio = 22.8

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT374_ALERT_2_A Long   N - N         Bond  N4     -   N5     ...       1.47 Ang.

Author Response: This is not an atypical bond length for a N-N zwitterion, see for example Cambridge data base entries BEDJOJ, GILYIJ, PABDIF, QOMBAV, TMABZA10, WEFHAQ, IPADAE and IPADEI.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?

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

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

---

Computing details

Data collection: COLLECT (Bruker, 1997–2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

1-(4-Chlorobenzoylamino)-4-(8-chloro-5H-dibenzo[b,e][1,4]diazepin-11-yl)- 1-methylhexahydropyrazin-1-ium dichloromethane solvate

Crystal data

C25H23Cl2N5O·CH2Cl2	F(000) = 1168
Mr = 565.31	Dx = 1.46 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 42938 reflections
a = 14.1386 (2) Å	θ = 3–30°
b = 9.9659 (1) Å	µ = 0.49 mm^−1
c = 18.2523 (3) Å	T = 123 K
β = 90.2765 (5)°	Acicular, yellow
V = 2571.79 (6) Å^3	0.35 × 0.08 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	Rint = 0.070
CCD rotation images, thick–slice π and ω scans	θmax = 30.0°, θmin = 3.0°
41694 measured reflections	h = −19→19
7441 independent reflections	k = −13→12
4972 reflections with I > 2σ(I)	l = −25→25

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.053	w = 1/[σ^2(Fo^2) + (0.0419P)^2 + 1.7861P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.111	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.58 e Å^−3
7441 reflections	Δρmin = −0.74 e Å^−3
326 parameters

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.

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

	x	y	z	Uiso*/Ueq
C1	0.34345 (14)	0.57370 (19)	0.16548 (11)	0.0166 (4)
C2	0.36519 (14)	0.67588 (19)	0.21372 (11)	0.0157 (4)
H2	0.3252	0.6927	0.2544	0.019*
C3	0.44580 (13)	0.75492 (18)	0.20316 (10)	0.0126 (4)
C4	0.50372 (13)	0.72724 (18)	0.14266 (11)	0.0136 (4)
C5	0.48043 (14)	0.62251 (18)	0.09509 (11)	0.0156 (4)
H5	0.5201	0.6042	0.0544	0.019*
C6	0.40054 (14)	0.54492 (19)	0.10620 (11)	0.0171 (4)
H6	0.3853	0.4734	0.0738	0.02*
C7	0.57366 (13)	0.94168 (19)	0.12127 (11)	0.0136 (4)
C8	0.60193 (14)	1.0028 (2)	0.05622 (11)	0.0174 (4)
H8	0.6325	0.9512	0.0195	0.021*
C9	0.58571 (15)	1.1379 (2)	0.04501 (11)	0.0199 (4)
H9	0.6064	1.1793	0.001	0.024*
C10	0.53941 (15)	1.2134 (2)	0.09746 (12)	0.0207 (5)
H10	0.5258	1.3054	0.0886	0.025*
C11	0.51306 (14)	1.15421 (19)	0.16277 (11)	0.0179 (4)
H11	0.4817	1.2062	0.1989	0.021*
C12	0.53197 (13)	1.01850 (18)	0.17630 (10)	0.0134 (4)
C13	0.51035 (13)	0.95792 (18)	0.24864 (10)	0.0133 (4)
C14	0.61698 (14)	1.11399 (19)	0.31533 (11)	0.0170 (4)
H14A	0.6059	1.1984	0.3426	0.02*
H14B	0.6398	1.1378	0.2658	0.02*
C15	0.69233 (14)	1.0320 (2)	0.35482 (11)	0.0171 (4)
H15A	0.7073	0.9513	0.3254	0.02*
H15B	0.7508	1.0861	0.3595	0.02*
C16	0.49448 (14)	0.99746 (19)	0.38074 (10)	0.0143 (4)
H16A	0.436	0.9438	0.3746	0.017*
H16B	0.4787	1.0777	0.4102	0.017*
C17	0.56754 (13)	0.91477 (18)	0.42143 (11)	0.0145 (4)
H17A	0.5428	0.8911	0.4704	0.017*
H17B	0.5789	0.8303	0.3943	0.017*
C18	0.73007 (15)	0.8951 (2)	0.46448 (12)	0.0221 (5)
H18A	0.7924	0.9379	0.466	0.033*
H18B	0.7335	0.8127	0.4354	0.033*
H18C	0.7101	0.8733	0.5144	0.033*
C19	0.71274 (14)	1.17942 (18)	0.49482 (10)	0.0137 (4)
C20	0.68653 (14)	1.29940 (18)	0.54135 (11)	0.0147 (4)
C21	0.59663 (15)	1.3555 (2)	0.53998 (12)	0.0195 (4)
H21	0.5475	1.3127	0.513	0.023*
C22	0.57773 (15)	1.4738 (2)	0.57762 (12)	0.0222 (5)
H22	0.5161	1.5118	0.5765	0.027*
C23	0.64951 (16)	1.5354 (2)	0.61670 (12)	0.0202 (4)
C24	0.73886 (15)	1.4797 (2)	0.62084 (12)	0.0213 (4)
H24	0.7873	1.5219	0.6488	0.026*
C25	0.75673 (15)	1.3612 (2)	0.58354 (11)	0.0177 (4)
H25	0.8177	1.3214	0.5868	0.021*
Cl1	0.24259 (4)	0.47669 (5)	0.18045 (3)	0.02410 (13)
Cl2	0.62642 (4)	1.68840 (5)	0.65948 (3)	0.03141 (15)
N1	0.47056 (11)	0.84316 (15)	0.26035 (9)	0.0136 (3)
N2	0.58846 (11)	0.80222 (15)	0.13265 (9)	0.0146 (3)
H1N	0.62	0.7737	0.0971	0.017*
N3	0.52781 (11)	1.04006 (16)	0.30872 (9)	0.0143 (3)
N4	0.65983 (11)	0.98928 (15)	0.43028 (9)	0.0143 (3)
N5	0.63786 (11)	1.10421 (15)	0.47812 (9)	0.0142 (3)
O1	0.79799 (9)	1.16459 (13)	0.47726 (7)	0.0171 (3)
C26	0.88926 (17)	1.0908 (2)	0.21372 (13)	0.0271 (5)
H26A	0.9492	1.1174	0.19	0.033*
H26B	0.8709	1.1631	0.248	0.033*
Cl3	0.90643 (4)	0.94086 (5)	0.26264 (3)	0.03211 (15)
Cl4	0.80044 (5)	1.07122 (7)	0.14634 (4)	0.0487 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0142 (10)	0.0148 (10)	0.0207 (11)	−0.0044 (7)	−0.0062 (8)	0.0025 (8)
C2	0.0147 (10)	0.0163 (10)	0.0161 (10)	0.0005 (7)	0.0004 (8)	−0.0002 (8)
C3	0.0130 (9)	0.0117 (9)	0.0132 (10)	0.0009 (7)	−0.0026 (7)	−0.0004 (7)
C4	0.0138 (10)	0.0129 (9)	0.0143 (10)	0.0017 (7)	−0.0008 (8)	0.0020 (7)
C5	0.0196 (10)	0.0133 (9)	0.0138 (10)	0.0027 (7)	−0.0006 (8)	−0.0011 (7)
C6	0.0217 (11)	0.0129 (9)	0.0166 (10)	0.0010 (7)	−0.0061 (8)	−0.0014 (8)
C7	0.0112 (9)	0.0147 (9)	0.0147 (10)	−0.0009 (7)	−0.0052 (7)	−0.0016 (7)
C8	0.0155 (10)	0.0229 (10)	0.0136 (10)	−0.0027 (8)	−0.0011 (8)	−0.0021 (8)
C9	0.0220 (11)	0.0225 (11)	0.0151 (10)	−0.0067 (8)	−0.0039 (8)	0.0049 (8)
C10	0.0250 (12)	0.0146 (10)	0.0225 (11)	−0.0021 (8)	−0.0089 (9)	0.0033 (8)
C11	0.0207 (11)	0.0157 (10)	0.0171 (10)	0.0004 (8)	−0.0044 (8)	−0.0037 (8)
C12	0.0136 (9)	0.0137 (9)	0.0130 (10)	−0.0028 (7)	−0.0036 (7)	−0.0012 (7)
C13	0.0113 (9)	0.0146 (9)	0.0139 (10)	0.0027 (7)	−0.0013 (7)	−0.0027 (7)
C14	0.0212 (11)	0.0169 (10)	0.0130 (10)	−0.0070 (8)	−0.0004 (8)	−0.0017 (8)
C15	0.0152 (10)	0.0228 (10)	0.0133 (10)	−0.0030 (8)	0.0026 (8)	−0.0036 (8)
C16	0.0137 (10)	0.0171 (10)	0.0122 (10)	−0.0015 (7)	0.0015 (7)	−0.0027 (7)
C17	0.0158 (10)	0.0137 (9)	0.0138 (10)	−0.0041 (7)	0.0010 (8)	−0.0022 (7)
C18	0.0234 (12)	0.0183 (10)	0.0243 (12)	0.0055 (8)	−0.0074 (9)	−0.0022 (9)
C19	0.0159 (10)	0.0147 (9)	0.0106 (9)	−0.0005 (7)	−0.0005 (7)	0.0046 (7)
C20	0.0164 (10)	0.0145 (9)	0.0132 (10)	−0.0030 (7)	0.0005 (8)	0.0030 (7)
C21	0.0177 (11)	0.0178 (10)	0.0229 (11)	−0.0034 (8)	−0.0018 (9)	−0.0016 (8)
C22	0.0191 (11)	0.0194 (10)	0.0280 (12)	0.0042 (8)	0.0003 (9)	−0.0009 (9)
C23	0.0278 (12)	0.0139 (10)	0.0187 (11)	−0.0016 (8)	0.0035 (9)	−0.0033 (8)
C24	0.0220 (11)	0.0244 (11)	0.0175 (11)	−0.0058 (8)	−0.0002 (9)	−0.0041 (9)
C25	0.0171 (10)	0.0200 (10)	0.0159 (10)	−0.0012 (8)	0.0006 (8)	−0.0007 (8)
Cl1	0.0201 (3)	0.0222 (3)	0.0299 (3)	−0.00928 (19)	−0.0035 (2)	−0.0009 (2)
Cl2	0.0376 (3)	0.0202 (3)	0.0364 (3)	0.0033 (2)	−0.0012 (3)	−0.0110 (2)
N1	0.0134 (8)	0.0127 (8)	0.0146 (8)	0.0003 (6)	−0.0004 (6)	−0.0031 (6)
N2	0.0148 (8)	0.0137 (8)	0.0152 (8)	0.0009 (6)	0.0042 (7)	−0.0012 (6)
N3	0.0167 (9)	0.0158 (8)	0.0104 (8)	−0.0031 (6)	0.0008 (6)	−0.0031 (6)
N4	0.0134 (8)	0.0147 (8)	0.0149 (8)	0.0014 (6)	−0.0012 (6)	−0.0027 (6)
N5	0.0158 (9)	0.0140 (8)	0.0128 (8)	0.0004 (6)	0.0011 (7)	−0.0050 (6)
O1	0.0143 (7)	0.0198 (7)	0.0172 (7)	−0.0012 (5)	0.0018 (6)	0.0003 (6)
C26	0.0269 (12)	0.0259 (12)	0.0285 (13)	−0.0058 (9)	−0.0076 (10)	0.0010 (10)
Cl3	0.0372 (3)	0.0217 (3)	0.0373 (3)	0.0053 (2)	−0.0080 (3)	−0.0010 (2)
Cl4	0.0470 (4)	0.0488 (4)	0.0499 (4)	−0.0179 (3)	−0.0292 (3)	0.0150 (3)

Geometric parameters (Å, º)

C1—C2	1.380 (3)	C15—H15B	0.99
C1—C6	1.383 (3)	C16—N3	1.462 (2)
C1—Cl1	1.745 (2)	C16—C17	1.513 (3)
C2—C3	1.400 (3)	C16—H16A	0.99
C2—H2	0.95	C16—H16B	0.99
C3—C4	1.405 (3)	C17—N4	1.509 (2)
C3—N1	1.408 (2)	C17—H17A	0.99
C4—C5	1.396 (3)	C17—H17B	0.99
C4—N2	1.425 (2)	C18—N4	1.500 (2)
C5—C6	1.385 (3)	C18—H18A	0.98
C5—H5	0.95	C18—H18B	0.98
C6—H6	0.95	C18—H18C	0.98
C7—C8	1.395 (3)	C19—O1	1.257 (2)
C7—C12	1.396 (3)	C19—N5	1.331 (2)
C7—N2	1.421 (2)	C19—C20	1.514 (3)
C8—C9	1.381 (3)	C20—C21	1.389 (3)
C8—H8	0.95	C20—C25	1.396 (3)
C9—C10	1.385 (3)	C21—C22	1.391 (3)
C9—H9	0.95	C21—H21	0.95
C10—C11	1.383 (3)	C22—C23	1.381 (3)
C10—H10	0.95	C22—H22	0.95
C11—C12	1.400 (3)	C23—C24	1.382 (3)
C11—H11	0.95	C23—Cl2	1.744 (2)
C12—C13	1.485 (3)	C24—C25	1.387 (3)
C13—N1	1.293 (2)	C24—H24	0.95
C13—N3	1.390 (2)	C25—H25	0.95
C14—N3	1.465 (2)	N2—H1N	0.8389
C14—C15	1.522 (3)	N4—N5	1.474 (2)
C14—H14A	0.99	C26—Cl3	1.757 (2)
C14—H14B	0.99	C26—Cl4	1.764 (2)
C15—N4	1.515 (3)	C26—H26A	0.99
C15—H15A	0.99	C26—H26B	0.99
C2—C1—C6	121.55 (18)	C17—C16—H16B	109.2
C2—C1—Cl1	119.25 (16)	H16A—C16—H16B	107.9
C6—C1—Cl1	119.20 (15)	N4—C17—C16	111.86 (15)
C1—C2—C3	120.43 (19)	N4—C17—H17A	109.2
C1—C2—H2	119.8	C16—C17—H17A	109.2
C3—C2—H2	119.8	N4—C17—H17B	109.2
C2—C3—C4	118.41 (17)	C16—C17—H17B	109.2
C2—C3—N1	116.70 (17)	H17A—C17—H17B	107.9
C4—C3—N1	124.16 (17)	N4—C18—H18A	109.5
C5—C4—C3	119.92 (18)	N4—C18—H18B	109.5
C5—C4—N2	120.57 (17)	H18A—C18—H18B	109.5
C3—C4—N2	119.43 (17)	N4—C18—H18C	109.5
C6—C5—C4	121.11 (19)	H18A—C18—H18C	109.5
C6—C5—H5	119.4	H18B—C18—H18C	109.5
C4—C5—H5	119.4	O1—C19—N5	129.62 (18)
C1—C6—C5	118.57 (18)	O1—C19—C20	118.26 (17)
C1—C6—H6	120.7	N5—C19—C20	112.12 (16)
C5—C6—H6	120.7	C21—C20—C25	118.72 (18)
C8—C7—C12	119.81 (17)	C21—C20—C19	122.32 (17)
C8—C7—N2	120.59 (17)	C25—C20—C19	118.83 (17)
C12—C7—N2	119.59 (17)	C20—C21—C22	120.70 (19)
C9—C8—C7	120.24 (19)	C20—C21—H21	119.7
C9—C8—H8	119.9	C22—C21—H21	119.7
C7—C8—H8	119.9	C23—C22—C21	119.29 (19)
C8—C9—C10	120.43 (19)	C23—C22—H22	120.4
C8—C9—H9	119.8	C21—C22—H22	120.4
C10—C9—H9	119.8	C22—C23—C24	121.25 (19)
C11—C10—C9	119.60 (19)	C22—C23—Cl2	118.74 (16)
C11—C10—H10	120.2	C24—C23—Cl2	119.99 (16)
C9—C10—H10	120.2	C23—C24—C25	118.96 (19)
C10—C11—C12	120.81 (19)	C23—C24—H24	120.5
C10—C11—H11	119.6	C25—C24—H24	120.5
C12—C11—H11	119.6	C24—C25—C20	121.02 (19)
C7—C12—C11	118.93 (18)	C24—C25—H25	119.5
C7—C12—C13	120.42 (16)	C20—C25—H25	119.5
C11—C12—C13	120.63 (17)	C13—N1—C3	122.47 (17)
N1—C13—N3	117.81 (17)	C7—N2—C4	114.11 (15)
N1—C13—C12	126.74 (17)	C7—N2—H1N	107.3
N3—C13—C12	115.19 (16)	C4—N2—H1N	111.8
N3—C14—C15	111.67 (16)	C13—N3—C16	118.80 (16)
N3—C14—H14A	109.3	C13—N3—C14	120.73 (16)
C15—C14—H14A	109.3	C16—N3—C14	110.69 (15)
N3—C14—H14B	109.3	N5—N4—C18	112.36 (15)
C15—C14—H14B	109.3	N5—N4—C17	105.13 (14)
H14A—C14—H14B	107.9	C18—N4—C17	107.88 (15)
N4—C15—C14	111.52 (16)	N5—N4—C15	112.70 (14)
N4—C15—H15A	109.3	C18—N4—C15	110.54 (15)
C14—C15—H15A	109.3	C17—N4—C15	107.87 (14)
N4—C15—H15B	109.3	C19—N5—N4	113.79 (15)
C14—C15—H15B	109.3	Cl3—C26—Cl4	110.86 (12)
H15A—C15—H15B	108	Cl3—C26—H26A	109.5
N3—C16—C17	112.16 (16)	Cl4—C26—H26A	109.5
N3—C16—H16A	109.2	Cl3—C26—H26B	109.5
C17—C16—H16A	109.2	Cl4—C26—H26B	109.5
N3—C16—H16B	109.2	H26A—C26—H26B	108.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O1^i	0.84	2.09	2.918 (2)	167

Symmetry code: (i) −x+3/2, y−1/2, −z+1/2.